JP7411283B2 - Sustained release mammalian repellent composition - Google Patents

Description

The present invention relates to a sustained release mammal repellent composition, a method for repelling mammals, and a method for producing a sustained release mammal repellent composition.

Wild animals cause significant damage in various industries. Among wild animals, rats cause serious damage to agriculture, forestry, and livestock farming by feeding on vegetables, soybeans, and rice, feeding on grain warehouses, feeding on young trees and bark, and transmitting infectious diseases. continues to give. For example, according to an epidemiological survey conducted by the Ministry of Agriculture, Forestry and Fisheries, rats are involved in transmitting the virus between farms or from wild animals as a factor in the outbreak of swine fever. has become an urgent issue. In addition, rats cause serious problems in commercial facilities such as restaurants, transmitting food poisoning, and gnaw through electrical wires, causing power outages and machinery breakdowns, causing serious damage not only to primary industries.

On the other hand, effective repellent techniques for wild animals including rats have not been sufficiently developed to date. The rat repellents currently on the market use the scent of wasabi or herbs as effective substances. All of these rat repellents have a weak repellent effect and have the problem of becoming habituated after repeated sniffing.

In recent years, in order to overcome the problems of conventional repellents, efforts have been made to develop new powerful and non-acclimating repellents based on thiazoline compounds (Patent Document 1, Non-Patent Document 1). Animals have a specialized olfactory system that picks up odors from objects that evolution has recognized as dangerous to the species, such as small animals or predators for herbivores. Thiazoline compounds are odor molecules that are accepted by this special olfactory system, and have an extremely strong repellent effect on small animals and herbivores such as rats, moles, rabbits, and deer. It also has the excellent property that no acclimatization occurs at all. Therefore, if thiazoline compounds are used as active ingredients in repellents, it will be possible to overcome the problem of acclimatization, which was a major drawback of conventional repellents, and to provide a new repellent that is strong and does not acclimate. (Patent Document 1).

Repellents for wild animals require long-term use indoors or outdoors. However, thiazoline compounds are highly volatile and tend to be denatured when exposed to air. Furthermore, thiazoline compounds are easily decomposed by moisture in the air, and their repellent effect is lost. For example, if a repellent containing a thiazoline compound is installed or applied to trees and then rain falls, the activity of the animal repellent will be impaired. 4E2MT (4-ethyl-2-methylthiazoline), which is a thiazoline compound, forms a dimer after a ring-opening reaction by hydrolysis and is modified into an inactive compound. These points are weaknesses in the long-term use of thiazoline compounds. In addition, the high volatility and easy denaturation properties are also obstacles to the application of thermal processing and sustained release techniques for formulation. Therefore, there is a need for a new technique that maintains the repellent effect of thiazoline compounds over a long period of time without impairing their activity.

Patent No. 5350496

Kobayakawa, K. , et al. , Nature, 2007, 450(7169): 503-8.

An object of the present invention is to provide a sustained-release mammal repellent composition that is capable of releasing a thiazoline compound over a long period of time without impairing the activity of the thiazoline compound.

In order to solve the above problems, the present inventors searched for an organic polymer that stably embeds a thiazoline compound and enables its sustained release. As a result, it was revealed that when a cured product obtained by crosslinking an organic polymer with siloxane bonds was used, the thiazoline compound was not modified by the curing reaction, and no curing failure occurred. Furthermore, it has been found that the thiazoline compounds are stably and continuously emitted from the cured product over a long period of time. The present invention is based on the above findings and provides the following.

（式中、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素、ハロゲン原子、Ｃ_１－６アルキル基又はＣ_１－６アルキルチオ基を示す。）
で示される化合物から選択される１又は２以上の化合物又はその塩からなり、前記シロキサン架橋型有機重合体は、２以上のオキシアルキレン重合体及び／又は（メタ）アクリル系重合体がシロキサン結合で架橋されているものである、前記徐放性哺乳動物忌避組成物。
（２）前記式（Ｉ）で示される化合物が、２－メチルチアゾール、２－エチルチアゾール、２－ブロモチアゾール、４－メチルチアゾール、及び２，４－ジメチルチアゾールから選択されるいずれかの化合物である、（１）に記載の徐放性哺乳動物忌避組成物。
（３）前記式（ＩＩ）又は（ＩＩＩ）で示される化合物が、２－メチル－２－チアゾリン、２－メチルチオ－２－チアゾリン、４－メチル－２－チアゾリン、２，４－ジメチル－２－チアゾリン、及び２，２－ジメチルチアゾリジンから選択されるいずれかの化合物である、（１）に記載の徐放性哺乳動物忌避組成物。
（４）前記式（ＩＶ）で示される化合物が、チオモルホリンである、（１）に記載の徐放性哺乳動物忌避組成物。
（５）前記式（Ｖ）で示される化合物が、２，５－ジメチル－２－チアゾリン及び５－メチル－２－チアゾリンから選択されるいずれかの化合物である、（１）に記載の徐放性哺乳動物忌避組成物。
（６）前記オキシアルキレン重合体のポリオキシアルキレン構造の構成単位であるオキシアルキレン基が炭素数１～６のオキシアルキレン基であり、前記オキシアルキレン重合体の数平均分子量が１，０００～３０，０００である、（１）～（５）のいずれかに記載の徐放性哺乳動物忌避組成物。
（７）前記（メタ）アクリル系重合体が主鎖にアクリル酸アルキルエステル単量体単位としてブチルアクリレートを含み、前記（メタ）アクリル系重合体の数平均分子量が２，０００～３０，０００である、（１）～（６）のいずれかに記載の徐放性哺乳動物忌避組成物。
（８）（１）～（７）のいずれかに記載の徐放性哺乳動物忌避組成物、及び前記徐放性哺乳動物忌避組成物を内部に包含する容器を含む、哺乳動物忌避装置。
（９）前記容器が、外界に接する１又は２以上の開放部を有する、（８）に記載の哺乳動物忌避装置。
（１０）前記開放部が、孔又は間隙である、（９）に記載の哺乳動物忌避装置。
（１１）哺乳動物の忌避方法であって、（１）～（７）のいずれかに記載の徐放性哺乳動物忌避組成物、又は（８）～（１０）のいずれかに記載の哺乳動物忌避装置を、哺乳動物を忌避させる空間に配置する工程を含む、前記忌避方法。(1) A sustained-release mammal repellent composition comprising a mammal repellent and a siloxane crosslinked organic polymer, the mammal repellent having the following formulas (I) to (VI):

(In the formula, R ₁ , R ₂ , and R ₃ each independently represent hydrogen, a halogen atom, a C _1-6 alkyl group, or a C _1-6 alkylthio group.)
The siloxane crosslinked organic polymer is composed of one or more compounds selected from the compounds represented by the formula or salts thereof, and the siloxane crosslinked organic polymer is composed of two or more oxyalkylene polymers and/or (meth)acrylic polymers with siloxane bonds. The sustained-release mammal repellent composition is cross-linked.
(2) The compound represented by formula (I) is any compound selected from 2-methylthiazole, 2-ethylthiazole, 2-bromothiazole, 4-methylthiazole, and 2,4-dimethylthiazole. The sustained-release mammal repellent composition according to (1).
(3) The compound represented by formula (II) or (III) is 2-methyl-2-thiazoline, 2-methylthio-2-thiazoline, 4-methyl-2-thiazoline, 2,4-dimethyl-2- The sustained-release mammal repellent composition according to (1), which is any compound selected from thiazoline and 2,2-dimethylthiazolidine.
(4) The sustained-release mammal repellent composition according to (1), wherein the compound represented by formula (IV) is thiomorpholine.
(5) The sustained release according to (1), wherein the compound represented by formula (V) is any compound selected from 2,5-dimethyl-2-thiazoline and 5-methyl-2-thiazoline. Sexual mammal repellent composition.
(6) the oxyalkylene group which is a constituent unit of the polyoxyalkylene structure of the oxyalkylene polymer is an oxyalkylene group having 1 to 6 carbon atoms, and the number average molecular weight of the oxyalkylene polymer is 1,000 to 30; 000, the sustained-release mammal repellent composition according to any one of (1) to (5).
(7) The (meth)acrylic polymer contains butyl acrylate as an acrylic acid alkyl ester monomer unit in the main chain, and the (meth)acrylic polymer has a number average molecular weight of 2,000 to 30,000. The sustained-release mammal repellent composition according to any one of (1) to (6).
(8) A mammal repellent device comprising the sustained release mammal repellent composition according to any one of (1) to (7) and a container containing the sustained release mammal repellent composition therein.
(9) The mammal repellent device according to (8), wherein the container has one or more openings that are in contact with the outside world.
(10) The mammal repellent device according to (9), wherein the opening is a hole or a gap.
(11) A method for repelling mammals, comprising the sustained-release mammal repellent composition according to any one of (1) to (7), or the mammal repellent composition according to any one of (8) to (10). The repellent method described above includes the step of arranging the repellent device in a space where mammals are to be repelled.

（式中、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素、ハロゲン原子、Ｃ_１－６アルキル基又はＣ_１－６アルキルチオ基を示す。）
で示される化合物から選択される１又は２以上の化合物又はその塩からなる哺乳動物忌避剤、加水分解性ケイ素基を有するオキシアルキレン重合体及び／又は（メタ）アクリル系重合体、及び硬化触媒を混合して架橋する混合架橋工程を含む、前記製造方法。
（１３）前記加水分解性ケイ素基を有するオキシアルキレン重合体のポリオキシアルキレン構造の構成単位であるオキシアルキレン基が炭素数１～６のオキシアルキレン基であり、前記加水分解性ケイ素基を有するオキシアルキレン重合体の数平均分子量が１，０００～３０，０００である、（１２）に記載の製造方法。
（１４）前記加水分解性ケイ素基を有する（メタ）アクリル系重合体が主鎖にアクリル酸アルキルエステル単量体単位としてブチルアクリレートを含み、前記加水分解性ケイ素基を有する（メタ）アクリル系重合体の数平均分子量が２，０００～３０，０００である、（１２）に記載の製造方法。
（１５）前記硬化触媒がカルボン酸又はアミン化合物である、（１２）に記載の製造方法。(12) A method for producing a sustained-release mammalian repellent composition, comprising the following formulas (I) to (VI):

(In the formula, R ₁ , R ₂ , and R ₃ each independently represent hydrogen, a halogen atom, a C _1-6 alkyl group, or a C _1-6 alkylthio group.)
A mammalian repellent consisting of one or more compounds selected from the compounds shown below or a salt thereof, an oxyalkylene polymer and/or (meth)acrylic polymer having a hydrolyzable silicon group, and a curing catalyst. The manufacturing method includes a mixing crosslinking step of mixing and crosslinking.
(13) The oxyalkylene group which is a constituent unit of the polyoxyalkylene structure of the oxyalkylene polymer having a hydrolyzable silicon group is an oxyalkylene group having 1 to 6 carbon atoms, and the oxyalkylene group having the hydrolyzable silicon group The production method according to (12), wherein the alkylene polymer has a number average molecular weight of 1,000 to 30,000.
(14) The (meth)acrylic polymer having the hydrolyzable silicon group contains butyl acrylate as an acrylic acid alkyl ester monomer unit in the main chain, and the (meth)acrylic polymer having the hydrolyzable silicon group The production method according to (12), wherein the number average molecular weight of the combined product is 2,000 to 30,000.
(15) The manufacturing method according to (12), wherein the curing catalyst is a carboxylic acid or an amine compound.

（式中、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素、ハロゲン原子、Ｃ_１－６アルキル基又はＣ_１－６アルキルチオ基を示す。）
で示される化合物から選択される１又は２以上の化合物又はその塩からなり、前記架橋型重合体は、（メタ）アクリル系重合体、オキシアルキレン重合体（ポリエーテル）、ポリエステル、ポリオレフィン、ポリサルファイト、ポリアルキルシロキサン、フッ素含有重合体、ゴム系重合体、及びエポキシ樹脂からなる群から選択される１又は２以上の重合体の架橋体である、前記徐放性哺乳動物忌避組成物。
［２］前記式（Ｉ）で示される化合物が、２－メチルチアゾール、２－エチルチアゾール、２－ブロモチアゾール、４－メチルチアゾール、及び２，４－ジメチルチアゾールから選択されるいずれかの化合物である、［１］に記載の徐放性哺乳動物忌避組成物。
［３］前記式（ＩＩ）又は（ＩＩＩ）で示される化合物が、２－メチル－２－チアゾリン、２－メチルチオ－２－チアゾリン、４－メチル－２－チアゾリン、２，４－ジメチル－２－チアゾリン、及び２，２－ジメチルチアゾリジンから選択されるいずれかの化合物である、［１］に記載の徐放性哺乳動物忌避組成物。
［４］前記式（ＩＶ）で示される化合物が、チオモルホリンである、［１］に記載の徐放性哺乳動物忌避組成物。
［５］前記式（Ｖ）で示される化合物が、２，５－ジメチル－２－チアゾリン及び５－メチル－２－チアゾリンから選択されるいずれかの化合物である、［１］に記載の徐放性哺乳動物忌避組成物。
［６］前記架橋体が、シロキサン架橋、ラジカル架橋、エポキシ架橋、酸エポキシ架橋、ウレタン架橋、及びエン／チオール反応による架橋からなる群から選択される架橋を含む、［１］～［５］のいずれかに記載の徐放性哺乳動物忌避組成物。
［７］前記架橋型重合体が、オキシアルキレン重合体及び／又は（メタ）アクリル系重合体のシロキサン架橋体である、［１］～［６］のいずれかに記載の徐放性哺乳動物忌避組成物。
［８］前記オキシアルキレン重合体のポリオキシアルキレン構造の構成単位であるオキシアルキレン基が炭素数１～６のオキシアルキレン基であり、前記オキシアルキレン重合体の数平均分子量が１，０００～３０，０００である、［７］に記載の徐放性哺乳動物忌避組成物。
［９］前記（メタ）アクリル系重合体が主鎖にアクリル酸アルキルエステル単量体単位としてブチルアクリレートを含み、前記（メタ）アクリル系重合体の数平均分子量が２，０００～３０，０００である、［７］又は［８］に記載の徐放性哺乳動物忌避組成物。
［１０］前記架橋型重合体が、（メタ）アクリル系重合体のラジカル架橋体である、［１］～［６］のいずれかに記載の徐放性哺乳動物忌避組成物。
［１１］前記架橋型重合体が、オキシアルキレン重合体又はポリオレフィン重合体のウレタン架橋体である、［１］～［６］のいずれかに記載の徐放性哺乳動物忌避組成物。
［１２］硬化触媒、開始剤、及び架橋剤からなる群から選択される少なくとも１つをさらに含む、［１］～［１１］のいずれかに記載の徐放性哺乳動物忌避組成物。
［１３］前記硬化触媒がカルボン酸、アミン化合物、又は有機金属触媒である、［１２］に記載の徐放性哺乳動物忌避組成物。
［１４］前記徐放性哺乳動物忌避組成物のＪＩＳ Ｋ６２５３－３：２０１２に記載のタイプＥデュロメータを用いて測定される硬度が０以上５０未満である、［１］～［１３］のいずれかに記載の徐放性哺乳動物忌避組成物。
［１５］前記徐放性哺乳動物忌避組成物の２５℃での水蒸気透過度が０．１（ｇ／ｍ^２・２４時間）以上１００（ｇ／ｍ^２・２４時間）以下である、［１］～［１４］のいずれかに記載の徐放性哺乳動物忌避組成物。
［１６］前記徐放性哺乳動物忌避組成物のＪＩＳ Ｋ６２５１：２０１７に記載の方法により３号ダンベルを用いて測定される破断強度が０．０１ＭＰａ以上であり、かつ破断伸びが５０％以上である、［１］～［１５］のいずれかに記載の徐放性哺乳動物忌避組成物。
［１７］前記徐放性哺乳動物忌避組成物の動的粘弾性測定時のガラス転移点における損失弾性率Ｅ”の貯蔵弾性率Ｅ’に対する比率として算出される損失正接（ｔａｎδ）が１．５以上である、［１］～［１６］のいずれかに記載の徐放性哺乳動物忌避組成物。
［１８］［１］～［１７］のいずれかに記載の徐放性哺乳動物忌避組成物、及び前記徐放性哺乳動物忌避組成物を内部に包含する容器を含む、哺乳動物忌避装置。
［１９］前記容器が、外界に接する１又は２以上の開放部を有する、［１８］に記載の哺乳動物忌避装置。
［２０］前記開放部が、孔又は間隙である、［１９］に記載の哺乳動物忌避装置。
［２１］哺乳動物の忌避方法であって、［１］～［１７］のいずれかに記載の徐放性哺乳動物忌避組成物、又は［１８］～［２０］のいずれかに記載の哺乳動物忌避装置を、哺乳動物を忌避させる空間に配置する工程を含む、前記忌避方法。The present invention further provides the following.
[1] A sustained-release mammal repellent composition comprising a mammal repellent and a crosslinked polymer, the mammal repellent having the following formulas (I) to (VI):

(In the formula, R ₁ , R ₂ , and R ₃ each independently represent hydrogen, a halogen atom, a C _1-6 alkyl group, or a C _1-6 alkylthio group.)
The crosslinked polymer is composed of one or more compounds selected from the following compounds or salts thereof, and the crosslinked polymer is a (meth)acrylic polymer, an oxyalkylene polymer (polyether), a polyester, a polyolefin, a polysal The sustained-release mammal repellent composition is a crosslinked product of one or more polymers selected from the group consisting of phytophytes, polyalkylsiloxanes, fluorine-containing polymers, rubber polymers, and epoxy resins.
[2] The compound represented by formula (I) is any compound selected from 2-methylthiazole, 2-ethylthiazole, 2-bromothiazole, 4-methylthiazole, and 2,4-dimethylthiazole. The sustained-release mammal repellent composition according to [1].
[3] The compound represented by formula (II) or (III) is 2-methyl-2-thiazoline, 2-methylthio-2-thiazoline, 4-methyl-2-thiazoline, 2,4-dimethyl-2- The sustained-release mammal repellent composition according to [1], which is any compound selected from thiazoline and 2,2-dimethylthiazolidine.
[4] The sustained-release mammal repellent composition according to [1], wherein the compound represented by formula (IV) is thiomorpholine.
[5] The sustained release according to [1], wherein the compound represented by formula (V) is any compound selected from 2,5-dimethyl-2-thiazoline and 5-methyl-2-thiazoline. Sexual mammal repellent composition.
[6] The crosslinked product of [1] to [5], wherein the crosslinked body includes a crosslinking selected from the group consisting of siloxane crosslinking, radical crosslinking, epoxy crosslinking, acid epoxy crosslinking, urethane crosslinking, and crosslinking by ene/thiol reaction. The sustained release mammalian repellent composition according to any one of the claims.
[7] The sustained-release mammal repellent according to any one of [1] to [6], wherein the crosslinked polymer is a siloxane crosslinked product of an oxyalkylene polymer and/or a (meth)acrylic polymer. Composition.
[8] The oxyalkylene group which is a constituent unit of the polyoxyalkylene structure of the oxyalkylene polymer is an oxyalkylene group having 1 to 6 carbon atoms, and the oxyalkylene polymer has a number average molecular weight of 1,000 to 30, 000, the sustained-release mammal repellent composition according to [7].
[9] The (meth)acrylic polymer contains butyl acrylate as an acrylic acid alkyl ester monomer unit in the main chain, and the number average molecular weight of the (meth)acrylic polymer is 2,000 to 30,000. The sustained-release mammal repellent composition according to [7] or [8].
[10] The sustained-release mammal repellent composition according to any one of [1] to [6], wherein the crosslinked polymer is a radically crosslinked (meth)acrylic polymer.
[11] The sustained-release mammal repellent composition according to any one of [1] to [6], wherein the crosslinked polymer is a urethane crosslinked product of an oxyalkylene polymer or a polyolefin polymer.
[12] The sustained-release mammal repellent composition according to any one of [1] to [11], further comprising at least one selected from the group consisting of a curing catalyst, an initiator, and a crosslinking agent.
[13] The sustained-release mammal repellent composition according to [12], wherein the curing catalyst is a carboxylic acid, an amine compound, or an organometallic catalyst.
[14] Any one of [1] to [13], wherein the sustained-release mammal repellent composition has a hardness of 0 or more and less than 50 as measured using a type E durometer described in JIS K6253-3:2012. The sustained release mammalian repellent composition described in .
[15] The sustained-release mammal repellent composition has a water vapor permeability at 25°C of 0.1 (g/m ^2.24 hours) or more and 100 (g/m ^2.24 hours) or less, [1 ] - [14] The sustained-release mammal repellent composition according to any one of [14].
[16] The sustained-release mammal repellent composition has a breaking strength of 0.01 MPa or more and an elongation at break of 50% or more, as measured by the method described in JIS K6251:2017 using a No. 3 dumbbell. , the sustained-release mammal repellent composition according to any one of [1] to [15].
[17] The sustained-release mammal repellent composition has a loss tangent (tan δ) of 1.5, which is calculated as the ratio of the loss modulus E'' to the storage modulus E' at the glass transition point during dynamic viscoelasticity measurement. The sustained-release mammal repellent composition according to any one of [1] to [16] above.
[18] A mammal repellent device comprising the sustained release mammal repellent composition according to any one of [1] to [17], and a container containing the sustained release mammal repellent composition therein.
[19] The mammal repellent device according to [18], wherein the container has one or more openings that are in contact with the outside world.
[20] The mammal repellent device according to [19], wherein the opening is a hole or a gap.
[21] A method for repelling mammals, comprising the sustained-release mammal repellent composition according to any one of [1] to [17], or the mammal repellent composition according to any one of [18] to [20]. The repellent method described above includes the step of arranging the repellent device in a space where mammals are to be repelled.

（式中、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素、ハロゲン原子、Ｃ_１－６アルキル基又はＣ_１－６アルキルチオ基を示す。）
で示される化合物から選択される１又は２以上の化合物又はその塩からなり、前記反応性官能基は、加水分解性シリル基、（メタ）アクリロイル基、アリル基、水酸基、及びオキシラン環からなる群から選択され、前記反応性官能基を有する重合体は、（メタ）アクリル系重合体、オキシアルキレン重合体（ポリエーテル）、ポリエステル、ポリオレフィン、ポリサルファイト、ポリアルキルシロキサン、フッ素含有重合体、ゴム系重合体、及びエポキシ樹脂からなる群から選択される、前記製造方法。
［２３］前記混合工程における前記反応性官能基を有する重合体が、加水分解性シリル基を有するオキシアルキレン重合体及び／又は（メタ）アクリル系重合体である、［２２］に記載の製造方法。
［２４］前記加水分解性シリル基を有するオキシアルキレン重合体のポリオキシアルキレン構造の構成単位であるオキシアルキレン基が炭素数１～６のオキシアルキレン基であり、前記加水分解性ケイ素基を有するオキシアルキレン重合体の数平均分子量が１，０００～３０，０００である、［２３］に記載の製造方法。
［２５］前記加水分解性シリル基を有する（メタ）アクリル系重合体が主鎖にアクリル酸アルキルエステル単量体単位としてブチルアクリレートを含み、前記加水分解性シリル基を有する（メタ）アクリル系重合体の数平均分子量が２，０００～３０，０００である、［２３］に記載の製造方法。
［２６］前記硬化触媒がカルボン酸、アミン化合物、又は有機金属触媒である、［２２］～［２５］のいずれかに記載の製造方法。
［２７］前記反応性官能基が水酸基であり、前記反応性官能基を有する重合体がポリオレフィン重合体であり、前記架橋剤がイソシアネート基含有化合物である、［２２］に記載の製造方法。
本明細書は本願の優先権の基礎となる日本国特許出願番号2021-037770号及び2020-089154号の開示内容を包含する。[22] A method for producing a sustained release mammalian repellent composition, the method comprising: a mammalian repellent; a polymer having at least one reactive functional group; and a curing catalyst, an initiator, and a crosslinking agent. and a crosslinking step of crosslinking the mixture obtained in the mixing step, the mammalian repellent having the following formulas (I) to (VI):

(In the formula, R ₁ , R ₂ , and R ₃ each independently represent hydrogen, a halogen atom, a C _1-6 alkyl group, or a C _1-6 alkylthio group.)
The reactive functional group is a group consisting of a hydrolyzable silyl group, a (meth)acryloyl group, an allyl group, a hydroxyl group, and an oxirane ring. The polymer having the reactive functional group is selected from (meth)acrylic polymer, oxyalkylene polymer (polyether), polyester, polyolefin, polysulfite, polyalkylsiloxane, fluorine-containing polymer, rubber. The above-mentioned manufacturing method is selected from the group consisting of polymers and epoxy resins.
[23] The production method according to [22], wherein the polymer having a reactive functional group in the mixing step is an oxyalkylene polymer and/or a (meth)acrylic polymer having a hydrolyzable silyl group. .
[24] The oxyalkylene group which is a constituent unit of the polyoxyalkylene structure of the oxyalkylene polymer having a hydrolyzable silyl group is an oxyalkylene group having 1 to 6 carbon atoms, and the oxyalkylene group having the hydrolyzable silicon group The production method according to [23], wherein the alkylene polymer has a number average molecular weight of 1,000 to 30,000.
[25] The (meth)acrylic polymer having the hydrolyzable silyl group contains butyl acrylate as an acrylic acid alkyl ester monomer unit in the main chain, and the (meth)acrylic polymer having the hydrolyzable silyl group The production method according to [23], wherein the number average molecular weight of the combined product is 2,000 to 30,000.
[26] The production method according to any one of [22] to [25], wherein the curing catalyst is a carboxylic acid, an amine compound, or an organometallic catalyst.
[27] The production method according to [22], wherein the reactive functional group is a hydroxyl group, the polymer having the reactive functional group is a polyolefin polymer, and the crosslinking agent is an isocyanate group-containing compound.
This specification includes the disclosure content of Japanese Patent Application Nos. 2021-037770 and 2020-089154, which are the basis of the priority of this application.

According to the sustained-release mammal repellent composition of the present invention, the thiazoline compound can be released over a long period of time without impairing the activity of the thiazoline compound.

(A) Whitening of the surface of the cured product that occurs when XMAP-3 or XMAP-4 is cured with a phenylguanidine/methanol catalyst system in the presence of a repellent; (B) Only the surface layer (arrow) is whitened. (C) is a cross-section of the cured product showing the wrinkle pattern seen when the whitened surface of the cured product is observed with an electron microscope. (A) A diagram showing the structure of 4-ethyl-2-methylthiazoline (4E2MT) and (B) the structure of dimerized 4E2MT. It is a figure showing (A) the appearance of the repellent composition installed in the field, and (B) the installation position. It is a figure which shows the dispersion|dissipation behavior of the repellent from the sample before field installation, the sample 5 months after field installation, and 4E2MT (undiluted solution). It is a figure showing a photograph of a vole. Voles form mouse holes in the apple fields where field tests were conducted and cause feeding damage to the bark of apples. (A) Distribution of rat holes before conducting the field test, (B) Location of plots with repellent composition, rat-proofing tape, sulfur + capsaicin, and wire mesh, and untreated plots, (C) Location of apple field. It is a diagram showing the wind direction in Hirosaki City. (C) shows the percentage of time when the average wind direction was in each direction, excluding the time when the average wind speed was less than 1.6 km/h (from https://ja.weatherspark.com). The field test period corresponds to the five months from November to March in the figure. FIG. 3 is a diagram showing the structure of the animal repellent device used in Comparative Examples 1 to 2 and Examples 5 to 9. A container (1), a membrane member (2), a void (air) (3), a cured product (4), and an animal repellent device (10) are shown. FIG. 3 is a diagram showing the experimental procedure of Comparative Example 3 and Examples 10 to 11.

1. Sustained-release mammal repellent composition 1-1. Overview A first aspect of the invention is a sustained release mammalian repellent composition. The sustained-release mammal repellent composition of the present invention contains a mammal repellent (hereinafter often referred to as "repellent") and a crosslinked polymer, and provides sustained release over a long period of time without inactivating the repellent. be able to.

1-2. Definitions Terms frequently used in this specification are defined below.
As used herein, "sustained release" refers to a substance being gradually released into space. In this specification, it specifically refers to the gradual release of odorants into the air. Specifically, it refers to the spontaneous release of odorants into the air at a slower rate than the rate at which odorants would be released under normal conditions. For example, odorants are released into the air at a slower rate than undiluted odorants or odorants diluted with commonly used solvents. When a repellent odorant is released in a sustained manner, the presence of odor molecules in the surrounding space for a long period of time allows animals to avoid the surrounding space.

As used herein, "long term" or "long term" means longer than the period during which odorants continue to be emitted under normal conditions. Specifically, it means longer than the period during which an undiluted odorant or an odorant diluted in a commonly used solvent continues to emit under the same conditions. The specific period varies depending on the type of odorant, but for example, 1 hour or more, 2 hours or more, 3 hours or more, 6 hours or more, half a day or more, 1 day or more, 2 days or more, 3 days or more, 1 week or more, 2 weeks or more, 1 month or more, 2 months or more, 3 months or more, 4 months or more, 5 months or more, 6 months or more, 1 year or more, 2 years or more, 3 years or more, 5 years or more, Or a period of 10 years or more is applicable.

The type of "mammal" used herein is not limited. Examples include all harmful mammals that cause damage to crops, forests, livestock, or human homes. Examples include mammals such as rats, moles, rabbits, weasels, deer, boars, monkeys, cats, and bears.

As used herein, the term "rat" is not limited as long as it is an animal belonging to the order Rodentia. The order Rodentia includes the suborders Porcupine, Rodentia, and Squirrel. Examples include, but are not limited to, a black rat, a brown rat, a mouse, a red rat, a vole, a bamboo rat, a squirrel, a porcupine, a degus, and a nutria.

As used herein, "deer" is an animal belonging to the family Cervidae. Examples include, but are not limited to, sika deer, Japanese deer, Japanese deer, Japanese deer such as Yakudeer, and muntjac.

As used herein, "mole" is an animal belonging to the family Moleidae. Examples include, but are not limited to, Kobe mole, Azuma mole, Sad mole, Echigo mole, and the like.

As used herein, "rabbit" is an animal belonging to the order Lagomorpha. Examples include, but are not limited to, rabbits and hares.

As used herein, "thiazoline compound" means a compound having a thiazoline ring or thiazolidine ring, or a compound having a thiomorpholine ring. For example, without limitation, compounds that are volatile and can be perceived by the animal's sense of smell, and as a result can induce aversive behavior in the animal, are preferred. Thiazoline compounds have an effect that mimics the substances contained in the urine of predators of small animals and herbivores, and are therefore effective against small animals and herbivores such as rats, moles, rabbits, and deer. It shows a strong repellent effect.

As used herein, the term "crosslinked polymer" refers to a polymer compound in which two or more polymers are crosslinked.

As used herein, the term "siloxane crosslinked organic polymer" refers to a polymeric organic compound in which two or more organic polymers are crosslinked with siloxane bonds.

1-3. Composition The sustained-release mammal repellent composition of the present invention contains a mammal repellent and a crosslinked polymer as essential components. The sustained-release mammalian repellent composition of the present invention may consist of a repellent and a crosslinked polymer, or may further contain other components.

1-3-1. Components (mammal repellent)
The mammal repellent contained in the sustained release mammal repellent composition of the present invention is selected from a heterocyclic compound represented by the following general formula (1) or a salt thereof, a chain sulfide compound, and an alkyl isothiocyanate. Contains at least one kind as an active ingredient.

（式中、環Ａは、窒素原子、硫黄原子及び酸素原子から選択される少なくとも１個のヘテロ原子を含む３－７員の複素環を示し、Ｒ_１及びＲ_２はそれぞれ独立して水素、ハロゲン原子、置換されていてもよいアルキル基、置換されていてもよいアルコキシ基、アシル基、エステル化されていてもよいカルボキシル基、置換されていてもよいチオール基、置換されていてもよいアミノ基又はオキソ基を示す。）

(In the formula, ring A represents a 3-7 membered heterocycle containing at least one hetero atom selected from a nitrogen atom, a sulfur atom, and an oxygen atom, and R ₁ and R ₂ are each independently hydrogen, Halogen atom, optionally substituted alkyl group, optionally substituted alkoxy group, acyl group, optionally esterified carboxyl group, optionally substituted thiol group, optionally substituted amino or oxo group)

Ring A of general formula (1) is a 3- to 7-membered member containing at least one (preferably 1 to 3, more preferably 1 or 2) heteroatoms selected from nitrogen atom, sulfur atom, and oxygen atom. The heterocycle is shown below. Ring A is preferably a 3- to 7-membered heterocycle containing a nitrogen atom and/or a sulfur atom. Ring A is more preferably a 3- to 7-membered heterocycle containing a nitrogen atom and a sulfur atom. The number of members in ring A is preferably 3 to 6, more preferably 5 or 6.

Examples of the heterocycle include, but are not limited to, pyrrole, pyridine, pyridazine, pyrimidine, pyrazine, piperazine, pyrrolidine, hexahydropyridazine, imidazole, imidazolidine, piperidine, ethylene sulfide, trimethylene sulfide, thiophene, thiolane, Tetrahydro-2H-thiopyran, thiazoline (e.g. 2-thiazoline, 3-thiazoline, 4-thiazoline), thiazole, thiazolidine, isothiazole, isothiazoline, thiomorpholine, thiadiazoline, thiadiazole, thiadiazolidine, 1,3-thiazane, 5 , 6-dihydro-4H-1,3-thiazine, furan, 2H-pyran, 4H-pyran, oxazole, isoxazole, morpholine, oxazoline and the like. Preferably, thiazoline (e.g. 2-thiazoline), thiazole, thiazolidine, isothiazole, isothiazoline, thiomorpholine, thiadiazoline, thiadiazole, thiadiazolidine, 1,3-thiazane, 5,6-dihydro-4H-1,3- Thiazine, more preferably thiazoline (eg, 2-thiazoline), thiazole, thiazolidine, 1,3-thiazane, 5,6-dihydro-4H-1,3-thiazine, and thiomorpholine.

A "halogen atom" as used herein is preferably selected from fluorine, chlorine, bromine and iodine.

As used herein, the term "alkyl group" (when used as a group or part of a group) refers to a straight or branched chain alkyl group having the specified number of carbon atoms. Examples of the alkyl group include a C _1-6 alkyl group, preferably a C _1-4 alkyl group. C _1-6 alkyl group means a straight-chain or branched alkyl group having 1 to 6 carbon atoms. Examples of C _1-6 alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, 1-methylpropyl group, 2-methylpropyl group, tert-butyl group, pentyl group, 1-methylbutyl group, 2 -Methylbutyl group, 3-methylbutyl group, 1,1-dimethylpropyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, hexyl group, 1-methylpentyl group, 2- Methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 1, These include, but are not limited to, 3-dimethylbutyl, 2,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, or 1-ethyl-2-methylpropyl. Preferred alkyl groups include, for example, linear or branched alkyl groups having 1 to 4 carbon atoms, with methyl, ethyl, propyl, isopropyl, butyl, and isobutyl groups being more preferred; Particularly preferred are groups.

The alkyl group may be substituted, and examples of the substituent include a halogeno group. Examples of the halogeno group include a fluoro group, a chloro group, a bromo group, and the like. A C _1-6 haloalkyl group means a C _1-6 alkyl group substituted with 1 to 5 halogeno groups, and when there are two or more halogeno groups, the types of each halogeno group may be the same or different. You can. Examples of the C _1-6 haloalkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a chlorodifluoromethyl group, a 1-fluoroethyl group, a 2-fluoroethyl group, a 2-chloroethyl group, and a 2-bromoethyl group. , 1,1-difluoroethyl group, 1,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 1,1,2,2,2 -Pentafluoroethyl group, 1-fluoropropyl group, 1,1-difluoropropyl group, 2,2-difluoropropyl group, 3-fluoropropyl group, 3,3,3-trifluoropropyl group, 4-fluorobutyl group , 4,4,4-trifluorobutyl group, 5-fluoropentyl group, 5,5,5-trifluoropentyl group, 6-fluorohexyl group, 6,6,6-trifluorohexyl group, etc. can.

As used herein, the term "alkoxy group" (when used as a group or part of a group) refers to an --O(alkyl) group having the specified number of carbon atoms. Examples of the alkoxy group include a C _1-6 alkoxy group. Examples of C _1-6 alkoxy groups include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 1-methylpropoxy group, 2-methylpropoxy group, tert-butoxy group, pentyloxy group, and 1-methylbutoxy group. group, 2-methylbutoxy group, 3-methylbutoxy group, 1,1-dimethylpropoxy group, 2,2-dimethylpropoxy group, 1,2-dimethylpropoxy group, 1-ethylpropoxy group, hexyloxy group, 1- Methylpentyloxy group, 2-methylpentyloxy group, 3-methylpentyloxy group, 4-methylpentyloxy group, 1,1-dimethylbutoxy group, 2,2-dimethylbutoxy group, 3,3-dimethylbutoxy group, Includes 1,2-dimethylbutoxy group, 1,3-dimethylbutoxy group, 2,3-dimethylbutoxy group, 1-ethylbutoxy group, 2-ethylbutoxy group, 1-ethyl-2-methylpropoxy group, etc. , but not limited to.

The alkoxy group may be substituted, and examples of the substituent include a halogeno group. Examples of the halogeno group include the same groups as the substituents for the alkyl group described above. A C _1-6 haloalkoxy group means a C _1-6 alkoxy group substituted with 1 to 5 halogeno groups, and when there are two or more halogeno groups, the types of each halogeno group may be the same or different. You can leave it there. Examples of the C _1-6 haloalkoxy group include fluoromethoxy group, difluoromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2-bromoethoxy group, 1 , 1-difluoroethoxy group, 1,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2-tetrafluoroethoxy group, 1,1,2,2,2-penta Fluoroethoxy group, 1-fluoropropoxy group, 1,1-difluoropropoxy group, 2,2-difluoropropoxy group, 3-fluoropropoxy group, 3,3,3-trifluoropropoxy group, 2,2,3,3 , 3-pentafluoropropoxy group, 4-fluorobutoxy group, 4,4,4-trifluorobutoxy group, 5-fluoropentyloxy group, 5,5,5-trifluoropentyloxy group, 6-fluorohexyloxy group , 6,6,6-trifluorohexyloxy group, and the like.

Examples of the "acyl group" used here include a formyl group and a C _1-6 alkyl-carbonyl group. Examples of the C _1-6 alkyl-carbonyl group include, but are not limited to, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, a hexanoyl group, and the like.

As used herein, the term "carboxyl group" (when used as a group or part of a group) refers to a -COOH group. The carboxyl group may be esterified. Specific examples of the carboxyl group which may be esterified include a carboxyl group and a C _1-6 alkoxycarbonyl group. The C _1-6 alkoxy moiety of the C _1-6 alkoxycarbonyl group has the same meaning as the C _1-6 alkoxy group in the optionally substituted alkoxy group.

As used herein, the term "thiol group" (when used as a group or part of a group) refers to a -SH group. The thiol group may be substituted, and examples of the substituent include a C _1-6 alkyl group, and the C _1-6 alkyl group is a C _1-6 alkyl group that may be substituted. It has the same meaning as an alkyl group. Specific examples of the optionally substituted thiol group include a thiol group and a C _1-6 alkylthio group. Examples of C _1-6 alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, butylthio, and the like.

As used herein, the term "amino group" (when used as a group or part of a group) refers to the group -NH ₂ . The amino group may be substituted with one or two substituents, and examples of the substituent include a C _1-6 alkyl group, -COR ₅ (wherein R ₅ is hydrogen or C _1-6 alkyl ), and the C _1-6 alkyl group has the same meaning as the C _1-6 alkyl group in the optionally substituted alkyl group. Specific examples of the optionally substituted amino group include an amino group, a C _1-6 alkylamino group, a di(C _1-6 alkyl)amino group, and -NR ₄ COR ₅ (in the formula, R ₄ and R ₅ each independently represents hydrogen or a C _1-6 alkyl group. Examples of the C _1-6 alkylamino group include a methylamino group, ethylamino group, and 1-methylethylamino group, and examples of the di(C _1-6 alkyl)amino group include a dimethylamino group, Examples include, but are not limited to, N-ethyl-N-methylamino group, bis(1-methylethyl)amino group, and the like.

As used herein, the term "oxo" (when used as a group or part of a group) refers to the group =O.

Suitable heterocyclic compounds used as the active ingredient of the mammal repellent contained in the sustained release mammal repellent composition of the present invention include, for example, thiazole, 2-methylthiazole, 2-ethylthiazole, 2-bromo Thiazole, 4-methylthiazole, 2-formylthiazole, 2-aminothiazole, 5-methylthiazole, 2,4-dimethylthiazole, 4,5-dimethylthiazole, 2-thiazoline, 2-methyl-2-thiazoline, 2- Ethyl-2-thiazoline, 2-bromo-2-thiazoline, 2,4-dimethyl-2-thiazoline, 4-methyl-2-thiazoline, 2-methylthio-2-thiazoline, 2-methyl-4-ethyl-2- Thiazoline, 2-amino-2-thiazoline, 5-methyl-2-thiazoline, 4,5-dimethyl-2-thiazoline, 2,5-dimethyl-2-thiazoline, 2-mercapto-2-thiazoline, 2-propyl- 2-Thiazoline, 2-(1-methylethyl)-2-thiazoline, 2-(1-methylpropyl)-2-thiazoline, thiazolidine, 2-methylthiazolidine, 4-methylthiazolidine, 5-methylthiazolidine, 2,4 -dimethylthiazolidine, 2,2-dimethylthiazolidine, 2,5-dimethylthiazolidine, 4,5-dimethylthiazolidine, 2,4,5-trimethylthiazolidine, 1,3-thiazane, 5,6-dihydro-4H-1, 3-thiazine, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-isopropyl-2-oxazoline, 2-propyl-2-oxazoline, 2,4,4-trimethyl-2-oxazoline, 4, Examples include, but are not limited to, 4-dimethyl-2-oxazoline, oxazole, thiophene, thiolane (tetrahydrothiophene), imidazole, thiomorpholine, morpholine, isobutylene sulfide, and the like.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammal repellent contained in the sustained release mammal repellent composition of the present invention is a compound represented by the following formulas (I) to (VIII). Examples include compounds selected from: or salts thereof.

Here, in the formula, R ₁ , R ₂ and R ₃ are each independently hydrogen, a halogen atom, a C _1-6 alkyl group, a C _1-6 haloalkyl group, a C _1-6 alkoxy group, a C _1-6 halo Alkoxy group, formyl group, C _1-6 alkyl-carbonyl group, carboxyl group, C _1-6 alkoxycarbonyl group, thiol group, C _1-6 alkylthio group, amino group, C _1-6 alkylamino group, di(C _1-6 alkyl) amino group, -NR ₄ COR ₅ or oxo group, and R ₄ and R ₅ each independently represent hydrogen or a C _1-6 alkyl group. However, in formula (I), R ₁ and R ₂ are not oxo groups, in formula (II), formula (VII), and formula (V), R ₁ is not an oxo group, and in formula (III), R ₁ and R ₃ may be taken together to form an oxo group.

More preferable examples of the compounds represented by the above formulas (I) to (VIII) include, where R ₁ , R ₂ and R ₃ are each independently hydrogen, a halogen atom, a C _1-6 alkyl group, or a C ₁ Examples include compounds exhibiting a _-6 alkylthio group or salts thereof.

In another preferred embodiment of the heterocyclic compound, in the heterocyclic compounds represented by formulas (I) to (VIII), the 2nd and/or 4th positions, or the 2nd and/or 5th positions are Examples include substituted thiazoles, thiazolines, thiazolidines, as well as thiophenes, thiomorpholines, and the like. Such heterocyclic compounds include substances generally known as reagents, and can be commercially available or obtained by known methods.

Preferred examples of the compounds represented by the above formula (I), (II), (III), (VII), or (VIII) include, in the formula, R ₁ , R ₂ and R ₃ are each independently hydrogen, Halogen atom, C _1-6 alkyl group, C _1-6 haloalkyl group, C _1-6 alkoxy group, C _1-6 haloalkoxy group, formyl group, C _1-6 alkyl-carbonyl group, carboxyl group, C _{1- 6} alkoxycarbonyl group, thiol group, C _1-6 alkylthio group, amino group, C _1-6 alkylamino group, di(C _1-6 alkyl)amino group, -NR ₄ COR ₅ or oxo group, R ₄ and R ₅ each independently represent hydrogen or a C _1-6 alkyl group, or a salt thereof. However, in formula (I), R ₁ and R ₂ are not oxo groups, in formula (II) and formula (VII), R ₁ is not an oxo group, and in formula (III), R ₁ and R ₃ are may be used to form an oxo group.

More preferred examples of compounds represented by formula (I), (II), (III), (VII), or (VIII) include, in the formula, R ₁ , R ₂ and R ₃ are each independently hydrogen; Examples include compounds having a halogen atom, a C _1-6 alkyl group, or a C _1-6 alkylthio group, or salts thereof.

Particularly preferred examples of compounds represented by formulas (I) to (III) include, where R ₁ , R ₂ and R ₃ are each independently hydrogen, a halogen atom, a C _1-6 alkyl group, or a C _1-6 alkyl group. Examples include compounds having ₆ alkylthio groups or salts thereof.

In formulas (I) to (III), R ₁ is hydrogen, a halogen atom (e.g., bromine atom), a C _1-6 alkyl group (e.g., methyl, ethyl), or a C _1-6 alkylthio group (e.g., methylthio). More preferred are compounds or salts thereof, in which R ₂ represents hydrogen or a C _1-6 alkyl group (eg, methyl), and R ₃ represents hydrogen or a C _1-6 alkyl group (eg, methyl).

More preferred are compounds or salts thereof in formulas (I) to (III) in which R ₁ , R ₂ and R ₃ each independently represent hydrogen or a C _1-6 alkyl group (eg, methyl, ethyl).

Other preferred embodiments of the heterocyclic compound used as the active ingredient of the mammal repellent contained in the sustained release mammal repellent composition of the present invention include the above formula (I) or (II), in which: R ₁ and R ₂ are each independently hydrogen, a halogen atom, a C _1-6 alkyl group, a C _1-6 alkoxy group, a formyl group, a C _1-6 alkyl-carbonyl group, a carboxyl group, an amino group, a thiol group, In the compound of formula (II), which represents a C _1-6 haloalkyl group, a C _1-6 alkylamino group, a di(C _1-6 alkyl)amino group, a C _1-6 alkylthio group, or -NR ₄ COR ₅ , R ₂ may represent an oxo group, and when either R ₁ or R ₂ is hydrogen, the other is not hydrogen, and R ₄ and R ₅ each independently represent hydrogen or a C _1-6 alkyl group. Examples include the compounds shown below or salts thereof.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention is, in the above formulas (I) to (VI), R ₁ represents hydrogen, a halogen atom (e.g., bromine atom), a C _1-6 alkyl group (e.g., methyl, ethyl), or a C _1-6 alkylthio group (e.g., methylthio), and R ₂ represents hydrogen or C _{1- 6} alkyl group (eg, methyl), and R ₃ is hydrogen or a C _1-6 alkyl group (eg, methyl), or a salt thereof.

In the above formulas (I) to (VI), compounds or salts thereof in which R ₁ , R ₂ and R ₃ are each independently hydrogen or a C _1-6 alkyl group (eg, methyl, ethyl) are more preferred.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained release mammalian repellent composition of the present invention is, in the above formula (I) or (II), R ₁ and R ₂ each independently represent hydrogen or a C _1-6 alkyl group (e.g., methyl, ethyl), and when either R ₁ or R ₂ is hydrogen, the other is a non-hydrogen compound or its Salt is an example.

Another preferred embodiment of the heterocyclic compound used as the active ingredient of the mammal repellent contained in the sustained release mammal repellent composition of the present invention is the above-mentioned formula (III) in which R ₁ , R ₂ and R ₃ each independently represent hydrogen or a C _1-6 alkyl group (eg, methyl), or a salt thereof.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained release mammalian repellent composition of the present invention is, in the formula (V), where R ₁ and R ₂ each independently represents hydrogen or a C _1-6 alkyl group (eg, methyl), or a salt thereof.

In formula (V), when either R ₁ or R ₂ is hydrogen, the other is more preferably a compound or a salt thereof that is not hydrogen.

Another preferred embodiment of the heterocyclic compound used as an active ingredient of the mammalian repellent contained in the sustained release mammalian repellent composition of the present invention is a heterocyclic compound of formula (VI) in which R ₁ and R ₂ are Compounds or salts thereof each independently exhibiting hydrogen or a C _1-6 alkyl group (eg, methyl) can be mentioned.

Preferred examples of the compound of formula (I) include 2-methylthiazole, 2-ethylthiazole, 2-bromothiazole, 4-methylthiazole, and 2,4-dimethylthiazole.

Preferred examples of the compound of formula (II) include 2-methyl-2-thiazoline, 2-methylthio-2-thiazoline, 4-methyl-2-thiazoline, and 2,4-dimethyl-2-thiazoline.

Preferred examples of the compound of formula (III) include thiazolidine, 2-methylthiazolidine, 2,2-dimethylthiazolidine, 4-methylthiazolidine, and 2,4-dimethylthiazolidine.

Preferred examples of the compound of formula (IV) include thiomorpholine and the like.

Preferred examples of the compound of formula (V) include 2,5-dimethyl-2-thiazoline and 5-methyl-2-thiazoline.

Preferred examples of the compound of formula (VI) include 5-methylthiazolidine and the like.

Preferred examples of compounds of formula (VII) include 5,6-dihydro-4H-1,3-thiazine, 2-methyl-5,6-dihydro-4H-1,3-thiazine or 2,4-dimethyl- Examples include 5,6-dihydro-4H-1,3-thiazine.

Preferred compounds of formula (VIII) include 1,3-thiazane, 2-methyl-tetrahydro-1,3-thiazine, and 2,4-dimethyl-tetrahydro-1,3-thiazine.

The compound having repellent activity contained in the mammalian repellent is not limited to the above-mentioned heterocyclic compounds, but may also be a compound that does not form a ring and has a chain structure (hereinafter also referred to as a chain compound). . The chain compound contains at least one heteroatom selected from nitrogen, sulfur and oxygen atoms. Preferred examples of the chain compound include chain sulfide compounds and alkyl isothiocyanates. Preferred examples of the chain sulfide compound include allyl methyl sulfide, but are not limited thereto. Preferred examples of the alkyl isothiocyanate include, but are not limited to, C _1-6 alkyl isothiocyanates such as ethyl isothiocyanate.

Salts of compounds constituting the mammalian repellent include all pharmaceutically, agriculturally, or industrially acceptable salts, including alkali metal salts such as sodium salts and potassium salts. ; alkaline earth metal salts such as magnesium salts, calcium salts; ammonium salts such as dimethylammonium salts, triethylammonium salts; inorganic acid salts such as hydrochlorides, perchlorates, sulfates, nitrates; acetates, Examples include organic acid salts such as methanesulfonate.

The mammalian repellent contained in the sustained-release mammalian repellent composition of the present invention may additionally contain a further compound having repellent activity in addition to the above. Such additional compounds that may be included include, but are not limited to, for example, mint and camphor, which are conventionally used as rat repellents.

The concentration of the mammal repellent contained in the sustained release mammal repellent composition of the present invention is 1 x 10 ^-6 weight % or more, 1 x 10 ^-5 weight % or more, 1 x 10 -4 weight % or more, 1 x 10 ^-4 weight % or more, ×10 ⁻³ % by weight or more, 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 50% by weight or more, and/ or 50% by weight or less, 20% by weight or less, 10% by weight or less, 5% by weight or less, 1% by weight or less, 0.1% by weight or less, 0.01% by weight or less, 1×10 ^-3 % by weight or less, 1 It may be less than x10 ^-4 weight %, less than 1 x 10 ^-5 weight %, or less than 1 x 10 ^-6 weight %.

(Crosslinked polymer)
The crosslinked polymer contained in the sustained release mammal repellent composition of the present invention is a crosslinked product of one or more polymers (hereinafter referred to as "polymer constituting the main chain of the crosslinked product"). be. The polymers that make up the main chain of the crosslinked product include (meth)acrylic polymers, oxyalkylene polymers (polyethers), polyesters, polyolefins, polysulfites, polyalkylsiloxanes, fluorine-containing polymers, and rubber polymers. It may be one or more polymers selected from the group consisting of , and epoxy resins.

The polymer constituting the main chain of the crosslinked product is preferably one that does not react with the thiazoline compound constituting the mammalian repellent. Therefore, the polymer constituting the main chain of the crosslinked product preferably does not have a substituent that can react with the thiazoline compound. For example, the polymer constituting the main chain of the crosslinked product has a reactive functional group (e.g., a hydrolyzable silyl group, (meth)acryloyl group, allyl group, hydroxyl group, isocyanate group, or oxirane ring) used in the crosslinking reaction. It may have no substituents other than the crosslinking group derived from and the unreacted group.

Specific examples of polyesters constituting the main chain of the crosslinked product include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyhydroxyalkanoate, polyhydroxybutyric acid, polybutylene succinate, polymethylene terephthalate, polytrimethylene terephthalate, Mention may be made of polybutylene naphthalate, monohydroxyethyl terephthalate, and bishydroxyethyl terephthalate.

Specific examples of the polyolefin constituting the main chain of the crosslinked product include polyethylene, polypropylene, polybutadiene, ethylene-propylene copolymer, hydrogenated polybutadiene, ethylene-vinyl acetate copolymer, and polycycloolefin.

Specific examples of polysulfite constituting the main chain of the crosslinked product include sodium polysulfide and ethylene polysulfite.

Specific examples of the polyalkylsiloxane constituting the main chain of the crosslinked product include polyalkyl(C1-20)siloxane, polyphenylsiloxane, and a cocondensate of alkylsiloxane and phenylsiloxane.

Specific examples of the fluorine-containing polymer that constitutes the main chain of the crosslinked product include PTFE (polytetrafluoroethylene), PCTFE (polychlorotrifluoroethylene), PFA (tetrafluoroethylene/perfluoroalkyl vinyl ether copolymer), FEP (tetrafluoroethylene/hexafluoropropylene copolymer), ETFE (tetrafluoroethylene/ethylene copolymer), PVDF (polyvinylidene fluoride), PCTFE (polychlorotrifluoroethylene), and ECTFE (chlorotrifluoroethylene/ethylene copolymer) (ethylene copolymer).

The rubber polymer constituting the main chain of the crosslinked product may be either diene rubber or non-diene rubber. Specific examples of diene rubber include butadiene rubber, isoprene rubber, natural rubber, and chloroprene rubber. Specific examples of non-diene rubber include butyl rubber, urethane rubber, silicone rubber, and acrylic rubber.

Specific examples of the epoxy resin constituting the main chain of the crosslinked product include bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol epoxy resin, hydrogenated bisphenol F epoxy resin, and epoxy cresol novolak resin.

The oxyalkylene polymer and (meth)acrylic polymer that constitute the main chain of the crosslinked product are as described below. Note that the polymer constituting the main chain of the crosslinked product is preferably one that is liquid at 25° C. before crosslinking, from the viewpoint of ease of handling.

In a crosslinked polymer, the polymer constituting the main chain of the crosslinked product is crosslinked. This crosslinking is preferably one that does not react with the thiazoline compound constituting the mammalian repellent before or after the crosslinking reaction. In one embodiment, the crosslinked polymers include siloxane crosslinks, radical crosslinks (crosslinks through carbon-carbon bonds, such as crosslinks through single carbon-carbon bonds), epoxy crosslinks, acid-epoxy crosslinks, urethane crosslinks (urethane bonds), and epoxy crosslinks (urethane bonds). /thiol reaction (ene/thiol crosslinking reaction) (thioether bond or sulfide bond).

In one embodiment, the crosslinked polymer may be a siloxane crosslinked organic polymer. Siloxane crosslinked organic polymers are preferred from the viewpoint of flexibility and durability of cured products.

The crosslinked polymer quickly completes curing (for example, within one week) in the presence of the mammalian repellent, and maintains the repellent activity of the thiazoline compound for a long period of time (for example, one year) without impairing the repellent activity of the thiazoline compound during the curing reaction. It is preferable that the cured product lasts for a long period of time (above), and that the surface of the cured product does not whiten. Examples of such crosslinked polymers include the following (a) to (d).
(a) Siloxane crosslinked product of oxyalkylene polymer (b) Siloxane crosslinked product of (meth)acrylic polymer (c) Radical crosslinked product of (meth)acrylic polymer (d) Urethane crosslinked product of polyolefin polymer

(Siloxane crosslinked organic polymer)
The crosslinked polymer contained in the sustained release mammal repellent composition of the present invention may be a siloxane crosslinked organic polymer. The siloxane crosslinked organic polymer is one in which two or more oxyalkylene polymers and/or (meth)acrylic polymers are crosslinked with siloxane bonds.

(A siloxane crosslinked organic polymer in which an oxyalkylene polymer is crosslinked with siloxane bonds)
When the oxyalkylene polymer of the siloxane crosslinked organic polymer is crosslinked with siloxane bonds, the siloxane crosslinked organic polymer contains at least two types of oxyalkylene polymers (hereinafter referred to as "first oxyalkylene polymer", " The second oxyalkylene polymer) may be crosslinked.

In addition, in the following description, "active hydrogen group" shall specify the position of the siloxane bond in the oxyalkylene polymer that constitutes the siloxane crosslinked organic polymer.

The first oxyalkylene polymer may be an oxyalkylene polymer having at least two active hydrogen groups, and the second oxyalkylene polymer may be an oxyalkylene polymer having one active hydrogen group.

The number average molecular weight of the first oxyalkylene polymer is preferably 4,000 or more per active hydrogen group, and if it is lower than 4,000, the elongation of the cured product of the hydrolyzable silicon group-containing oxyalkylene polymer may decrease. There is. The number average molecular weight is preferably 5,000 or more, particularly preferably 7,000 or more.

On the other hand, the molecular weight of the second oxyalkylene polymer is preferably 0.6 times or less, and more than 0.6 times, the GPC (gel permeation chromatography) peak top molecular weight of the first oxyalkylene polymer. If it is large, there is a problem that the viscosity-reducing effect becomes small. The same molecular weight is more preferably 0.5 times or less, and particularly preferably 0.4 times or less. On the other hand, if the molecular weight of the second oxyalkylene polymer is too low, a large amount of silicon compound will be required to convert active hydrogen groups into hydrolyzable silicon groups, leading to increased costs. A molecular weight of 2,000 or more is realistic and preferable.

In the first and/or second oxyalkylene polymer, the oxyalkylene group that is a constituent unit of the polyoxyalkylene structure is preferably an oxyalkylene group having 1 to 6 carbon atoms. As the first and/or second oxyalkylene polymer, it is preferable to use an oxyalkylene polymer in which the constituent unit of the polyoxyalkylene structure is an oxypropylene group because of its compatibility with other resins, fast curing property, and transparency. Particularly preferred in this respect.

Further, the first and/or second oxyalkylene polymer preferably has a number average molecular weight of 1,000 to 30,000, more preferably 5,000 to 20,000.

Further, the viscosity of the second oxyalkylene polymer is preferably 3/4 or less of the viscosity of the polymer in which the first and second oxyalkylene polymers coexist, and if it is larger than 3/4, the viscosity reducing effect is reduced. It is considered small.

The second oxyalkylene polymer is preferably present in an amount of 300 parts by weight or less with respect to 100 parts by weight of the first oxyalkylene polymer, and if it is more than 300 parts by weight, the hydrolyzable silicon finally obtained The curability of the group-containing oxyalkylene polymer may deteriorate significantly, and in some cases, it may not be cured. It is more preferably 200 parts by weight or less, particularly preferably 100 parts by weight or less. However, if the amount is too small, the expected viscosity-reducing effect cannot be obtained, so the amount is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, particularly preferably 10 parts by weight or more. Most preferably it is 20 parts by weight or more.

In one embodiment, the oxyalkylene group that is a constituent unit of the polyoxyalkylene structure of the oxyalkylene polymer is an oxyalkylene group having 1 to 6 carbon atoms, and the number average molecular weight of the oxyalkylene polymer is 1,000 to 30, It may be 000.

Specific examples of oxyalkylene polymers include MS Polymer S203H (Kaneka), MS Polymer S303H (Kaneka), MS Polymer 15A (Kaneka), Cylyl SAT030 (Kaneka), Cylyl SAT200 (Kaneka), Cylyl SAX400 (Kaneka), and Excester. Examples include S2410 (Asahi Glass), Excestar S2420 (Asahi Glass), and Excestar S3430 (Asahi Glass).

(Siloxane crosslinked organic polymer in which (meth)acrylic polymer is crosslinked with siloxane bonds)
In the following description, the term "crosslinkable silyl group" or "hydrolyzable silicon group" specifies the position of the siloxane bond in the (meth)acrylic polymer constituting the siloxane crosslinked organic polymer.

When the (meth)acrylic polymer of the siloxane crosslinked organic polymer is crosslinked with a siloxane bond, the siloxane crosslinked organic polymer has at least one crosslinkable silyl group (or hydrolyzable silicon group) at the end. 100 parts by mass of a (meth)acrylic polymer (A) having a monovalent or divalent aliphatic or alicyclic hydrocarbon group having 8 or more carbon atoms, which may be branched, and a primary 0.1 to 100 parts by mass of a diamine compound (B) having at least one amino group, an optionally branched monovalent aliphatic or alicyclic hydrocarbon group having 8 or more carbon atoms, and a crosslinkable silyl Contains 0.1 to 100 parts by mass of a diamine compound (C) having a group and/or a (meth)acryloyl group.

Moreover, the siloxane crosslinked organic polymer may further contain a photopolymerizable initiator (D) from the viewpoint of further improving low staining properties.

Below, the (meth)acrylic polymer (A), diamine compound (B), and diamine compound (C) contained in the siloxane crosslinked organic polymer, and the photopolymerization initiator (D) contained if desired, will be explained in detail. .

<(meth)acrylic polymer (A)>
The above (meth)acrylic polymer (A) has at least one crosslinkable silyl group shown below at the terminal, and has an acrylic acid alkyl ester monomer unit and/or a methacrylic acid alkyl ester monomer unit in the main chain. It is a polymer containing units.

Here, the crosslinkable silyl group refers to, for example, a silicon-containing group having a hydrolyzable group bonded to a silicon atom, a hydrolyzable silicon group, or a silanol group, which can be used as needed in the presence of moisture or a crosslinking agent. It refers to a group that causes a condensation reaction by using a catalyst or the like, and representative examples thereof include a group represented by the following general formula (2).

In the formula, R ⁶ and R ⁷ are each independently represented by an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ⁸ ) ₃ SiO-. and when two or more R ⁶ or R ⁷ are present, they may be the same or different.

Here, R ⁸ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R ^8s may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y's are present, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2, respectively.

Furthermore, b in the t groups represented by the following general formula (3) may be different. t represents an integer from 0 to 19. However, it is assumed that a+t×b≧1 is satisfied.

The hydrolyzable group represented by Y above is not particularly limited, and may be any conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amido groups, aminooxy groups, mercapto groups and alkenyloxy groups are preferred, and methoxy Particularly preferred are alkoxy groups such as groups.

Among the crosslinkable silyl groups, a crosslinkable silyl group represented by the following general formula (4) is preferred from the viewpoint of easy availability. In the following general formula (4), R ⁷ , Y, and a have the same meanings as R ⁷ , Y, and a described above.

Specific examples of R ⁶ and R ⁷ in the above general formula (2) include alkyl groups such as methyl group and ethyl group; alicyclic hydrocarbon groups such as cyclohexyl group; aryl groups such as phenyl group; benzyl group aralkyl groups such as; triorganosiloxy groups represented by (R ⁸ ) ₃ SiO-, where R ⁸ is a methyl group, a phenyl group, etc.; and the like. A methyl group is particularly preferred as R ⁶ , R ⁷ and R ⁸ .

On the other hand, examples of the acrylic acid alkyl ester monomer unit forming the main chain of the (meth)acrylic polymer (A) include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, and isobutyl acrylate. Acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, lauryl acrylate , tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, bephenylacrylate, phenyl acrylate, tolyl acrylate, benzyl acrylate, biphenylacrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2- Hydroxypropyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, Fluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro Examples include acrylic esters such as hexadecylethyl acrylate and methacrylic esters corresponding thereto.
These may be used alone or in combination of two or more.

Further, the main chain of the (meth)acrylic polymer (A) is not particularly limited as long as it contains an acrylic acid alkyl ester monomer unit and/or a methacrylic acid alkyl ester monomer unit; The content of these monomer units is preferably more than 50% by mass, more preferably 70% by mass or more, because the obtained cured product has good weather resistance and flexibility at low temperatures.

Furthermore, the main chain of the (meth)acrylic polymer (A) contains, in addition to acrylic acid alkyl ester monomer units and/or methacrylic acid alkyl ester monomer units, monomers that are copolymerizable with these. May include body units. For example, monomer units containing a carboxy group such as acrylic acid and methacrylic acid; monomer units containing an amide group such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide; glycidyl acrylate, glycidyl Monomer units containing epoxy groups such as methacrylate; monomer units containing amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and aminoethyl vinyl ether; polyoxyethylene acrylate, polyoxyethylene methacrylate, etc. Copolymerization effects can be expected in terms of curability and internal curability.

Other examples include monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

The monomer composition of the (meth)acrylic polymer (A) is appropriately selected depending on the use, purpose, etc.

For example, if the alkyl chain of the alkyl ester portion of the monomer is long, the glass transition temperature will be low and the physical properties of the cured product will be soft and rubbery. Conversely, when the length is short, the glass transition temperature becomes high and the physical properties of the cured product become hard.
On the other hand, the physical properties after curing largely depend on the molecular weight of the polymer.

Therefore, the monomer composition of the (meth)acrylic polymer (A) may be appropriately selected depending on the desired viscosity, physical properties after curing, etc., while considering the molecular weight.

The molecular weight of the (meth)acrylic polymer (A) is not particularly limited, but those having a number average molecular weight of 500 to 100,000 in terms of polystyrene in gel permeation chromatography (GPC) are preferred during polymerization. Preferable in terms of difficulty, compatibility, and handling viscosity. Among these, those with a number average molecular weight of 1,000 to 50,000 are preferred from the viewpoint of balance between strength and viscosity, and those with a number average molecular weight of 2,000 to 30,000 are preferred from the viewpoint of ease of handling such as workability, adhesiveness, etc. And more preferable.

The above (meth)acrylic polymer (A) may be used alone or in combination of two or more. As such a (meth)acrylic polymer (A), known ones can be used. Specific examples include Kaneka Telechelic Polyacrylate-SA100S, SA110S, SA120S, and SA310S manufactured by Kaneka Corporation.

<Diamine compound (B)>
The diamine compound (B) contained in the siloxane crosslinked organic polymer has a monovalent or divalent aliphatic or alicyclic hydrocarbon group having 8 or more carbon atoms, which may be branched, and has a primary A compound having at least one amino group.

Here, as the diamine compound (B), for example, a diamine compound represented by the following formula (5) used for producing the diamine compound (C) described below, a diamine compound represented by the following formula (6), etc. etc.
R ¹ -NH-R ² -NH ₂ (5)
NH ₂ -R ⁹ -NH ₂ (6)
In the above formula (5), R ¹ represents a monovalent aliphatic or alicyclic hydrocarbon group having 8 or more carbon atoms, preferably 12 to 21 carbon atoms, and more preferably 14 to 18 carbon atoms, which may be branched. .

Here, specific examples of the monovalent aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and the like. More specifically, preferred examples include alkyl groups such as dodecyl, hexadecyl, and octadecyl (stearyl); alkenyl groups such as oleyl, lyl, and lilunyl.

Further, specific examples of the monovalent alicyclic hydrocarbon group include a monocyclic cycloalkyl group and a polycyclic alicyclic cycloalkyl group. More specifically, monocyclic cycloalkyl groups such as cyclooctyl, cyclodecyl, and cyclododecyl groups; polycyclic alicyclic cycloalkyl groups such as isobornyl group, tricyclodecyl, tetracyclododecyl, and adamantyl; alicyclic groups such as these; Some of the hydrogen atoms of the monovalent hydrogen group can be replaced with, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group. Examples include groups substituted with one or more types of linear, branched, or cyclic alkyl groups having 1 to 4 carbon atoms, or groups substituted with one or more groups.

Among these, as R ¹ , a stearyl group or an oleyl group is preferred because they are easily available and the obtained cured product has excellent stain resistance.

On the other hand, in the above formula (5), R ² is a divalent carbon having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms, and more preferably 2 to 4 carbon atoms, which may contain an oxygen atom and may be branched. Represents a hydrogen group.

Here, specific examples of the divalent hydrocarbon group include alkylene groups and the like. More specifically, preferred examples include ethylene group, 1,2-propylene group, 1,3-propylene group, and 1,4-butylene group.
Among these, a propylene group is preferred because it is easily available.

In the above formula (6), R ⁹ is an optionally branched divalent aliphatic or alicyclic hydrocarbon group having 8 or more carbon atoms, preferably 8 to 20 carbon atoms, more preferably 10 to 14 carbon atoms. represents.

Here, specific examples of the divalent aliphatic hydrocarbon group include alkylene groups and the like. More specifically, undecane group, dodecane group, etc. are preferably exemplified because they are easily available and the resulting cured product has excellent stain resistance.

The diamine compound (B) may be composed of one kind, or may contain several kinds, of the compounds represented by the formula (5) or (6), for example.

In the present invention, the content of the diamine compound (B) is 0.1 to 100 parts by mass, and 1 to 10 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer (A). The amount is preferably 2 to 5 parts by mass, and more preferably 2 to 5 parts by mass.

When the content of the diamine compound (B) is within this range, the resulting siloxane crosslinked organic polymer will not have surface tack after curing. This is because when the siloxane crosslinked organic polymer is exposed to the atmosphere, the diamine compound (B) that bleeds out onto the surface of the cured product reacts with carbon dioxide gas in the air, producing crystalline carbamic acid. However, this is thought to be because the carbamic acid crystals function as a protective film.

In addition, in the present invention, as such diamine compound (B), hydrogenated beef tallow propylene diamine (trade name: Asfasol #10, manufactured by NOF Corporation), beef tallow propylene diamine (trade name: Asfasol #20, manufactured by NOF Corporation), Commercial products such as oleylpropylene diamine (trade name: Amine DOB, manufactured by NOF Corporation) can be used.

<Diamine compound (C)>
The diamine compound (C) contained in the siloxane crosslinked organic polymer includes an optionally branched monovalent aliphatic or alicyclic hydrocarbon group having 8 or more carbon atoms, a crosslinkable silyl group, and/or It is a compound having a (meth)acryloyl group.

In the present invention, the content of the diamine compound (C) is 0.1 to 100 parts by mass, and 1 to 10 parts by mass, based on 100 parts by mass of the (meth)acrylic polymer (A). The amount is preferably 2 to 5 parts by mass, and more preferably 2 to 5 parts by mass.

When the content of the diamine compound (C) is within this range, the resulting siloxane crosslinked organic polymer can maintain low staining properties over a long period of time from the initial stage of construction. This is because, like the diamine compound (B) above, when the siloxane crosslinked organic polymer is exposed to the atmosphere, the diamine compound (C) bleeds out onto the surface of the cured product and reacts with carbon dioxide gas in the air. to produce crystalline carbamic acid, and the crosslinkable silyl group in the diamine compound (C) is bonded to the crosslinkable silyl group of the (meth)acrylic polymer (A), and/or A crystalline protective film is immobilized on the surface of the cured product by bonding the (meth)acryloyl group in the diamine compound (C) with the (meth)acrylic polymer (A) through a radical reaction. This is thought to be because it prevents peeling due to surface deterioration over time and runoff due to rainwater.

In the present invention, the diamine compound (C) is a reaction product of a diamine compound (c11) represented by the following formula (5), an epoxysilane (c12), and a (meth)acryloyl group-containing compound (c13). (C1) is preferred.
R ¹ -NH-R ² -NH ₂ (5)
The diamine compound (C) may be determined with reference to International Publication WO2010/150361.

<Photopolymerization initiator (D)>
The photopolymerization initiator (D) optionally contained in the siloxane crosslinked organic polymer is not particularly limited as long as the monomer can be polymerized by light.

As the photopolymerization initiator (D), a photoradical initiator and a photoanion initiator are preferable, and a photoradical initiator is particularly preferable.

Examples of the photopolymerization initiator (D) include acetophenone compounds, benzoin ether compounds, benzophenone compounds, sulfur compounds, azo compounds, peroxide compounds, and phosphine oxide compounds.

Specifically, for example, acetophenone, propiophenone, benzophenone, xanthol, fluorein, benzaldehyde, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-methylacetophenone, 3-pentylacetophenone, 2,2- Diethoxyacetophenone, 4-methoxyacetophenone, 3-bromoacetophenone, 4-allylacetophenone, p-diacetylbenzene, 3-methoxybenzophenone, 4-methylbenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4- Chloro-4'-benzylbenzophenone, 3-chloroxanthone, 3,9-dichloroxanthone, 3-chloro-8-nonylxanthone, benzoyl, benzoin methyl ether, benzoin butyl ether, bis(4-dimethylaminophenyl) ketone , benzylmethoxyketal, 2-chlorothioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenylpropane -1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2 -hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2- Benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one, bis(2, 4,6-trimethylbenzoyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, etc. Can be mentioned.

These initiators may be used alone or in combination with other compounds. Specifically, combinations with amines such as diethanolmethylamine, dimethylethanolamine, and triethanolamine, combinations with iodonium salts such as diphenyliodonium chloride, and combinations with dyes such as methylene blue and amines are listed. It will be done.

In addition, when using the above-mentioned photopolymerization initiator, polymerization inhibitors such as hydroquinone, hydroquinone monomethyl ether, benzoquinone, and para-tertiary butylcatechol can also be added if necessary.

Among these, 2,2-dimethoxy-1,2-diphenylethan-1-one (IRGACURE651, Ciba Japan), 2-hydroxy-1-{4- [4-(2-hydroxy-2-methyl-propionyl)-benzyl]phenyl}-2-methyl-propan-1-one (IRGACURE127, Ciba Japan) and the like are more preferred.

In the present invention, the content ratio when the photopolymerization initiator (D) is contained is 0.01 to 10 parts by mass based on 100 parts by mass of the (meth)acrylic polymer (A). Preferably, the amount is more preferably 0.1 to 3 parts by mass, from the viewpoint of good stain resistance of the resulting cured product and economical efficiency.

In one embodiment, the (meth)acrylic polymer includes butyl acrylate as an acrylic acid alkyl ester monomer unit in the main chain, and may have a number average molecular weight of 2,000 to 30,000. A specific example of the (meth)acrylic polymer is XMAP SA120S (Kaneka), which has a molecular weight of 14,000, an acrylic component of butyl acrylate, and a silyl group terminal (two functional groups).

(A siloxane crosslinked organic polymer in which an oxyalkylene polymer and a (meth)acrylic polymer are crosslinked with siloxane bonds)
When two or more oxyalkylene polymers and (meth)acrylic polymers in the siloxane crosslinked organic polymer are crosslinked with siloxane bonds, the ratio of the oxyalkylene polymers and (meth)acrylic polymers to both They can be mixed and used as long as they do not phase separate. If the proportion of the oxyalkylene polymer is large, the water vapor permeability will increase and the hydrolysis of the repellent will be promoted, so a composition containing a large amount of (meth)acrylic polymer is preferable.

(Other ingredients)
The sustained-release mammal repellent composition of the present invention may contain components other than the mammal repellent and the crosslinked polymer. Other components are not limited as long as they do not inactivate the repellent or do not easily inactivate the repellent and do not impair or substantially impair the sustained release properties of the repellent. Other components are as described in the fourth aspect.

In one embodiment, the sustained release mammalian repellent composition of the present invention may further include at least one selected from the group consisting of a curing catalyst, an initiator, and a crosslinking agent. Examples of curing catalysts include acid catalysts (e.g. carboxylic acids), amine catalysts (e.g. amine compounds), acid/amine catalysts (e.g. a combination of carboxylic acids and amine compounds), or organometallic catalysts (e.g. organotin catalysts). etc. Examples of crosslinking agents include isocyanate group-containing compounds. Other examples of the curing catalyst, initiator, and crosslinking agent are as described in the fourth embodiment.

1-3-2. Physical properties of cured product (hardness)
The hardness of the cured product constituting the sustained-release mammal repellent composition of the present invention is 0 or more, such as 1 or more, 5 or more, 10 or more, 20 or more, 30 or more, or 40 or more, and/or less than 50. , for example, preferably 40 or less, 30 or less, 20 or less, 10 or less, 5 or less, or 1 or less. When the hardness of the sustained-release mammal repellent composition is 0 or more and less than 50, the cured product constituting the sustained-release mammal repellent composition has low water vapor permeability and has rubber elasticity, so that it may not be included in the cured product. Contact between the animal repellent and moisture in the air can be suppressed. Therefore, it becomes possible to diffuse the animal repellent over a long period of time without impairing the activity of the animal repellent containing the thiazoline compound as an active ingredient. In addition, the cured product with rubber elasticity has a moderately low crosslinking density and low barrier properties for fat-soluble gases, so the animal repellent embedded in the cured product is gradually stabilized and dissipated into the air. It has the advantage of being able to On the other hand, if the hardness as measured by a type E durometer is 50 or more, the cured product loses its rubber elasticity, has high barrier properties against fat-soluble gases, and becomes difficult to release animal repellents from the cured product.

The method for measuring hardness is not particularly limited and can be appropriately selected depending on the purpose. For example, it can be measured based on the provisions of JIS K6253-3:2012 "Vulcanized rubber and thermoplastic rubber - How to determine hardness."

In one embodiment, the hardness of the sustained-release mammal repellent composition of the present invention measured using a type E durometer described in JIS K6253-3:2012 may be 0 or more and less than 50.

(water vapor permeability)
The water vapor permeability of the cured product constituting the sustained-release mammal repellent composition of the present invention at 25° C. is 0.1 (g/m ^2.24 hours) or more, for example, 1 (g/m ^2.24 hours) or more. , 5 (g/m ^2.24 hours) or more, 10 (g/ ^m 2.24 hours) or more, 30 (g/m ^2.24 hours) or more, 50 (g/m ^2.24 hours) or more, 70 (g/m ^2.24 hours) or more, or 100 (g/ ^m 2.24 hours) or more, and/or 100 (g/m ^2.24 hours) or less, for example 70 (g/m ^2.24 hours). Below, 50 (g/ ^m 2.24 hours) or less, 30 (g/m ^2.24 hours) or less, 10 (g/m ^2.24 hours) or less, 5 (g/m ^2.24 hours) or less, It is preferably less than 1 (g/m ² ·24 hours) or less than 0.1 (g/m ² ·24 hours).

If the water vapor permeability is 0.1 (g/m ² 24 hours) or more and 100 (g/m ² 24 hours) or less, the water vapor permeability of the cured product constituting the animal repellent composition is low; It is possible to suppress the contact between the animal repellent contained in the cured product and moisture in the air, and the animal repellent can be used for a long period of time without impairing the activity of the animal repellent containing a thiazoline compound as an active ingredient. It becomes possible to dissipate. On the other hand, if the water vapor permeability exceeds 100 (g/m ² 24 hours), moisture in the air will permeate into the cured product of the animal repellent composition, and the animal repellent contained in the cured product will Animal repellents containing thiazoline compounds as active ingredients may be hydrolyzed when the agent comes into contact with moisture in the air.

The method for measuring water vapor permeability is not particularly limited and can be appropriately selected depending on the purpose. For example, the water vapor permeability at 25° C. can be measured based on JIS Z0208:1976 (moisture permeability test method for moisture-proof packaging materials (cup method)).

In one embodiment, the sustained-release mammal repellent composition of the present invention has a water vapor permeability at 25°C of 0.1 (g/m ^2.24 hours) or more and 100 (g/m ^2.24 hours) or less. There may be.

(Breaking strength and breaking elongation)
The breaking strength of the cured No. 3 dumbbell constituting the sustained release mammal repellent composition of the present invention is 0.01 MPa or more, 0.1 MPa or more, 0.2 MPa or more, 0.5 MPa or more, 1 MPa or more, 2 MPa or more, It may be 3 MPa or more, or 5 MPa or more, and/or 5 MPa or less, 3 MPa or less, 2 MPa or less, 1 MPa or less, 0.5 MPa or less, 0.2 MPa or less, 0.1 MPa or less, or 0.01 MPa or less.

Further, the elongation at break of the No. 3 dumbbell of the sustained release mammal repellent composition of the present invention is 50% or more, 80% or more, 100% or more, 200% or more, 300% or more, or 500% or more, and/or 500% or more. % or less, 300% or less, 200% or less, 100% or less, 80% or less, or 50% or less.

When the breaking strength of the cured product of the animal repellent composition is 0.01 MPa or more and the breaking elongation is 50% or more, the cured product has low water vapor permeability and has rubber elasticity, so that it is not included in the cured product. Contact between the animal repellent and moisture in the air can be suppressed. Therefore, it becomes possible to diffuse the animal repellent over a long period of time without impairing the activity of the animal repellent containing the thiazoline compound as an active ingredient. In addition, the cured product with rubber elasticity has a moderately low crosslinking density and low barrier properties for fat-soluble gases, so the animal repellent embedded in the cured product is gradually stabilized and dissipated into the air. It has the advantage of being able to On the other hand, if the breaking strength of the No. 3 dumbbell is less than 0.01 MPa and the breaking elongation is less than 50%, the cured product loses its rubber elasticity and has a high barrier property for fat-soluble gases. It becomes difficult for the repellent to dissipate.

The method for measuring the breaking strength and breaking elongation is not particularly limited, and can be appropriately selected depending on the purpose. For example, it can be measured using a No. 3 dumbbell-shaped test piece based on the provisions of JIS K6251:2017 "Vulcanized rubber and thermoplastic rubber - How to determine tensile properties".

In one embodiment, the sustained-release mammal repellent composition has a breaking strength of 0.01 MPa or more and an elongation at break of 50% or more, as measured using a No. 3 dumbbell by the method described in JIS K6251:2017. There may be.

(loss tangent tanδ)
The loss tangent tan δ at the glass transition point during dynamic viscoelasticity measurement of the cured product constituting the sustained-release mammal repellent composition of the present invention is 1.5 or more, 1.7 or more, 2.0 or more, or 2. It may be 2 or more, and/or 2.2 or less, 2.0 or less, 1.7 or less, or 1.5 or less.

When the loss tangent tan δ at the glass transition point is 1.5 or more, the cured product of the animal repellent composition has low water vapor permeability and has rubber elasticity, so that the animal repellent contained in the cured product and the air Contact with the moisture inside can be suppressed. Therefore, it becomes possible to diffuse the animal repellent over a long period of time without impairing the activity of the animal repellent containing the thiazoline compound as an active ingredient. In addition, the cured product with rubber elasticity has a moderately low crosslinking density and low barrier properties for fat-soluble gases, so the animal repellent embedded in the cured product is gradually stabilized and dissipated into the air. It has the advantage of being able to On the other hand, if the loss tangent tan δ at the glass transition point is less than 1.5, the cured product loses its rubber elasticity, the barrier properties for fat-soluble gases become high, and the animal repellent becomes difficult to diffuse from the cured product.

The loss tangent tan δ at the glass transition point during dynamic viscoelasticity measurement is determined by heating the sample piece with a heater, applying a load to the sample in tensile mode, and calculating the stress applied to the sample and the detected strain using the displacement detection unit. , calculate various viscoelastic quantities such as elastic modulus and viscosity modulus. The temperature at which the loss modulus E'' obtained in the measurement at each temperature peaks is the glass transition temperature, and the value is the tangent of the ratio of the loss modulus E'' calculated at that temperature and the storage modulus E'. can get.

In one embodiment, the loss tangent (tan δ) calculated as the ratio of the loss modulus E'' at the glass transition point to the storage modulus E' during dynamic viscoelasticity measurement of the sustained-release mammal repellent composition is 1. It may be 5 or more.

1-3-3. Dosage form The dosage form of the sustained-release mammal repellent composition of the present invention does not inactivate or denature the mammal repellent, or does not easily inactivate or denature the mammal repellent, and the sustained-release mammal repellent composition of the present invention There is no limitation as long as it does not impair or substantially impair the sustained release properties of the sexual mammal repellent composition. Examples include block-like, plate-like, linear, and combinations thereof.
The sustained-release mammal repellent composition of the present invention may be used by being included in a container described below, or may be placed or applied to a target space without being included in a container.

1-3-4. Method of use The method of using the sustained release mammal repellent composition of the present invention is according to the description in the third aspect.

1-4. Effects According to the sustained-release mammal repellent composition of the present invention, the thiazoline compound can be released over a long period of time without impairing the activity of the thiazoline compound.
The crosslinked polymer contained in the sustained-release mammal repellent composition of the present invention does not inactivate the repellent or is difficult to inactivate it when mixed with the repellent and cured. Enables long-term sustained release of drugs.

2. Mammal repellent device 2-1. Overview A second aspect of the present invention is a mammal repellent device. The mammal repellent device of the present invention includes the sustained release mammal repellent composition of the first aspect inside a container. According to the mammal repellent device of the present invention, the repellent can be released slowly and animals can be repelled over a long period of time.

2-2. Configuration The mammal repellent device of the present invention includes a sustained release mammal repellent composition and a container containing the sustained release mammal repellent composition. The composition of the sustained release mammalian repellent composition is as described in the first embodiment. Therefore, other configurations will be described below.

2-2-1. Container The term "container" as used herein refers to a container that has a storage space inside. The mammal repellent device of this aspect is characterized in that the container contains the sustained release mammal repellent composition according to the first aspect. The shape of the container is not particularly limited. Examples include a polyhedral shape, a cylindrical shape, a pyramid shape, a conical shape, a spherical shape, an ellipsoidal shape, a spindle shape, an irregular shape, or a combination thereof.

The container containing the sustained release mammalian repellent composition therein may have an opening. For example, the container may have one or more openings to the outside world. If the container has an opening, the repellent can be mainly released to the outside world through the opening. The shape and size of the opening can be appropriately selected in consideration of the diffusion rate of the repellent.
The opening may be a hole or a gap.

The container may have no or substantially no openings. If the container has no or substantially no openings, the repellent may be dissipated into the outside world from the sides of the container. In this case, the material and thickness of the container can be appropriately selected in consideration of the diffusion rate of the repellent. Further, even if the container does not substantially have an opening, it is possible to diffuse the repellent from a minute gap between the container and the lid of the container.

The container can be, for example, a standing type or a hanging type container, depending on usage conditions such as the installation location.

The volume of the container is, for example, 0.1 mL or more, 0.5 mL or more, 1 mL or more, 5 mL or more, 10 mL or more, 15 mL or more, 20 mL or more, 30 mL or more, 50 mL or more, 100 mL or more, 200 mL or more, 300 mL or more, 400 mL or more, 500mL or more, 1L or more, 2L or more, 3L or more, 4L or more, 5L or more, or 10L or more, and/or 10L or less, 5L or less, 4L or less, 3L or less, 2L or less, 1L or less, 500mL or less, 400mL or less, 300mL Hereinafter, the amount may be 200 mL or less, 100 mL or less, 50 mL or less, 30 mL or less, 20 mL or less, 15 mL or less, 10 mL or less, 5 mL or less, 1 mL or less, 0.5 mL or less, or 0.1 mL or less.

The material of the container may be made entirely or partially of a polymer compound. The polymer compound is selected from the group consisting of, for example, a polyolefin polymer, an acrylic polymer, a urethane polymer, a polyvinyl chloride polymer, a polyester polymer, a polyvinyl polymer, a vinylidene polymer, an epoxy resin, and a polystyrene polymer. The polymer may be one or more polymers, but is not limited to these.

Polyolefin polymers are high molecular compounds synthesized using alkenes as monomers. Examples include, but are not limited to, polyethylene, polypropylene (PP), ethylene-ethyl acrylate copolymer (EEA), ethylene-vinyl acetate copolymer (EVA), and ethylene-styrene copolymer.

2-3. Effects According to the mammal repellent device of the present invention, the repellent can be released in a sustained manner over a long period of time, and animals can be repelled over a long period of time.

3. Mammal repellent method 3-1. Summary The third aspect of the present invention is a method for repelling mammals. According to the repellent method of this aspect, the sustained-release mammal repellent composition according to the first aspect is installed in a closed space or an open space, and the sustained-release mammal repellent composition is placed within a predetermined range in the space. By slowly releasing the repellent contained in the composition, it is possible to repel animals over a long period of time and prevent animals from entering the space.

3-2. Method The mammal repellent method of the present invention includes a placement step as an essential step.
The "placement step" is a step of placing the sustained-release mammal repellent composition according to the first aspect or the mammal repellent device according to the second aspect in a space where mammals are to be repelled.

As used herein, "a space that repels animals" means a space where animals to be repelled live or may enter, such as fields, orchards, forests, livestock farms, roads, and expressways. , railways, airports, golf courses, dust collection sites, parks, gardens, gardens, flower beds, parking lots, buildings, houses, factories, warehouses, stores, commercial facilities, restaurants, kitchens, washrooms, balconies, storerooms, under floors, Examples include, but are not limited to, attics, telephone poles, electric wires, communication cables, wire mesh, fences, etc.

The repellent composition or repellent device may be installed either indoors or outdoors.
The repellent composition or repellent device may be used for, but not limited to, for example, 1 hour or more, 2 hours or more, 3 hours or more, 6 hours or more, half a day or more, 1 day or more, 2 days or more, 3 days or more, 1 week or more, 2 1 week or more, 1 month or more, 2 months or more, 3 months or more, 4 months or more, 5 months or more, 6 months or more, 1 year or more, 2 years or more, 3 years or more, 5 years or more, or 10 years or more, and/or 10 years or less, 5 years or less, 3 years or less, 2 years or less, 1 year or less, 6 months or less, 5 months or less, 4 months or less, 3 months or less, 2 months Use for a period of less than 1 month, less than 2 weeks, less than 1 week, less than 3 days, less than 2 days, less than 1 day, less than half a day, less than 6 hours, less than 3 hours, less than 2 hours, or less than 1 hour. can do.

The animals to be repelled by the repellent composition or repellent device are not particularly limited. For example, harmful animals that cause damage to crops, forests, livestock, or human homes are targeted. Examples of harmful animals include mammals such as rats, moles, rabbits, weasels, deer, boars, monkeys, cats, and bears, birds such as pigeons and crows, reptiles such as snakes, ants, centipedes, grasshoppers, and cockroaches. Examples include insects.

The sustained release mammalian repellent compositions of the present invention can be used such that the repellent is released in effective concentrations. As used herein, "effective concentration" is the concentration of odor molecules in the air that allows the repellent to repel the target animal. This effective concentration varies depending on the type of repellent used and the combination of animals to be repelled, but for example, 0.01 ppm or more, 0.1 ppm or more, 0.2 ppm or more, 0.3 ppm or more, 0.4 ppm. 0.5ppm or more, 1ppm or more, 5ppm or more, or 10ppm or more, and/or 10ppm or less, 5ppm or less, 1ppm or less, 0.5ppm or less, 0.4ppm or less, 0.3ppm or less, 0.2ppm or less, 0 .1 ppm or less, or 0.01 ppm or less. For example, it is 5 ppm or more and 10 ppm or less. The concentration of odor molecules in the air can be directly measured under the conditions of use, but in cases where measurement is difficult, such as outdoors, values measured in a closed space can also be used as a reference value.

In addition to the above, the content of the repellent, the capacity of the repellent composition or repellent device, the installation location, the installation density, etc. are determined by the type of target animal, dosage form, usage conditions such as outdoor or indoor use, and/or temperature. It can be determined as appropriate depending on weather conditions such as weather and humidity.

The installation density of the repellent composition or repellent device is, for example, one or more per ^500m2 , one or more per ^100m2 , one or more per ^50m2 , one or more per ^40m2 , one or more per ^30m2 , and one or more per ^20m2. 1 or more per area, or 1 or more per ^10m2 , and/or 1 or less per ^10m2 , 1 or less per ^20m2 , 1 or less per ^30m2 , 1 or less per ^40m2 , ^{1 or} less per 50m2 , no more than one per ^100m2 , or no more than one per ^500m2 .

The installation position is not limited. If it is outdoors, it may be installed upwind of a space where animals are to be repelled, taking into account the wind direction. Further, it may be installed underground, on the ground, or at a position higher than the ground.

According to the avoidance method of this aspect, for example, 1 hour or more, 2 hours or more, 3 hours or more, 6 hours or more, half a day or more, 1 day or more, 2 days or more, 3 days or more, 1 week or more, 2 weeks or more, 1 month or more, 2 months or more, 3 months or more, 4 months or more, 5 months or more, 6 months or more, 1 year or more, 2 years or more, 3 years or more, 5 years or more, or 10 years or more can be used to repel mammals.

4. Method for producing sustained release mammalian repellent composition 4-1. Overview The fourth aspect of the present invention is a method for producing a sustained release mammalian repellent composition. According to the method for producing a sustained-release mammal repellent composition of the present embodiment, a sustained-release mammal repellent composition capable of discharging a repellent over a long period of time without impairing the activity of the repellent is produced. can do. Further, a sustained release mammal repellent composition produced by the method for producing a sustained release mammal repellent composition of this embodiment is also provided.

4-2. Method The manufacturing method of this embodiment includes a mixing step and a crosslinking step as essential steps.
The "mixing step" is a step of mixing a mammalian repellent, a polymer having at least one reactive functional group, and at least one selected from the group consisting of a curing catalyst, an initiator, and a crosslinking agent. The state of the mixture obtained in this step is not limited, but may be liquid or powder, preferably liquid.

（式中、Ｒ_１、Ｒ_２、及びＲ_３はそれぞれ独立して水素、ハロゲン原子、Ｃ_１－６アルキル基又はＣ_１－６アルキルチオ基を示す。）
で示される化合物から選択される１又は２以上の化合物又はその塩であってもよい。The mammal repellent may be any of the mammal repellents described in the first aspect. For example, the following formulas (I) to (VI):

(In the formula, R ₁ , R ₂ , and R ₃ each independently represent hydrogen, a halogen atom, a C _1-6 alkyl group, or a C _1-6 alkylthio group.)
It may be one or more compounds selected from the compounds represented by or salts thereof.

In one embodiment, the reactive functional group can be selected from the group consisting of hydrolyzable silyl groups, (meth)acryloyl groups, allyl groups, hydroxyl groups, isocyanate groups, and oxirane rings.

In one embodiment, the polymer having a reactive functional group is a (meth)acrylic polymer, an oxyalkylene polymer (polyether), a polyester, a polyolefin, a polysulfite, a polyalkylsiloxane, a fluorine-containing polymer, or a rubber. It can be selected from the group consisting of polymers and epoxy resins. The polymer having a reactive functional group is preferably one that does not react with the thiazoline compound constituting the mammalian repellent. For example, a polymer having a reactive functional group may be substituted with a reactive functional group other than the reactive functional group used in the crosslinking reaction (e.g., hydrolyzable silyl group, (meth)acryloyl group, allyl group, hydroxyl group, isocyanate group, and oxirane ring). It may also be a polymer without groups.

In one embodiment, the polymer having a reactive functional group may be an oxyalkylene polymer and/or a (meth)acrylic polymer having a hydrolyzable silyl group.

Curing catalysts include, but are not limited to, acid catalysts, amine catalysts, acid/amine catalysts, organometallic catalysts, and the like.

The acid catalyst may be, for example, without limitation, an inorganic acid (eg, hydrochloric acid or sulfuric acid) or an organic acid (eg, a sulfonic acid or carboxylic acid). Examples of carboxylic acids include versatic acid (neodecanoic acid), acetic acid, propionic acid, butyric acid, octylic acid, 2-ethylhexanoic acid, lauric acid, oleic acid, linoleic acid, palmitic acid, and stearic acid.

The amine catalyst is not limited as long as it is an amine compound, and may be a primary amine, a secondary amine, or a tertiary amine, and may be an aliphatic amine or an aromatic amine. It may also be a monoamine or a polyamine. For example, it may be amines, polyamines, or amino alcohols. Specific examples of the amine catalyst include 3-diethylaminopropylamine, ethylenediamine, dicyanamide, triethylamine, hexylamine, laurylamine, guanidine, morpholine, and diazabicycloundecene.

The acid/amine catalyst is not limited as long as it is a combination of an acid catalyst and an amine catalyst, and for example, any combination of the above acid catalyst and amine catalyst can be used. Examples of acid/amine catalysts include a combination of versatic acid and 3-diethylaminopropylamine, a combination of versatic acid and diazabicycloundecene, and the like.

The organometallic catalyst may be, for example, without limitation, an organotin compound, an organoaluminium compound, an organotitanium compound, an organozirconium compound, or an organopalladium compound. Specific examples of the organometallic catalyst include monobutyltin, dibutyltin, dioctyltin, a condensate of dibutyltin and silicate, and a condensate of dioctyltin and silicate.

Examples of the initiator include, but are not limited to, photopolymerization initiators and thermal polymerization initiators. Examples of photoinitiators include radical photopolymerization initiators (e.g., benzophenone-based, thioxanthone-based, acetophenone-based, or acylphosphine-based radical photopolymerization initiators), photoacid generators, and photobase generators. . Examples of thermal polymerization initiators include thermal radical polymerization initiators (for example, azo compounds and peroxides) and thermal cationic polymerization initiators. Specific examples of the initiator include α-hydroxyacetophenone and bis(2,4,6-trimethylbenzoyl).

The crosslinking agent can be appropriately selected depending on the polymer to be crosslinked. Examples include, but are not limited to, radical crosslinking agents, epoxy crosslinking agents, thiol compounds, and compounds containing isocyanate groups.

The isocyanate group-containing compound may be any compound having an isocyanate group in its molecule. More specifically, it may be an isocyanate group-containing compound containing one, two, three, or four or more isocyanate groups in one molecule. The isocyanate group-containing compound may be an aliphatic polyisocyanate, an araliphatic polyisocyanate, or an alicyclic polyisocyanate (for example, an isocyanurate-type polyisocyanate). Specific examples of the isocyanate group-containing compound include nurate-type isocyanate compounds and billet-type isocyanate compounds.

The combination of polymer, curing catalyst, initiator, or crosslinking agent that is mixed in the mixing step is cured quickly (for example, within one week) in the presence of a mammal repellent in the next crosslinking step, and then the crosslinking step is completed. It is preferable that the repellent activity of the thiazoline compound lasts for a long period of time (for example, one year or more) in the cured product obtained afterwards, and the surface of the cured product obtained after the crosslinking step does not whiten. preferable. The following (a) to (g) are exemplified as combinations of such polymers, curing catalysts, initiators, or crosslinking agents.
(a) an oxyalkylene polymer having a reactive functional group (e.g. a hydrolyzable silyl group) and an organometallic catalyst (e.g. an organotin catalyst)
(b) An oxyalkylene polymer having a reactive functional group (e.g., a hydrolyzable silyl group) and an amine catalyst (e.g., an amine compound)
(c) (meth)acrylic polymer having a reactive functional group (e.g. hydrolyzable silyl group) and an organometallic catalyst (e.g. organotin catalyst)
(d) A (meth)acrylic polymer having a reactive functional group (e.g. a hydrolyzable silyl group) and an amine catalyst (e.g. an amine compound)
(e) A (meth)acrylic polymer having a reactive functional group (e.g., a hydrolyzable silyl group) and an acid/amine combination catalyst (e.g., a carboxylic acid/amine compound)
(f) A (meth)acrylic polymer having a reactive functional group (for example, a (meth)acryloyl group) and a radical crosslinking agent (g) A polyolefin polymer having a reactive functional group (for example, a hydroxyl group) and containing an isocyanate group Compound

The "crosslinking step" is a step of crosslinking the mixture obtained in the mixing step. The crosslinking method in the crosslinking step is not limited. For example, temperature change, heating (thermal curing), drying, dehydration, ultraviolet irradiation (UV curing), gamma ray irradiation, and/or electron beam irradiation can be used. In this step, the polymer is crosslinked by crosslinking such as siloxane crosslinking, radical crosslinking, epoxy crosslinking, acid epoxy crosslinking, urethane crosslinking, or crosslinking by ene/thiol reaction.

The crosslinking step may be performed simultaneously with the mixing step (in this case, particularly referred to as a "mixed crosslinking step"), or may be performed after the mixing step. In particular, when a curing catalyst, initiator, or crosslinking agent is mixed in the mixing step, the crosslinking reaction may proceed together with the mixing.

The mixing step and/or the crosslinking step is preferably performed in a temperature range in which the repellent does not volatilize, inactivate, or denature, or is difficult to volatilize, inactivate, or denature. For example, mixing and / Alternatively, crosslinking can be performed. For example, mixing and/or crosslinking may be performed at room temperature.

(Method for producing sustained-release mammal repellent composition containing siloxane crosslinked product of oxyalkylene polymer and/or (meth)acrylic polymer)
In one embodiment, the manufacturing method of this aspect may be a method for manufacturing a sustained-release mammal repellent composition containing a siloxane crosslinked product of an oxyalkylene polymer and/or a (meth)acrylic polymer.
In the present embodiment, the method for producing a sustained release mammal repellent composition containing a siloxane crosslinked product of an oxyalkylene polymer and/or a (meth)acrylic polymer includes a hydrolyzable silicon group (hydrolyzable silyl group) The process is different depending on whether an oxyalkylene polymer having a hydrolyzable silicon group (hydrolyzable silyl group) is used or a (meth)acrylic polymer having a hydrolyzable silicon group (hydrolyzable silyl group).

(Method for producing a sustained-release mammal repellent composition containing a siloxane crosslinked product of an oxyalkylene polymer and/or a (meth)acrylic polymer using an oxyalkylene polymer having a hydrolyzable silicon group)
When using an oxyalkylene polymer having a hydrolyzable silicon group, the manufacturing method of this embodiment includes a mixing step and a crosslinking step as essential steps. In this embodiment, the mixing step may be a step of mixing the mammalian repellent, the oxyalkylene polymer having a hydrolyzable silicon group, and the curing catalyst.

In this embodiment, the mammal repellent, the oxyalkylene polymer having hydrolyzable silicon groups, and the curing catalyst may be mixed in any order as long as the repellent is mixed before curing of the resin is completed. There may be. For example, the curing catalyst may be mixed after mixing the repellent and the oxyalkylene polymer having hydrolyzable silicon groups, or the oxyalkylene polymer having hydrolyzable silicon groups may be mixed after the repellent and the curing catalyst are mixed. The mammalian repellent, the oxyalkylene polymer having hydrolyzable silicon groups, and the curing catalyst may be mixed together.

The first oxyalkylene polymer may be an oxyalkylene polymer having at least two active hydrogen groups, and the second oxyalkylene polymer may be an oxyalkylene polymer having one active hydrogen group.

The number average molecular weight of the first oxyalkylene polymer is preferably 4,000 or more per active hydrogen group, and if it is lower than 4,000, the elongation of the cured product of the hydrolyzable silicon group-containing oxyalkylene polymer may decrease. There is. The number average molecular weight is preferably 5,000 or more, particularly preferably 7,000 or more.

On the other hand, the molecular weight of the second oxyalkylene polymer is preferably 0.6 times or less, and more than 0.6 times, the GPC (gel permeation chromatography) peak top molecular weight of the first oxyalkylene polymer. If it is large, there is a possibility that the viscosity-reducing effect will be reduced. The same molecular weight is more preferably 0.5 times or less, and particularly preferably 0.4 times or less. On the other hand, if the molecular weight of the second oxyalkylene polymer is too low, a large amount of silicon compound will be required to convert active hydrogen groups into hydrolyzable silicon groups, leading to increased costs. A molecular weight of 2,000 or more is realistic and preferable.

In the first and/or second oxyalkylene polymer, the oxyalkylene group that is a constituent unit of the polyoxyalkylene structure is preferably an oxyalkylene group having 1 to 6 carbon atoms. As the first and/or second oxyalkylene polymer, it is preferable to use an oxyalkylene polymer in which the constituent unit of the polyoxyalkylene structure is an oxypropylene group because of its compatibility with other resins, fast curing property, and transparency. Particularly preferred in this respect.

Further, the first and/or second oxyalkylene polymer preferably has a number average molecular weight of 1,000 to 30,000, more preferably 5,000 to 20,000.

Further, the viscosity of the second oxyalkylene polymer is preferably 3/4 or less of the viscosity of the polymer in which the first and second oxyalkylene polymers coexist, and if it is larger than 3/4, the viscosity reducing effect is reduced. It is considered small.

The second oxyalkylene polymer is preferably present in an amount of 300 parts by weight or less with respect to 100 parts by weight of the first oxyalkylene polymer, and if it is more than 300 parts by weight, the hydrolyzable silicon finally obtained The curability of the group-containing oxyalkylene polymer may deteriorate significantly, and in some cases, it may not be cured. It is more preferably 200 parts by weight or less, particularly preferably 100 parts by weight or less. However, if the amount is too small, the expected viscosity-reducing effect cannot be obtained, so the amount is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, particularly preferably 10 parts by weight or more. Most preferably it is 20 parts by weight or more.

The first and/or second oxyalkylene polymer may be an alkali metal catalyst, a metal porphyrin catalyst (see Japanese Patent Application Laid-Open No. 61-197631, etc.), or a multi-metal cyanide complex catalyst (USP3278457, USP3278458, USP3278459, USP3427256, USP4055188). , USP 4721818, etc.), a compound catalyst having a P=N bond (see JP-A-11-106500, JP-A-10-36499, JP-A-11-302371, etc.) in the presence of at least one catalyst. It can be produced by polymerizing an alkylene oxide or the like with an initiator such as a hydroxy compound having a hydroxyl group. Among these catalysts, it is preferable to use a multimetal cyanide complex catalyst or a compound catalyst having a P=N bond, which yields a high molecular weight, uncolored oxyalkylene polymer, and a multimetal cyanide complex catalyst is particularly preferable.

Examples of the multimetal cyanide complex catalyst include Zn[Fe(CN) ₆ ] ₂ , Zn ₃ [Co(CN) ₆ ] ₂ , Fe[Fe(CN) ₆ ], Fe[Co(CN) ₆ ], etc. It will be done. More preferably, it has a structure in which Zn ₃ [Co(CN) ₆ ] ₂ (ie, zinc hexacyanocobaltate complex) is used as a catalyst skeleton and an organic ligand is coordinated thereto.

Such a catalyst can be produced, for example, by coordinating an organic ligand to a reaction product obtained by reacting a metal halide salt with an alkali metal cyanometalate in water. As the metal of the metal halide salt, Zn(II) or Fe(II) is preferable, and Zn(II) is particularly preferable. As the metal halide salt, zinc chloride is particularly preferable, and as the metal constituting the cyanometalate of the alkali metal cyanometalate, Co(III) or Fe(III) is preferable, and Co(III) is particularly preferable. As the alkali metal cyanometalate, potassium hexacyanocobaltate is preferred. As the organic ligand, alcohol and/or ether are preferred. Alcohols such as tert-butyl alcohol, a compound represented by the following formula 7, ethanol, sec-butyl alcohol, n-butyl alcohol, isobutyl alcohol, tert-pentyl alcohol, isopentyl alcohol, and isopropyl alcohol, and ethylene glycol dimethyl ether ( Hereinafter, one or more ethers selected from ethers such as glyme), diglyme (diethylene glycol dimethyl ether), triglyme (triethylene glycol dimethyl ether), dioxane, and polyethers having an Mn of 150 to 5,000 are preferred. Among these, one or more selected from tert-butyl alcohol, a compound represented by the following formula 7, and glyme are particularly preferred.
R ⁴ -C(CH ₃ ) ₂ (OR ⁵ ) _n OH (7)
(In the formula, R ⁴ is a methyl group or an ethyl group, R ⁵ is an ethylene group or a group in which the hydrogen atom of the ethylene group is substituted with a methyl group or an ethyl group, and n is 1, 2 or 3.)

As the compound represented by formula 7, ethylene glycol mono-tert-butyl ether, propylene glycol mono-tert-butyl ether, ethylene glycol mono-tert-pentyl ether, propylene glycol mono-tert-pentyl ether are preferable, and ethylene glycol mono-tert-pentyl ether is preferred. Particularly preferred is tert-butyl ether.

A multimetal cyanide complex catalyst is produced by reacting a metal halide salt with an alkali metal cyanometalate, stirring the catalyst skeleton in an organic ligand, aging it, and then filtering and washing it by a known method. , can be produced by drying.

As the initiator, active hydrogen-containing compounds can be used, including the following compounds: monovalent primary and secondary compounds such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, and decanol. , tertiary alcohol. Monovalent unsaturated group-containing alcohols such as allyl alcohol, methallyl alcohol, and propenyl alcohol. And, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4 - monovalent unsaturated group-containing alcohols such as the monoallyl etherified product of the monoallyl etherified product of cyclohexanediol etc. and the above monovinyl etherified product of the monovinyl etherified product, and the above mentioned monoalkyl etherified product Monohydric saturated alcohols such as monoalkyl etherified products. Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4- Polyhydric alcohols such as cyclohexanediol, glycerin, diglycerin, trimethylolpropane, pentaerythritol, glucose, sorbitol, sucrose, and methyl glycoside. Alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. Phenol compounds such as bisphenol A, bisphenol F, bisphenol S, resorcinol, and hydroquinone. Aliphatic amines such as ethylene diamine, diethylene triamine, hexamethylene diamine, etc., or oxyalkylene polymers having a lower molecular weight than the hydrolyzable silicon group-containing oxyalkylene polymer that is the target product obtained by reacting an alkylene oxide with the above-mentioned initiator. Combined.

The above initiators may be used alone or in combination of two or more. However, the first initiator used to polymerize the first oxyalkylene polymer is preferably a compound mainly containing at least two active hydrogen groups. The first oxyalkylene polymer is a component that is converted into a hydrolyzable silicon group-containing oxyalkylene polymer and then cured by moisture etc. to become a rubber-like elastic body.For that purpose, it contains at least two active hydrogen groups. It is preferable that it is a compound that mainly contains.

On the other hand, the second initiator used to polymerize the second oxyalkylene polymer is preferably a compound mainly containing one active hydrogen group. The second oxyalkylene polymer is coexisting for the purpose of reducing the viscosity of the oxyalkylene polymer, and therefore has a relatively small molecular weight. Therefore, if a large amount of a compound containing two or more active hydrogen groups is contained, a cured product of a hydrolyzable silicon group-containing oxyalkylene polymer consisting of an oxyalkylene polymer in which the first and second oxyalkylene polymers coexist The flexibility decreases, resulting in a hard and brittle cured product. When using an oxyalkylene polymer polymerized with a compound containing one active hydrogen group as the second initiator, the hydrolyzable silicon group-containing oxy In order not to reduce the flexibility of the cured alkylene polymer, the second initiator used to polymerize the second oxyalkylene polymer is preferably a compound mainly containing one active hydrogen group. It is particularly preferable to use an initiator represented by Formula 8.
R ¹ -OH (8)
(In the formula, R ¹ is a monovalent organic group having no unsaturated group and containing one or more constituent atoms selected from the group consisting of carbon, hydrogen, oxygen, and nitrogen.)

In addition, the amount of initiator in the second oxyalkylene polymer is 5 or less in molar ratio to the amount of initiator in the first oxyalkylene polymer, and when it is more than 5, the hydrolyzable silicon group finally obtained is The curability of the oxypropylene polymer contained therein may deteriorate significantly, and in some cases, it may not be cured. The molar ratio is preferably 3 or less, particularly preferably 2 or less.

Examples of alkylene oxides include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide, epichlorohydrin, epibutymohydrin, methyldalicidyl ether, allyl glycidyl ether, butyldalicidyl ether, 2-ethyl Examples include hexylene glycidyl ether and trifluoropropylene oxide. These may be used alone or in combination of two or more. Among these, propylene oxide is preferred.

As a method for producing an oxyalkylene polymer in which a first oxyalkylene polymer having at least two active hydrogen groups and a second oxyalkylene polymer having one active hydrogen group coexist, After polymerizing the alkylene polymer, there is a method in which an initiator for the second oxyalkylene polymer is added (post-addition method), and a method in which initiators for the first and second oxyalkylene polymers are coexisted and polymerized simultaneously (co-polymerization method). (initiation method), and either method may be used for polymerization. Alternatively, a method may be used in which the components are polymerized separately and then mixed.

In the post-addition method, the GPC peak top molecular weights of the first and second oxyalkylene polymers and their ratio can be adjusted arbitrarily by changing the timing of adding the initiator of the second oxyalkylene polymer and the amount of alkylene oxide supplied. It can be applied as a method to effectively reduce the viscosity of oxyalkylene polymers.

The initiator for the second oxyalkylene polymer is preferably added after the first oxyalkylene polymer has been polymerized to around the target molecular weight. In the polymerization of alkylene oxide using a multi-metal cyanide complex, when initiators with different GPC peak top molecular weights coexist, the polymerization of the initiator with a lower molecular weight proceeds preferentially, and the polymerization of the initiator with a higher molecular weight occurs mostly. It has the characteristic of not progressing. This trend continues until the GPC peak top molecular weight ratio of oxyalkylene polymers obtained from initiators with different molecular weights approaches the active hydrogen group number ratio of the initiator, and then the molecular weight of each initiator increases to maintain that ratio. do. Therefore, in order to arbitrarily determine the GPC peak top molecular weight ratio of the first and second oxyalkylene polymers, it is necessary to polymerize the first oxyalkylene polymer to around the target molecular weight and then polymerize the second oxyalkylene polymer. It is preferable to add an initiator (that is, an initiator having one active hydrogen group).

The molecular weight of the second oxyalkylene polymer can be arbitrarily determined by the amount of alkylene oxide supplied after addition of the initiator of the second oxyalkylene polymer. The amount of alkylene oxide fed is less than or equal to 0.6 times and greater than 0.6 times the amount of alkylene oxide fed per molar amount of the first initiator fed when polymerizing the first oxyalkylene polymer. In this case, the molecular weight of the second oxyalkylene polymer becomes large, which is not preferable. The amount of alkylene oxide supplied is preferably 0.5 times or less, particularly preferably 0.4 times or less.

On the other hand, in the co-initiation method, the GPC peak top molecular weight ratio of the first and second oxyalkylene polymers cannot be determined arbitrarily, but the second oxyalkylene polymer can be polymerized together with the first oxyalkylene polymer. Therefore, an oxyalkylene polymer coexisting with a second oxyalkylene polymer having a large molecular weight and a large ratio thereof can be easily obtained. Since such oxyalkylene polymers have a large molecular weight, their viscosity reduction effect is small, and because the number of molecular ends is small, the amount of hydrolyzable silicon groups introduced is reduced, which is advantageous in terms of cost. It can be applied as a method that can impart appropriate flexibility to a cured product that is cured by moisture or the like after introduction.

The hydrolyzable silicon group-containing oxyalkylene polymer can be obtained by introducing a hydrolyzable silicon group into an oxyalkylene polymer containing active hydrogen groups by an appropriate method.

The hydrolyzable silicon group in the present invention may be any silicon group that undergoes hydrolysis and crosslinking reaction in the presence of moisture, and generally known hydrolyzable silicon groups can be used.

For example, a silicon group represented by Formula 9 is preferable.
-SiX _a R _3-a (9)
(In the formula, R is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms, preferably an alkyl group, phenyl group, or fluoroalkyl group having 8 or less carbon atoms. Particularly preferably, a methyl group, (Ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, phenyl group, etc.)
X is a hydrolyzable group, such as a halogen atom, an alkoxy group, an acyloxy group, an amide group, an amino group, an aminooxy group, a ketoximate group, and the like.

Among these, the number of carbon atoms in the hydrolyzable group having carbon atoms is preferably 6 or less, particularly preferably 4 or less. Preferred hydrolyzable groups include lower alkoxy groups having 4 or less carbon atoms, particularly methoxy, ethoxy, propoxy, and propenyloxy groups. a is 1, 2 or 3, particularly preferably 2 or 3.

The method of introducing the silicon group represented by Formula 9 into the oxyalkylene polymer is not particularly limited, but it can be introduced, for example, by the following methods (A) to (D). In addition, when introducing a hydrolyzable silicon group by the following method (A) or (D), it is used after converting into an unsaturated group-containing oxyalkylene polymer. However, in this case, it is necessary to use an initiator represented by Formula 8 as the initiator of the second oxyalkylene polymer having one active hydrogen group.
R ¹ -OH (8)
(In the formula, R ¹ is a monovalent organic group having no unsaturated group and containing one or more constituent atoms selected from the group consisting of carbon, hydrogen, oxygen, and nitrogen.)

When the second oxyalkylene polymer is polymerized using an initiator having an unsaturated group in ^R1 , converting the active hydrogen group contained in the second oxyalkylene polymer into an unsaturated group results in at least two unsaturated groups. It becomes an oxyalkylene polymer with saturated groups. Therefore, the flexibility of the cured product of the hydrolyzable silicon group-containing oxyalkylene polymer that is cured by moisture or the like decreases, resulting in a hard and brittle cured product.

Therefore, when introducing a hydrolyzable silicon group by the method (A) or (D) below, the initiator represented by formula 8 is used as the initiator of the second oxyalkylene polymer having one active hydrogen group. It is necessary to use it.

In addition, in methods (B) and (C) for introducing hydrolyzable silicon groups, due to side reactions that occur when reacting active hydrogen groups and isocyanate compounds, methods (A) and (D) However, when using an oxyalkylene polymer in which the first and second oxyalkylene polymers having active hydrogen groups coexist, the viscosity increases more easily than when hydrolyzable silicon groups are introduced. The viscosity of the oxyalkylene polymer containing a hydrolyzable silicon group can be effectively reduced.

(A) After converting the active hydrogen group contained in the oxyalkylene polymer into an unsaturated group (formula 10) to obtain an unsaturated group-containing oxyalkylene polymer, a silicon hydride compound represented by formula 11 is reacted. Method.
-O-R ² (10)
(In the formula, ^R2 is a monovalent organic group containing one or more constituent atoms selected from the group consisting of carbon, hydrogen, oxygen, and nitrogen having unsaturated bonds.)
HSiX _a R _3-a (11)
(In the formula, R, X, and a are the same as in formula 9 above.)
The method for introducing an unsaturated group here is to react a compound having an unsaturated group and a functional group with an active hydrogen group of an oxyalkylene polymer, and bond it with an ether bond, an ester bond, a urethane bond, a carbonate bond, etc. or a method in which an unsaturated group-containing epoxy compound such as allyl glycidyl ether is added and copolymerized during polymerization of alkylene oxide, thereby introducing an unsaturated group into the side chain.

(B) A method of reacting an active hydrogen group contained in an oxyalkylene polymer with a compound represented by Formula 12.
R _3-a -SiX _a -R ³ NCO (12)
(In the formula, R, X, and a are the same as above, and R ³ is a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms.)

(C) After reacting the active hydrogen group contained in the oxyalkylene polymer with a polyisocyanate compound such as tolylene diisocyanate to convert it into an isocyanate group, the W group of the silicon compound represented by formula 13 is reacted with the isocyanate group. How to do it.
R _3-a -SiX _a -R ³ W (13)
(In the formula, R, R ³ , X, and a are the same as above, and W is an active hydrogen-containing group selected from a hydroxyl group, a carboxyl group, a mercapto group, and an amino group (primary or secondary).)

(D) A method of converting an active hydrogen group contained in an oxyalkylene polymer into an unsaturated group, and reacting the unsaturated group with a silicon compound represented by formula 13 in which W is a mercapto group.

The composition of the present invention may contain various known curing catalysts, fillers, and various additives. Furthermore, if necessary, a plasticizer etc. can also be included.

The hydrolyzable silicon group content of the first and second oxyalkylene polymers is preferably 40% or more and 100% or less, and 50% or less, based on the active hydrogen groups contained in the oxyalkylene polymer used as the raw material. It is more preferably 100% or less, and particularly preferably 60% or more and 100% or less.

The hydrolyzable silicon group-containing oxyalkylene polymer obtained by the production method of the present invention can be used as it is or by adding various additives to form a room-temperature curable composition.

As the curing catalyst, a wide variety of conventionally known catalysts can be used. Specific examples include titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, and titanium tetraacetylacetonate; dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin diotatate, dibutyltin diethyl hexalt, dibru maleate, and dibutyltin dioctyl maleate. , dibutyltin ditridecyl maleate, dibutyltin dibenzyl maleate, dibutyltin diacetate, dioctyltin diethyl maleate, dioctyltin dioctyl maleate, dibutyltin dimethoxide, dibutyltin diyulfenoxide, dibutenyltin oxide, dibutyltin diacetylacetate Tetravalent tin compounds such as dibutyltin diethylacetoacetonate, dibutyltin oxide and phthalate ester; divalent tin compounds such as tin octylate, tin naphthenate, tin stearate, tin versatate; aluminum Organoaluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate; zirconium compounds such as zirconium tetraacetylacetonate; lead octylate; Carboxylic acids: butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenyl Daanidine, 2,4,6-tris(dimethylaminomethyl)phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo(5,4,0)undecene-7 Amine compounds such as (DBU), or salts of these amine compounds with carboxylic acids, etc.; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; reaction products between excess polyamines and epoxy compounds; Silanol condensation catalysts such as silane coupling agents having amino groups such as 1-aminopropyltrimethoxysilane and N-(β-aminoethyl)aminopropylmethyldimethoxysilane, as well as other acidic catalysts and basic catalysts. Examples include known silanol condensation catalysts. Preferably, carboxylic acids such as versatic acid and/or amine compounds can be used. These catalysts may be used alone or in combination of two or more.

The amount of these curing catalysts used is preferably about 0.1 to 20 parts by weight based on 100 parts by weight of the oxyalkylene polymer. If the amount of curing catalyst used is too small, the curing rate will be slow and the curing reaction will be difficult to proceed sufficiently, which is not preferable. On the other hand, if the amount of curing catalyst used is too large, local heat generation and foaming will occur during curing, making it difficult to obtain a good cured product, which is not preferable.

In the composition of the present invention, in order to further enhance the activity of the condensation catalyst, a silicon compound represented by the general formula R _4-a Si(OR) _a (wherein R and a are the same as above) is added. I don't mind. Examples of the silicon compound include, but are not limited to, phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane, etc., in which R is the number of carbon atoms. Those having 6 to 20 aryl groups are preferred because they have a large effect of accelerating the curing reaction of the composition. In particular, diphenyldimethoxysilane and diphenyljethoxysilane are particularly preferred because they are low cost and easily available. The compounding amount of this metering compound is preferably about 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the oxyalkylene polymer. If the amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, if the amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

A silane coupling agent, a reactant of the silane coupling agent, or a compound other than the silane coupling agent can be added to the composition of the present invention as an adhesion imparting agent. Specific examples of the silane coupling agent include isocyanate group-containing silanes such as γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, and γ-isocyanatepropylmethyldimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-( 2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl)aminopropylmethyldiethoxysilane, γ-ureidopropyltrimethoxysilane, N- Amino group-containing silanes such as phenyl γ-aminopropyltrimethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ - Mercapto group-containing silanes such as mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane; γ-glycidoxypropylmethyldimethoxysilane, β-(3,4-epoxycyclo Epoxy group-containing silanes such as hexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxyethyl phenylbis(2- Carboxysilanes such as methoxyethoxy)silane, N-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, γ- Vinyl-type unsaturated group-containing silanes such as acryloyloxypropylmethyltriethoxysilane; halogen-containing silanes such as γ-chloropropyltrimethoxysilane; isocyanurate silanes such as tris(trimethoxysilyl)isocyanurate, etc. be able to. In addition, modified derivatives of these, such as amino-modified silyl polymers, silylated aminopolymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, and silylated polyesters, can also be used as silane coupling agents. . The silane coupling agent used in the present invention is usually used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the oxyalkylene polymer. In particular, it is preferable to use it in a range of 0.5 to 10 parts by weight.

The effect of the silane coupling agent added to the composition can be applied to various adherends, such as inorganic base materials such as glass, aluminum, stainless steel, zinc, copper, and mortar, as well as vinyl chloride, acrylic, polyester, polyethylene, polypropylene, and polycarbonate. When used on organic substrates such as the following, it shows a remarkable effect of improving adhesion under non-primer conditions or under primer treatment conditions. When used under non-primer conditions, the effect of improving adhesion to various adherends is particularly remarkable. Specific examples other than the silane coupling agent include, but are not particularly limited to, epoxy resins, phenol resins, sulfur, alkyl titanates, aromatic polyisocyanates, and the like. The above-mentioned adhesion imparting agent may be used alone or in combination of two or more types. By adding these adhesion imparting agents, the adhesion to the adherend can be improved.

The composition of the present invention can contain various fillers. Fillers include reinforcing fillers such as fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, and carbon black; ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate. , diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, fine aluminum powder, flint powder, zinc oxide, activated zinc white, shirasu balloon, glass microballoon, phenolic resin and vinylidene chloride. Fillers such as organic microballoons of resin, resin powders such as PVC powder and PMMA powder; fibrous fillers such as asbestos, glass fibers and filaments, and the like. When a filler is used, the amount used is 1 to 300 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the oxyalkylene polymer.

If you want to obtain a cured product with high strength by using these fillers, use mainly fume silica, precipitated silica, crystalline silica, fused silica, dolomite, anhydrous silicic acid, hydrous silicic acid, carbon black, surface-treated fine Fillers selected from calcium carbonate, calcined clay, clay, activated zinc white, etc. are preferably used in an amount of 1 to 200 parts by weight based on 100 parts by weight of the oxyalkylene polymer, and preferable results can be obtained. In addition, when it is desired to obtain a cured product with low strength and high elongation at break, fillers mainly selected from titanium oxide, calcium carbonate, magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloon, etc. Preferable results can be obtained if the amount of the compound is used in the range of 5 to 200 parts by weight per 100 parts by weight of the oxyalkylene polymer. In general, the larger the specific surface area of calcium carbonate, the greater the effect of improving the breaking strength, elongation at break, and adhesiveness of the cured product. Of course, these fillers may be used alone or in a mixture of two or more. Fatty acid surface-treated colloidal calcium carbonate and calcium carbonate having a particle size of 1 μm or more, such as ground calcium carbonate that has not been surface-treated, can be used in combination.

In order to improve the workability (sharpness, etc.) of the composition and to make the surface of the cured product matte, it is preferable to add an organic balloon or an inorganic balloon. These fillers can be surface-treated and may be used alone or in combination of two or more. In order to improve workability (cutting, etc.), the particle size of the balloon is preferably 0.1 mm or less. In order to make the surface of the cured product matte, the thickness is preferably 5 to 300 μm.

A physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the composition of the present invention, if necessary. Physical property modifiers are not particularly limited, but include, for example, alkylalkoxysilanes such as rutrimethoxysilane; dimethyldiisopropenoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyldimethylmethoxysilane. , γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)aminopropylmethyldimethoxysilane; silicone varnishes; polysiloxanes, and the like. By using the physical property modifier, it is possible to increase the hardness of the composition of the present invention when it is cured, or conversely to decrease the hardness and cause elongation at break. The above physical property modifiers may be used alone or in combination of two or more.

The physical property modifier is used in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the oxyalkylene polymer.

If necessary, a thixotropic agent (anti-sagging agent) may be added to the composition in order to prevent sagging and improve workability. Further, anti-sag agents include, but are not particularly limited to, polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate, and barium stearate. These thixotropic agents (anti-sagging agents) may be used alone or in combination of two or more. The thixotropic agent is used in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the oxyalkylene polymer.

In the composition of the present invention, a compound containing an epoxy group in one molecule can be used. When a compound having an epoxy group is used, the restorability of the cured product can be improved. Examples of compounds having an epoxy group include epoxidized unsaturated oils and fats, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, di-(2-ethylhexyl) 4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl Examples include stearate, epoxybutyl stearate, and the like. Among these, E-PS is particularly preferred. For the purpose of improving the restorability of the cured product, it is preferable to use a compound having one epoxy group in the molecule. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight per 100 parts by weight of the oxyalkylene polymer.

Photocurable materials can be used in the compositions of the present invention. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. A photocurable substance is one whose molecular structure undergoes a chemical change in a fairly short period of time due to the action of light, resulting in physical changes such as hardening. Many compounds of this type are known, including organic monomers, oligomers, resins, and compositions containing them, and any commercially available compounds may be employed. Typical examples include unsaturated acrylic compounds, vinyl polycinnamates, and azidized resins. Examples of unsaturated acrylic compounds include monomers, oligomers, or mixtures thereof having one or several acrylic or methacrylic unsaturated groups, such as propylene (or butylene, ethylene) glycol di(meth)arylate, neo Monomers such as pentyl glycol di(meth)dimethacrylate or oligoesters having a molecular weight of 10,000 or less are exemplified. Specifically, for example, special atarylate, bifunctional Aronix M-210, Aronix M-215, Aronix M-220, Aronix M-233, Aronix M-240, Aronix M-245; trifunctional Aronix M-305. , Aronix M-309, Aronix M-310, Aronix M-315, Aronix M-320, Aronix M-325, and polyfunctional Aronix M-400, but compounds containing an acrylic functional group are particularly preferred. Further, compounds containing on average three or more of the same functional groups in one molecule are preferable (all of the above Aronix are products of Toagosei Kagaku Kogyo Co., Ltd.).

Examples of vinyl polycinnamates include photosensitive resins having a cinnamoyl group as a photosensitive group, which is obtained by esterifying polyvinyl alcohol with cinnamic acid, and many vinyl polycinnamate derivatives. Azide resin is known as a photosensitive resin that has an azide group as a photosensitive group, and is usually used in addition to rubber photosensitive liquids containing diazide compounds as photosensitizers. (Published by Printing Society Publishing Department, pages 93-, 106-, and 117-) have detailed examples, and these can be used alone or in combination, with a sensitizer added if necessary. Can be done. Note that the effect may be enhanced by adding a sensitizer such as ketones or nitro compounds or a promoter such as amines.

The amount of the photocurable substance used is preferably 0.01 to 20 parts by weight, and more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the oxyalkylene polymer. If it is less than 0.01 part by weight, the effect of improving weather resistance is small, and if it is more than 20 parts by weight, the cured product becomes too hard and cracks occur, which is not preferable.

Oxygen curable materials can be used in the compositions of the present invention. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, which reacts with oxygen in the air to form a cured film near the surface of the cured product, causing the surface to become sticky or to the surface of the cured product. It acts by preventing the adhesion of dirt and dust. Specific examples of oxygen-curable substances include drying oils such as tung oil and linseed oil; various alkyd resins obtained by modifying these compounds; acrylic polymers and epoxy resins modified with drying oils. , silicone resin; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers, etc. obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Liquid copolymers such as NBR and SBR obtained by copolymerizing liquid polymers and monomers such as atarylonitrile and styrene that are copolymerizable with these diene compounds so that the diene compound is the main component. Examples include coalescence and various modified products thereof (maleated modified products, boiled oil modified products, etc.). These may be used alone or in combination of two or more. Among these, tung oil and liquid diene polymers are particularly preferred. Further, the effect may be enhanced by using a catalyst or a metal dryer that promotes the oxidative hardening reaction. Examples of these catalysts and metal driers include metal salts such as cobalt naphthenate, lead naphthenate, zirconium naphthenate, cobalt octylate, and zirconium octylate, and amine compounds. The amount of the oxygen-curable substance to be used is preferably 0.1 to 20 parts by weight, and more preferably 1 to 10 parts by weight, based on 100 parts by weight of the oxyalkylene polymer. If the amount used is less than 0.1 part by weight, the staining property will not be improved sufficiently, and if it exceeds 20 parts by weight, the tensile properties etc. of the cured product will tend to be impaired. As described in JP-A-3-160053, oxygen-curable substances are preferably used in combination with photo-curable substances.

Antioxidants (antiaging agents) can be used in the compositions of the invention. Use of an antioxidant can improve the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred. Similarly, Tinuvin 622LD, Tinuvin 144; CHIMASSORB944LD, CHIMASSORB119FL (all manufactured by Nippon Ciba Geigy); MARK LA-57, MARK LA-62, MARK LA-67, MARK LA-63, MARK LA-68 (all of the above) Sanol LS-770, Sanol LS-765, Sanol LS-292, Sanol LS-2626, Sanol LS-1114, Sanol LS-744 (all manufactured by Sankyo Co., Ltd.) It is also possible to use hindered amine light stabilizers. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731. The amount of antioxidant used is preferably 0.1 to 10 parts by weight, and more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the oxyalkylene polymer.

Light stabilizers can be used in the compositions of the invention. Use of a light stabilizer can prevent photooxidative deterioration of the cured product. Examples of light stabilizers include benzotriazole compounds, hindered amine compounds, and benzoate compounds, with hindered amine compounds being particularly preferred. The amount of the light stabilizer to be used is preferably 0.1 to 10 parts by weight per 100 parts by weight of the oxyalkylene polymer, and more preferably 0.2 to 5 parts by weight. Specific examples of light stabilizers are also described in JP-A-9-194731.

When a photocurable substance is used in combination with the composition of the present invention, especially when an unsaturated acrylic compound is used, a tertiary amine-containing hindered amine can be used as a hindered amine light stabilizer as described in JP-A-5-70531. It is preferable to use a light stabilizer to improve the storage stability of the composition. Tertiary amine-containing hindered amine light stabilizers include Tinuvin 622LD, Tinuvin 144; CHIMASSORB119F (all manufactured by Nippon Ciba Geigy); MARKLA-57, LA-62, LA-67, LA-63 (all manufactured by Adeka Argus); Examples include light stabilizers such as Sanol LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all manufactured by Sankyo Co., Ltd.).

Ultraviolet absorbers can be used in the compositions of the invention. Use of an ultraviolet absorber can improve the surface weather resistance of the cured product. Examples of ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl and metal chelate compounds, with benzotriazole being particularly preferred. The amount of the ultraviolet absorber used is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the oxyalkylene polymer, and more preferably in the range of 0.2 to 5 parts by weight. It is preferable to use a phenolic or hindered phenolic antioxidant, a hindered amine light stabilizer, and a benzotriazole ultraviolet absorber in combination.

The composition of the present invention can also be used as an elastic adhesive or the like by adding an epoxy resin. Epoxy resins include epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame-retardant epoxy resins such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A glycidyl ether type epoxy resin of propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane modified epoxy resin, various alicyclic epoxy resins, Glycidyl ethers of polyhydric alcohols such as N,N-diglycidylaniline, N,N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether, glycerin, hydantoin type epoxy resins, petroleum resins, etc. Examples include epoxidized products of unsaturated polymers, but the present invention is not limited thereto, and commonly used epoxy resins may be used. Those containing at least two epoxy groups in the molecule are preferred because they have high reactivity during curing and the cured product tends to form a three-dimensional network. More preferred examples include bisphenol A type epoxy resins and novolac type epoxy resins. The ratio by weight of these epoxy resins and oxyalkylene polymers is in the range of oxyalkylene polymer/epoxy resin=100/1 to 1/100. When the ratio of the oxyalkylene polymer/epoxy resin of the present invention is less than 1/100, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin, and the ratio of the oxyalkylene polymer/epoxy resin is less than 1/100. If it exceeds /1, the strength of the cured oxyalkylene polymer will be insufficient. The preferred usage ratio cannot be determined unconditionally because it varies depending on the use of the curable resin composition, but for example, when improving the impact resistance, flexibility, toughness, peel strength, etc. of a cured epoxy resin, The oxyalkylene polymer is preferably used in an amount of 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, per 100 parts by weight of the epoxy resin. On the other hand, in order to improve the strength of the cured product of the present invention, it is preferable to use 1 to 200 parts by weight, more preferably 5 to 100 parts by weight, of the epoxy resin per 100 parts by weight of the oxyalkylene polymer.

When using an epoxy resin, a curing agent for curing the epoxy resin can be used in combination. There are no particular limitations on the epoxy resin curing agent that can be used, and commonly used epoxy resin curing agents can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated Primary and secondary amines such as polyether; tertiary amines such as 2,4,6-tris(dimethylaminomethyl)phenol and tripropylamine, and salts of these tertiary amines; polyamide resins ; Imidazoles; Dicyandiamides; Carboxylic acid anhydrides such as boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride, etc. Examples include, but are not limited to, alcohols; phenols; carboxylic acids; diketone complex compounds of aluminum or zirconium. Further, the curing agent may be used alone or in combination of two or more. When an epoxy resin curing agent is used, the amount used is in the range of 0.1 to 300 parts by weight per 100 parts by weight of the epoxy resin.

Ketimine can be used as a curing agent for epoxy resins. Ketimine exists stably in a moisture-free state, and is decomposed by moisture into a primary amine and a ketone, and the resulting primary amine becomes a room-temperature curing agent for epoxy resins. When ketimine is used, a one-component composition can be obtained. Such ketimine can be obtained by a condensation reaction between an amine compound and a carbonyl compound.

For the synthesis of ketimine, known amine compounds and carbonyl compounds may be used. For example, amine compounds include ethylenediamine, propylene diamine, trimethylene diamine, tetramethylene diamine, 1,3-diaminobutane, 2,3-diaminobutane, Diamines such as pentamethylenediamine, 2,4-diaminopentane, hexamethylenediamine, p-phenylenediamine, p,p'-biphenylenediamine; 1,2,3-triaminopropane, triaminobenzene, tris(2- Polyvalent amines such as aminoethyl)amine and tetra(aminomethyl)methane; polyalkylene polyamines such as diethylenetriamine, triethylenetriamine, and tetraethylenepentamine; polyoxyalkylene polyamines; γ-aminopropyltriethoxysilane, N-( Aminosilanes such as β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(β-aminoethyl)-γ-aminopropylmethyldimethoxysilane; and the like can be used. Carbonyl compounds include aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, diethylacetaldehyde, glyoxal, and benzaldehyde; cyclic compounds such as cyclopentanone, trimethylcyclopentanone, cyclohexanone, and trimethylcyclohexanone. Ketones; Aliphatic ketones such as acetone, methyl ethyl ketone, methyl dipropyl ketone, diisopropyl ketone, dibutyl ketone, diisobutyl ketone; acetylacetone, methyl acetoacetate, ethyl acetoacetate, dimethyl malonate, diethyl malonate, methyl malonate 3-dicarbonyl compounds such as ethyl and dibenzoylmethane can be used.

When an imino group is present in ketimine, the imino group may be reacted with styrene oxide; glycidyl ethers such as butyl dalicidyl ether and allyl glycidyl ether; glycidyl esters and the like. These ketimines may be used alone or in combination of two or more types. 1 to 100 parts by weight are used per 100 parts by weight of epoxy resin, and the amount used varies depending on the type of epoxy resin and ketimine. .

If necessary, various additives may be added to the composition of the present invention for the purpose of adjusting various physical properties of the curable composition or cured product. Examples of such additives include flame retardants, curing modifiers, radical inhibitors, metal deactivators, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, blowing agents, Examples include solvents and fungicides. These various additives may be used alone or in combination of two or more. Specific examples of additives other than those listed in this specification include, for example, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Application Publication No. 63-254149, Japanese Patent Application Publication No. 64-22904, It is described in various publications such as JP-A No. 2001-72854.

The composition of the present invention can also be prepared as a one-component type in which all the ingredients are mixed in advance, sealed and stored, and cured by moisture in the air after application. It can also be prepared as a two-component type, in which components such as a drug, water, etc. are blended in advance, and the blended materials and the polymer composition are mixed before use.

When the curable composition is a one-component type, all components are blended in advance, so components containing water are either dehydrated and dried before use, or dehydrated by reduced pressure or the like during compounding and kneading. is preferable. When the curable composition is a two-component type, there is no need to add a curing catalyst to the main component containing a polymer having a reactive silicon group, so even if the compound contains a small amount of water, it will not gel. However, if long-term storage stability is required, dehydration and drying is preferable. As the dehydration and drying method, suitable methods include heat drying in the case of solid materials such as powder, and vacuum dehydration methods in the case of liquid materials, or dehydration methods using synthetic zeolite, activated alumina, silica gel, etc. Alternatively, a small amount of isocyanate and a compound may be blended and the isocyanate group may be reacted with water for dehydration. In addition to such dehydration drying methods, lower alcohols such as methanol and ethanol; n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxy Storage stability is further improved by adding an alkoxysilane compound such as silane.

The amount of a dehydrating agent, particularly a silicon compound capable of reacting with water such as vinyltrimethoxysilane, is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the oxyalkylene polymer. A range is preferred.

In one embodiment, the oxyalkylene group that is a constituent unit of the polyoxyalkylene structure of the oxyalkylene polymer having a hydrolyzable silicon group is an oxyalkylene group having 1 to 6 carbon atoms, and the oxyalkylene group having the hydrolyzable silicon group The number average molecular weight of the oxyalkylene polymer may be 1,000 to 30,000.

Specific examples of oxyalkylene polymers having hydrolyzable silicon groups that can be used in the production method of the present invention include MS Polymer S203H (Kaneka), MS Polymer S303H (Kaneka), MS Polymer 15A (Kaneka), Cylyl Examples include SAT030 (Kaneka), Cyrill SAT200 (Kaneka), Cyrill SAX400 (Kaneka), Excestar S2410 (Asahi Glass), Excestar S2420 (Asahi Glass), Excestar S3430 (Asahi Glass), and the like.

(Method for producing a sustained-release mammal repellent composition containing a siloxane crosslinked product of an oxyalkylene polymer and/or a (meth)acrylic polymer using a (meth)acrylic polymer having a hydrolyzable silicon group)
When using a (meth)acrylic polymer having a hydrolyzable silicon group, the production method of this embodiment includes a mixing step and a crosslinking step as essential steps. In this embodiment, the mixing step may be a step of mixing a mammal repellent, a (meth)acrylic polymer having a hydrolyzable silicon group, and a curing catalyst.

In this embodiment, the order of mixing the mammalian repellent, the (meth)acrylic polymer having hydrolyzable silicon groups, and the curing catalyst may be as long as the repellent is mixed before curing of the resin is completed. Any order is acceptable. For example, a curing catalyst may be mixed after mixing a repellent and a (meth)acrylic polymer having hydrolyzable silicon groups, or a curing catalyst may be mixed after mixing a repellent and a curing catalyst and then a (meth)acrylic polymer having hydrolyzable silicon groups. ) An acrylic polymer may be mixed, or a mammalian repellent, a (meth)acrylic polymer having hydrolyzable silicon groups, and a curing catalyst may be mixed simultaneously.

When using a (meth)acrylic polymer having a hydrolyzable silicon group in the "mixing step" and/or "crosslinking step", at least one crosslinkable polymer is used in the "mixing step" and/or "crosslinking step". 100 parts by mass of a (meth)acrylic polymer (A) having a silyl group (or hydrolyzable silicon group) at the end, 0.1 to 100 parts by mass of optionally branched carbon atoms (B), and branched A diamine compound having a monovalent aliphatic or alicyclic hydrocarbon group having 8 or more carbon atoms, which may have at least 8 carbon atoms, and having at least one primary amino group, or 0.1 to 100 parts by mass of a diamine compound (C) having an alicyclic hydrocarbon group and a crosslinkable silyl group and/or (meth)acryloyl group are mixed.

Moreover, the siloxane crosslinked organic polymer may further be mixed with a photopolymerizable initiator (D) from the viewpoint of further improving the low staining property.

The (meth)acrylic polymer (A) will be explained in detail below. The diamine compound (B), the diamine compound (C), and the optionally contained photopolymerization initiator (D) are as described in the first embodiment.

<(meth)acrylic polymer (A)>
The above (meth)acrylic polymer (A) has at least one crosslinkable silyl group shown below at the terminal, and has an acrylic acid alkyl ester monomer unit and/or a methacrylic acid alkyl ester monomer unit in the main chain. It is a polymer containing units.

Here, the crosslinkable silyl group refers to, for example, a silicon-containing group having a hydrolyzable group bonded to a silicon atom, a hydrolyzable silicon group, or a silanol group, which can be used as needed in the presence of moisture or a crosslinking agent. It refers to a group that causes a condensation reaction by using a catalyst or the like, and representative examples thereof include a group represented by the following general formula (2).

In the formula, R ⁶ and R ⁷ are each independently represented by an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or (R ⁸ ) ₃ SiO-. and when two or more R ⁶ or R ⁷ are present, they may be the same or different.

Here, R ⁸ is a monovalent hydrocarbon group having 1 to 20 carbon atoms, and the three R ^8s may be the same or different. Y represents a hydroxyl group or a hydrolyzable group, and when two or more Y's are present, they may be the same or different. a represents 0, 1, 2 or 3, and b represents 0, 1 or 2, respectively.

Furthermore, b in the t groups represented by the following general formula (3) may be different. t represents an integer from 0 to 19. However, it is assumed that a+t×b≧1 is satisfied.

The hydrolyzable group represented by Y above is not particularly limited, and may be any conventionally known hydrolyzable group. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Among these, hydrogen atoms, alkoxy groups, acyloxy groups, ketoximate groups, amino groups, amido groups, aminooxy groups, mercapto groups and alkenyloxy groups are preferred, and methoxy Particularly preferred are alkoxy groups such as groups.

Among the crosslinkable silyl groups, a crosslinkable silyl group represented by the following general formula (4) is preferred from the viewpoint of easy availability. In the following general formula (4), R ⁷ , Y, and a have the same meanings as R ⁷ , Y, and a described above.

Specific examples of R ⁶ and R ⁷ in the above general formula (2) include alkyl groups such as methyl group and ethyl group; alicyclic hydrocarbon groups such as cyclohexyl group; aryl groups such as phenyl group; benzyl group aralkyl groups such as; triorganosiloxy groups represented by (R ⁸ ) ₃ SiO-, where R ⁸ is a methyl group, a phenyl group, etc.; and the like. A methyl group is particularly preferred as R ⁶ , R ⁷ and R ⁸ .

On the other hand, examples of the acrylic acid alkyl ester monomer unit forming the main chain of the (meth)acrylic polymer (A) include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, and isobutyl acrylate. Acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, n-heptyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, undecyl acrylate, dodecyl acrylate, lauryl acrylate , tridecyl acrylate, myristyl acrylate, cetyl acrylate, stearyl acrylate, bephenylacrylate, phenyl acrylate, tolyl acrylate, benzyl acrylate, biphenylacrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-hydroxyethyl acrylate, 2- Hydroxypropyl acrylate, glycidyl acrylate, 2-aminoethyl acrylate, trifluoromethylmethyl acrylate, 2-trifluoromethylethyl acrylate, 2-perfluoroethylethyl acrylate, 2-perfluoroethyl-2-perfluorobutylethyl acrylate, Fluoroethyl acrylate, perfluoromethyl acrylate, diperfluoromethylmethyl acrylate, 2-perfluoromethyl-2-perfluoroethylethyl acrylate, 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl acrylate, 2-perfluoro Examples include acrylic esters such as hexadecylethyl acrylate and methacrylic esters corresponding thereto.
These may be used alone or in combination of two or more.

Further, the main chain of the (meth)acrylic polymer (A) is not particularly limited as long as it contains an acrylic acid alkyl ester monomer unit and/or a methacrylic acid alkyl ester monomer unit; The content of these monomer units is preferably more than 50% by mass, more preferably 70% by mass or more, because the obtained cured product has good weather resistance and flexibility at low temperatures.

Furthermore, the main chain of the (meth)acrylic polymer (A) contains, in addition to acrylic acid alkyl ester monomer units and/or methacrylic acid alkyl ester monomer units, monomers that are copolymerizable with these. May include body units. For example, monomer units containing a carboxy group such as acrylic acid and methacrylic acid; monomer units containing an amide group such as acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide; glycidyl acrylate, glycidyl Monomer units containing epoxy groups such as methacrylate; monomer units containing amino groups such as diethylaminoethyl acrylate, diethylaminoethyl methacrylate, and aminoethyl vinyl ether; polyoxyethylene acrylate, polyoxyethylene methacrylate, etc. Copolymerization effects can be expected in terms of curability and internal curability.

Other examples include monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

The monomer composition of the (meth)acrylic polymer (A) is appropriately selected depending on the use, purpose, etc.

For example, if the alkyl chain of the alkyl ester portion of the monomer is long, the glass transition temperature will be low and the physical properties of the cured product will be soft and rubbery. Conversely, when the length is short, the glass transition temperature becomes high and the physical properties of the cured product become hard.
On the other hand, the physical properties after curing largely depend on the molecular weight of the polymer.

Therefore, the monomer composition of the (meth)acrylic polymer (A) may be appropriately selected depending on the desired viscosity, physical properties after curing, etc., while considering the molecular weight.

The molecular weight of the (meth)acrylic polymer (A) is not particularly limited, but those having a number average molecular weight of 500 to 100,000 in terms of polystyrene in gel permeation chromatography (GPC) are preferred during polymerization. Preferable in terms of difficulty, compatibility, and handling viscosity. Among these, those with a number average molecular weight of 1,000 to 50,000 are preferred from the viewpoint of balance between strength and viscosity, and those with a number average molecular weight of 2,000 to 30,000 are preferred from the viewpoint of ease of handling such as workability, adhesiveness, etc. And more preferable.

The above (meth)acrylic polymer (A) may be used alone or in combination of two or more. As such a (meth)acrylic polymer (A), known ones can be used. Specific examples include Kaneka Telechelic Polyacrylate-SA100S, SA110S, SA120S, and SA310S manufactured by Kaneka Corporation.

The synthesis of the (meth)acrylic polymer (A) is not particularly limited, and can be synthesized by a known method.

As a known method, for example, a telechelic polymer having a hydroxyl group at the terminal synthesized using a hydroxyl group-containing initiator disclosed in JP-A No. 61-271306 is injected with a functional group capable of reacting with a hydroxyl group and the above-mentioned crosslinking. A method of introducing a crosslinkable silyl group at the end of a polymer by reacting a compound containing an alkenyl group (for example, isocyanate silanes, etc.); By using a dithiocarbamate or diallyl sulfide as a chain transfer agent, a polymer having an alkenyl group at both ends is used, and a compound having a functional group that can react with this alkenyl group and the crosslinkable silyl group (for example, Examples include a method of introducing the above-mentioned crosslinkable silyl group at the end of the polymer by reacting methoxyhydrosilane, methyldimethoxyhydrosilane, etc.

Furthermore, as disclosed in JP-A-6-211922, an acrylic polymer having a hydroxyl group at the end is produced using a hydroxyl group-containing polysulfide or an alcohol compound as a chain transfer agent, and further, by utilizing the reaction of the hydroxyl group. Also included is a method for producing an acrylic polymer having an alkenyl group at the end. Using an acrylic polymer having an alkenyl group at the end, it is possible to similarly introduce the crosslinkable silyl group at the end of the polymer.

Furthermore, Japanese Patent Publication No. 3-14068 discloses that (meth)acrylic monomers are polymerized in the presence of a crosslinkable silyl group-containing mercaptan, a crosslinkable silyl group-containing disulfide, or a radical polymerization initiator having a crosslinkable silyl group. A method for introducing a crosslinkable silyl group into the terminal of a polymer is disclosed.

Furthermore, Japanese Patent Publication No. 4-55444 discloses a method of polymerizing an acrylic monomer in the presence of a crosslinkable silyl group-containing hydrosilane compound or a tetrahalosilane compound.

Furthermore, JP-A-5-97921 discloses that an acrylic monomer is anionically polymerized using a stable carbanion having a crosslinkable silyl group as an initiator, and the polymer terminal is reacted with a difunctional electrophilic compound to form a polymer terminal. A method of introducing a crosslinkable silyl group is disclosed.

A (meth)acrylic polymer having a crosslinkable silyl group at the end obtained by these methods can be used as the above (meth)acrylic polymer (A), but for the following reasons, it cannot be obtained by other methods. (Meth)acrylic polymers may be more preferable.

In other words, with these methods, it is usually difficult to reliably introduce a crosslinkable silyl group at the end of the polymer due to low reactivity, or the raw material compounds are expensive and uneconomical. There are drawbacks such as In addition, the polymers obtained by these free radical polymerization methods generally have a large molecular weight distribution value of 2 or more and have a problem of high viscosity. Furthermore, because a chain transfer agent is used, it is difficult to obtain a (meth)acrylic polymer with a high molecular weight, resulting in a short molecular weight between crosslinking points, resulting in poor elongation and durability when used as a sealing material. There is a drawback.

Therefore, as a method for obtaining a (meth)acrylic polymer with a narrow molecular weight distribution and low viscosity, and in which a crosslinking functional group is reliably introduced at the end of the polymer, a living Radical polymerization can be used.

In particular, Matyjaszewski et al., Journal of the American Chemical Society (J.Am.Chem.Soc.) 1995, vol. 117, p. 5614, JP-A-9-272714, JP-A-2000-154205, and Among the living radical polymerization methods, JP-A No. 2000-178456 describes an "atom transfer method" in which (meth)acrylic monomers are polymerized using an atom transfer organic halide or a halogenated sulfonyl compound as an initiator and a transition metal complex as a catalyst. "radical polymerization method" is disclosed.

In addition to the above-mentioned characteristics of the "living radical polymerization method," this method has a terminal halogen, etc., which is relatively advantageous for functional group conversion reactions, and has a high degree of freedom in designing the initiator and catalyst. It is more preferable as a method for producing a (meth)acrylic polymer having a functional group.

Radical polymerization reactions generally have a fast polymerization rate and are prone to termination reactions due to coupling between radicals, so it is generally considered difficult to control the reaction, but atom transfer living radical polymerization This method is characterized in that side reactions such as termination reactions at the terminals of polymer growth are unlikely to occur, and furthermore, the molecular weight can be freely controlled by adjusting the charging ratio of monomer and initiator.

In addition, since the molecular weight distribution of polymers obtained by atom transfer radical polymerization can be controlled extremely narrowly to 1.6 or less, it is possible to synthesize (meth)acrylic polymers with the same number average molecular weight. In this case, it is possible to obtain a (meth)acrylic polymer with a lower viscosity compared to conventional free radical polymerization methods. Therefore, the sealant using the polymer obtained by this method has low viscosity and excellent workability.

In addition, in the atom transfer radical polymerization method, it is possible to introduce functional groups at the ends of polymers with high efficiency, and when an organic halide or sulfonyl halide having two or more starting points is used as an initiator, It is possible to synthesize telechelic polymers having functional groups at both ends. Therefore, since a cured product with a long molecular weight between crosslinking points can be obtained, the sealing material using the polymer obtained by this method is different from the conventional one using a (meth)acrylic polymer having a functional group in the side chain of the molecule. It has high elongation and excellent durability compared to the conventional case.

When the siloxane crosslinked organic polymer is a (meth)acrylic polymer crosslinked with siloxane bonds, the siloxane crosslinked organic polymer may contain polyether as a main chain to the extent that the effects of the present invention are not impaired. A polymer with a crosslinkable silyl group that can be crosslinked, a curing catalyst, a dehydrating agent, a plasticizer, a filler, a reinforcing agent, an anti-sagging agent, a coloring agent (pigment), an anti-aging agent, a contact accelerator, etc. Good too.

Specific examples of the curing catalyst include zinc octoate, iron octoate, manganese octoate, tin octoate, zinc naphthenate, iron naphthenate, tin butanoate, tin caprylate, and tin oleate. Carboxylic acid metal salts; carboxylic acids such as versatic acid; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate, dioctyltin dilaurate, diphenyltin diacetate, dibutyltin oxide, dibutyltin oxide and phthalate esters reaction products with organotin compounds such as dibutyltin dimethoxide, dibutyltin (triethoxysiloxy); tin chelate compounds such as dibutyltin diacetylacetonate; tetraethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, tetra- Titanate esters such as 2-ethylhexyloxytitanium, tetraisopropenyloxytitanium; diisopropoxytitanium bis(acetylacetonate), diisopropoxytitanium bis(ethylacetoacetate), 1,3-propanedioxytitanium bis(acetylacetonate) ), 1,3-propanedioxytitanium bis(ethylacetoacetate), titanium tris(acetylacetonate); zirconium alkoxides such as tetraisopropoxyzirconium, tetrabutoxyzirconium, tributoxyzirconium stearate; Zirconium chelate compounds such as zirconium tetra(acetylacetonate); aluminum alkoxides such as triethoxyaluminum, tripropoxyaluminum, tributoxyaluminum; diisopropoxyaluminum (ethylacetoacetate), aluminum tris(acetylacetonate), aluminum Aluminum chelate compounds such as tris(ethyl acetoacetate); primary amines such as butylamine, hexylamine, octylamine, dodecylamine, oleylamine, cyclohexylamine, benzylamine; secondary amines such as dibutylamine; diethylenetriamine , triethylenetetramine, guanidine, diphenylguanidine, xylylenediamine; triethylenediamine, morpholine, N-methylphorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo[5.4.0] Cyclic amines such as -7-undecene; aminoalcohol compounds such as monoethanolamine, diethanolamine, triethanolamine; amine compounds such as aminophenolic compounds such as 2,4,6-tris(dimethylaminomethyl)phenol; carboxylic acid salts thereof; quaternary ammonium salts such as benzyltriethylammonium acetate; low molecular weight amide resins obtained from excess polyamines and polybasic acids; reaction products of excess polyamines and epoxy compounds; and 3- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyl(methyl)trimethoxysilane Examples include amino group-containing silanes such as. In addition, known compounds effective for hydrolysis and/or condensation reactions of silyl groups can be used. Preferably, carboxylic acids such as versatic acid, and/or amine compounds such as primary amines, secondary amines, polyamines, and cyclic amines can be used. Further, as the components of the curing catalyst, among the curing catalysts exemplified above, one type may be used or two or more types may be used in combination.

Among these, metal compounds are preferred because they are difficult to volatilize during storage and handling, and among them, organotin compounds, tin chelate compounds, and titanate esters are preferred because excellent catalytic performance can be obtained with a small amount of compounding.

Specific examples of the dehydrating agent include methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, trimethyl orthopropionate, triethyl orthopropionate, trimethyl orthoisopropionate, triethyl orthoisopropionate, Hydrolyzable ester compounds such as trimethyl orthobutyrate, triethyl orthobutyrate, trimethyl orthoisobutyrate, triethyl orthoisobutyrate; or dimethoxymethane, 1,1-dimethoxyethane, 1,1-dimethoxypropane, 1,1-dimethoxybutane; or , ethyl silicate (tetramethoxysilane), methyl silicate (tetramethoxysilane), methyltrimethoxysilane; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ- Aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethoxydiethoxysilylpropylamine, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N - Aminosilanes such as β(aminoethyl)γ-aminopropylmethyldimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylethyldiethoxysilane; Examples include vinylsilanes such as methoxysilane and vinyltriethoxysilane. Among these, aminosilane and vinylsilane are preferably used from the viewpoint of dehydration effect. These may be used alone or in combination of two or more.

Plasticizers are used to adjust viscosity and physical properties, and generally include derivatives of benzoic acid, phthalic acid, trimellitic acid, pyromellitic acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citric acid, etc. , polyester, polyether, epoxy, and the like.

Various fillers can be blended to adjust mechanical properties, and calcium carbonate, talc, silica, carbon black, etc. are generally used. The activity, particle shape, pH, presence or absence of surface treatment, etc. of the filler greatly affect the storage stability, curing rate, physical properties, and foaming, so care must be taken when determining the type and amount. In particular, calcium carbonate treated with a fatty acid ester or a higher alcohol urethane compound is preferably used.

Specific examples of colorants (pigments) include inorganic pigments such as titanium oxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride, and sulfate; azo pigments; Phthalocyanine pigments, quinacridone pigments, quinacridone quinone pigments, dioxazine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, perinone pigments, diketopyrrolopyrrole pigments, quinonaphthalone pigments, anthraquinone pigments, thioindigo pigments , benzimidazolone pigments, isoindoline pigments, carbon black, and other organic pigments.

As specific examples of the anti-aging agent, commonly used antioxidants, ultraviolet absorbers, light stabilizers and the like can be appropriately used. Examples include hindered amine-based, benzotriazole-based, benzophenone-based, benzoate-based, cyanoacrylate-based, acrylate-based, hindered phenol-based, phosphorus-based, and sulfur-based compounds.

In one embodiment, the (meth)acrylic polymer having a crosslinkable silyl group or a hydrolyzable silicon group contains butyl acrylate as an acrylic acid alkyl ester monomer unit in the main chain, and has a number average molecular weight of 2,000. It may be between 30,000 and 30,000.

Specific examples of (meth)acrylic polymers having hydrolyzable silicon groups that can be used in the production method of the present invention include XMAP SA120S (Kaneka) and telechelic polyacrylates (SA100S, SA110S, or SA310S ( Kaneka)) etc. are exemplified. A specific example of the (meth)acrylic polymer is XMAP SA120S (Kaneka), which has a molecular weight of 14,000, an acrylic component of butyl acrylate, and a silyl group terminal (two functional groups).

The mixing ratio of the repellent and the siloxane crosslinked organic polymer is such that the repellent composition can be cured without inactivating the repellent. If the ratio of the siloxane cross-linked organic polymer is too small, the repellent will bleed out and will not be uniform; on the other hand, if the ratio of the repellent is too small, the amount of repellent released will be small, which is not preferable. For example, the repellent is equal to or more than 1 times, 2 times or more, 3 times or more, 4 times or more, 5 times or more, 10 times or more, 100 times or more, or 1000 times or more, and/or 1000 times or less, 100 times Below, 10 times or less, 5 times or less, 4 times or less, 3 times or less, 2 times or less, or 1 times or less of the siloxane crosslinked organic polymer can be mixed.

The method for producing the repellent composition of the present invention is not particularly limited, and for example, it can be produced by mixing using a roll, kneader, extruder, universal stirrer, or the like.

<Example 1: Curing conditions of siloxane crosslinked organic polymer>
(the purpose)
It is confirmed that siloxane crosslinked organic polymers can be cured in the presence of thiazoline compounds.

(Method and results)
(1) Curing Catalyst Experiments were conducted in which resins were cured using different curing catalysts in the presence of repellents.
As repellents, 2MT (2-methyl-2-thiazoline, Tokyo Kasei Kogyo Co., Ltd.) and 4E2MT (4-ethyl-2-methylthiazoline, Tokyo Kasei Kogyo Co., Ltd.) were used.

S-1, U-50/V10, PG-F/MeOH, and DEAPA were used as curing catalysts. S-1 is a tin-based catalyst Neostan S-1 (Nitto Kasei, High Activity). U-50/V10 is a tin-based catalyst Neostan U-50/Versatic 10 (Nitto Kasei), and Versatic 10 is a promoter (mixing ratio 1:1). PG-F/MeOH (Nippon Carbide) is an amine catalyst, and the mixing ratio of phenylguanidine is 2:1. DEAPA (Koei Chemical, low activity, used in combination with Versatic 10) is an amine catalyst.

The blending ratio was resin/repellent/catalyst=100/10/appropriate amount. The blending ratio of the catalyst is as shown in the table.

Table 1 below shows the results of curing MS resin (Kaneka, S257, Mn20000, D-terminus) composed of an oxyalkylene polymer in the presence of a repellent. The curing showed surface curing, and curing after 120 minutes was confirmed the next morning.

Next, an XMAP resin (Kaneka, SA120S, Mn14000, D-terminal) composed of a (meth)acrylic polymer was cured in the presence of a repellent, and the results are shown in Table 2 below.

The amine catalyst did not cause significant curing retardation for either the PG-F/MeOH or DEAPA systems.

The results of comparing the curing times of the curing catalysts are shown in Table 3 below. The blending ratio was XMAP (Kaneka, SA120S, Mn14000, D terminal)/repellent/catalyst=100/10/appropriate amount. The blending ratio of the catalyst is as shown in the table. Neostan S-1 (Nitto Kasei) was used as the organic tin catalyst, Neostan U-50 (Nitto Kasei) was used as the inorganic tin catalyst, and DEAPA (Koei Chemical) was used as the amine catalyst. For the acid/amine catalyst, neodecanoic acid (Momentive Specialty Chemicals, V10), which is a Versatic acid, was used as the acid, and 3-diethylaminopropylamine (Koei Kagaku Kogyo) was used as the amine. Curing was confirmed in the presence of a repellent no matter which curing catalyst was used.

(2) Resin Next, we investigated resin.
The viscosity of the cured product before curing was measured with a BH type viscometer (No. 7 rotor, rotation speed 20 rpm). The following two types of curing time (TFT-1 and TFT-2) were measured. TFT-1 shows the surface curing time (Tack-Free-Time) at 23° C. and 50% RH, and was measured under the condition of resin/curing catalyst (amine catalyst DEAPA) = 100/5. TFT-2 shows the surface curing time (Tack-Free-Time) at 23°C and 50% RH, and resin/curing catalyst (Versatic acid)/curing catalyst (amine-based catalyst DEAPA) = 100/3/0.5. Measured under the following conditions.

The results of curing MS polymers composed of oxyalkylene polymers in the presence of repellents are shown in Table 4 below. The curing time when 10 parts of 4E2MT is blended as a repellent is shown in parentheses in the TFT-2 column.

Next, the XMAP plasticizer diluted product composed of a (meth)acrylic polymer was cured in the presence of a repellent, and the results are shown in Table 5 below. The curing time when 10 parts of 4E2MT is blended as a repellent is shown in parentheses for TFT-2. UP-1021 shown in the composition indicates an all-acrylic plasticizer (Toagosei), and DINCH indicates DINP hydrogenation (BASF Japan).

(3) Whitening of the surface of the cured product A phenylguanidine/methanol catalyst system (PG-F (3 phr)/MeOH (0.5 phr)) is mixed with XMAP-3 or XMAP-4, which is composed of a (meth)acrylic polymer. However, as a result of curing by leaving it open for 48 hours at 23° C. and 50% RH, a phenomenon in which the surface of the cured product turned white was observed (FIGS. 1A and B). No surface whitening was observed without catalyst and with DEAPA (5 phr) (Fig. 1A,B).

As a result of observing the whitened surface of the cured product using an electron microscope, a wrinkle pattern was observed on the surface (FIG. 1C). The surface whitening observed when using the phenylguanidine/methanol catalyst system is believed to be due to the fine surface structure. In this curing system, volatilization of methanol occurs, so this was considered to be the effect. Whitening of the surface of the cured product is undesirable because it may impair the appearance of the product and reduce the repellent effect of thiazoline compounds.

<Example 2: Measurement of repellent emission amount>
(the purpose)
A repellent composition was prepared by plasticizing 4-ethyl-2-methylthiazoline (4E2MT, FIG. 2A) into an acrylic elastomer (XMAP) as a repellent, and the sustained release properties of 4E2MT were examined.

(Method)
After adding and mixing 6.5 g of 4E2MT (2-methyl-4-ethylthiazoline, Tokyo Kasei Kogyo Co., Ltd.) to 16.5 g of XMAP SA120S (Kaneka), 0.0 g of neodecanoic acid (Yasu Pharmaceutical Co., Ltd.) was added as a curing agent. 65 g and 0.22 g of 3-diethylaminopropylamine (Koei Kagaku Co., Ltd.) were added and mixed. The resulting mixture was poured into a 30 mL PET screw vial (JST-30, MSD Research Scientific Instruments Co., Ltd.) and cured for about 3 hours. XMAP SA120S (Kaneka) is an acrylic elastomer with a molecular weight of 14,000, an acrylic component of butyl acrylate, and a silyl group terminal (two functional groups). The above screw vial was covered with polyethylene wrap (New Poly Wrap, 30 cm x 50 m, Ube Film Co., Ltd.) and tied with hemp string, and the entire screw vial was wrapped with vinyl tape and placed in an outdoor field (Figure 3A, B). .

After 5 months, the screw vials were collected and the dispersion behavior of the repellent into the space when left in a closed space was measured using an odor sensor (Shin Cosmos Electric Co., Ltd., Odor Sensor XP-329m). The odor concentration was determined from this measured value based on a calibration curve that associates the odor sensor detection value with the odor concentration. A calibration curve was created using standard air containing 0.3 ppm, 1 ppm, 3 ppm, and 10 ppm of 4E2MT. Standard air was prepared by mixing compressed air with air in which the repellent had been volatilized at a constant temperature using a gas mixing device (Permeator PD-1B-2, GL Sciences).

(result)
Figure 4 shows the dispersion behavior of the repellent from the sample before field installation and the sample 5 months after field installation. The dispersion behavior of the repellent was almost the same before and after field installation, and it was shown that it exceeded the threshold of 0.5 ppm, which is the standard for showing repellent effect.

This result showed that 4E2MT was stably maintained in the acrylic elastomer for more than 5 months and could be released in a sustained manner over a long period of time. Furthermore, dimerization of 4E2MT (FIG. 2B) was suppressed, indicating that denaturation of the repellent was suppressed.

<Example 3: Repellent effect in apple field>
(the purpose)
The repellent composition prepared in Example 2 is installed in an apple field to verify its repellent effect on voles.

(Method)
In order to verify the repellent effect on voles, the repellent composition prepared in Example 2 was placed in an apple field (FIG. 3B). Voles (Fig. 5) formed mouse holes in the apple fields that were the subject of field tests, causing feeding damage every year. The distribution of mouse holes in voles before field testing is shown in Figure 6A.

The repellent composition was placed in a location where there were many mouse holes (Figure 6B). In addition, an untreated area, rat-proof tape, sulfur + capsaicin, and wire mesh were installed (Figure 6B).

Five months after installing the repellent composition, the presence or absence of feeding damage to the apple bark in each plot was examined.

(result)
As a result of checking the field conditions after the field test period (November to March), no trace of feeding damage was observed on the bark of any apple trees in the field.

No traces of feeding damage were observed in areas other than those where the repellent composition was installed (untreated area, rodent tape, sulfur + capsaicin, wire mesh), which is thought to be the result of the diffusion of the odor molecules of the repellent composition. It will be done. When the wind direction in the field during the field test period (November to March) was confirmed, it was found that the wind was mainly blowing from the west during the field test period, and the repellent composition was located upwind. On the other hand, in farm fields, nest holes are formed over a wide area on the ground surface, nest entrances have been confirmed at the base of apple trees, and voles have been successfully captured. It is clear that these rats were present in the field. Therefore, although voles were present in the field during the field test, the odor molecules slowly released from the repellent composition located upwind continued to be diffused into the surrounding area and all test plots located downwind. It was considered that no feeding damage occurred to the apple bark in the entire test plot.

<Example 4: Dispersion of repellent into the ground>
(the purpose)
The damage caused by voles to apples also extends to the roots of the apples, which are located underground, where voles live. For example, when planting young apple trees in a field, there are cases where the roots are eaten by voles living in the field, so countermeasures are needed. Therefore, in this example, a study was conducted on dispersing the repellent into the ground.

(Method and results)
Up to 500 mL of gardening soil was placed in a 2 L plastic beaker in which an odor sensor (Shin Cosmos Electric Co., Ltd., Odor Sensor XP-329m) was placed at the bottom of the container. A 30 mL screw vial (height 6.8 cm, uncapped) containing the same repellent composition as in Example 2 was placed in or on this gardening soil, and after 1 day in a laboratory fume hood, the odor sensor detected Measurements were recorded. The odor concentration in the soil was determined from this measured value. The odor concentration was determined using the calibration curve created in Example 2. Since gardening soil itself has an odor, measurements were taken as a blank in which a vial containing a composition containing no repellent was placed.

The measurement results are shown in Table 6 below. "Vial position" indicates the depth at which the vial is buried in the soil (distance from the soil surface to the bottom of the vial). 0 cm means that the vial was placed on the soil surface.

It has been shown that by placing the repellent composition of the present invention underground, the repellent can be released into the surrounding ground at a concentration that can be repelled by animals.

<Comparative example 1>
(1) Preparation and curing of animal repellent composition In a 200 mL depot cup, 100 parts by mass of crosslinked polymer S203H, 40 parts by mass of animal repellent 4E2MT, 3 parts by mass of curing catalyst VA, and 0.5 parts by mass of curing catalyst DEAPA After adding parts by mass and thoroughly mixing with a medicine spoon, defoaming was performed to prepare an animal repellent composition.
After filling the obtained animal repellent composition into a polystyrene container (reagent bottle) with a capacity of 30 mL (diameter Φ 33 mm x height 65 mm), the animal repellent composition was cured for 7 days under conditions of 23° C. and 55% RH. hardened.

(2) Preparation of animal repellent device Thereafter, as shown in Figure 7, a polyethylene wrap (New Poly Wrap, 30 cm x 50 cm, manufactured by Ube Film Co., Ltd.) is attached as a membrane member to the top of the head of the gap, and the surrounding area is covered. An animal repellent device containing the cured product of the animal repellent composition of Comparative Example 1 was produced by fixing with vinyl tape.

(3) Physical property evaluation Regarding the cured product of the animal repellent composition of Comparative Example 1, the water vapor permeability at 25°C specified by JIS Z0208:1976 (moisture permeability test method for moisture-proof packaging materials (cup method)) was 140 g/ ( ^m2・24 hours).
Furthermore, regarding the cured product of the animal repellent composition of Comparative Example 1, the 100% modulus of the No. 3 dumbbell specified in JIS K6251:2017 "Vulcanized rubber and thermoplastic rubber - How to determine tensile properties" was 0.14 MPa. The breaking strength of the No. 3 dumbbell was less than 0.01 MPa, and the breaking elongation was less than 50%. In addition, the hardness as determined by type E durometer measurement specified in JIS K6253-3:2012 "Vulcanized rubber and thermoplastic rubber - How to determine hardness" is 50, and the glass transition point when measuring dynamic viscoelasticity is 50. The loss tangent tan δ is 1.9 when the tangent of the ratio of the loss modulus E'' calculated at the glass transition temperature and the storage modulus E' is 1.9, and the cured product of Comparative Example 1 has rubber elasticity. It was shown that

(4) Repellent Effect An animal repellent device containing the cured product of the animal repellent composition of Comparative Example 1 was installed in an apple orchard, and its repellent effect on rats was evaluated over a period of one year. As a result, although the repellent effect against rats was observed in the initial stage of installation, the repellent effect had been lost after one year had passed. This is because the cured product has a very high water vapor permeability, so the animal repellent deteriorates in quality due to hydrolysis and loses its repellent effect. From the above results, the cured product of the animal repellent composition according to Comparative Example 1 does not have a sustained repellent effect and is unable to release the animal repellent over a long period of time.

<Comparative example 2>
(1) Preparation and curing of animal repellent composition and production of animal repellent device In Comparative Example 1, crosslinked polymer S203H was changed to polymer jER (registered trademark) 828, and animal repellent 4E2MT was changed to animal repellent 2MT. An animal repellent device containing a cured product of the animal repellent composition of Comparative Example 2 was produced in the same manner as Comparative Example 1, except that the curing catalyst VA and the curing catalyst DEAPA were changed to ethylenediamine.

(2) Evaluation of physical properties The cured product of the animal repellent composition of Comparative Example 2 has a water vapor permeability of 2.2 at 25°C as specified in JIS Z0208:1976 (moisture permeability test method for moisture-proof packaging materials (cup method)). It was 3g/( ^m2・24 hours).
In addition, regarding the cured product of the animal repellent composition of Comparative Example 2, the breaking strength and elongation of a No. 3 dumbbell specified in JIS K6251:2017 "Vulcanized rubber and thermoplastic rubber - How to determine tensile properties" are the same as those of the cured product. The strength was too high to be measured, and the hardness measured by a type E durometer as specified in JIS K6253-3:2012 "Vulcanized rubber and thermoplastic rubber - How to determine hardness" exceeded the upper limit of measurement. . Further, the loss tangent tan δ at the glass transition point during dynamic viscoelasticity measurement measured in the same manner as Comparative Example 1 was as small as 0.9, and the rubber elasticity of Comparative Example 2 was not observed at all.

(3) Repellent effect The repellent effect of the animal repellent composition of Comparative Example 2 was evaluated in the same manner as in (4) Repellent effect of Comparative Example 1. As a result, in the animal repellent device containing the cured product of the animal repellent composition of Comparative Example 2, no sufficient repellent effect against rats was observed either at the initial stage of installation or after one year had elapsed. Since the cured product of the animal repellent composition of Comparative Example 2 had high strength and high crosslink density, it was assumed that the animal repellent was not sufficiently released.

<Example 5>
(1) Preparation and curing of animal repellent composition, production of animal repellent device The same procedure as in Comparative Example 1 was repeated except that the crosslinked polymer S203H in Comparative Example 1 was changed to crosslinked polymer SA100S. An animal repellent device containing a cured animal repellent composition was produced.

(2) Physical property evaluation Regarding the cured product of the animal repellent composition of Example 5, the water vapor permeability at 25°C specified by JIS Z0208:1976 (moisture permeability test method for moisture-proof packaging materials (cup method)) was 40 g/ ( ^m2・24 hours).
Furthermore, regarding the cured product of the animal repellent composition of Example 5, the breaking strength of a No. 3 dumbbell specified in JIS K6251:2017 "Vulcanized rubber and thermoplastic rubber - How to determine tensile properties" was 0.25 MPa, and the breaking strength was 0.25 MPa at break. The elongation was 100%. The hardness measured by a type E durometer specified in JIS K6253-3:2012 "Vulcanized rubber and thermoplastic rubber - How to determine hardness" was 28, and the dynamic viscosity measured in the same manner as Comparative Example 1 was 28. The loss tangent tan δ at the glass transition point during elasticity measurement was 2.0. This result showed that the cured product of Example 5 had rubber elasticity.

(3) Repellent effect The repellent effect of the animal repellent composition of Example 5 was evaluated in the same manner as (4) Repellent effect of Comparative Example 1. In the animal repellent device containing the cured product of the animal repellent composition of Example 5, the repellent effect against rats was not only observed at the initial stage of installation, but also after one year had passed from the installation of the device. . Therefore, it was shown that the cured product of the animal repellent composition of Example 5 could diffuse the animal repellent over a long period of time without impairing the activity of the animal repellent and maintain the repellent effect. From this, it can be concluded that if the cured product of the animal repellent composition of Example 5 has sufficiently low water vapor permeability and rubber elasticity, it is possible to dissipate the animal repellent for a long period of time. Guessed.

<Example 6>
(1) Preparation and curing of animal repellent composition In a 200 mL depot cup, 100 parts by mass of crosslinked polymer RC100C, 40 parts by mass of animal repellent 4E2MT, 0.02 parts by mass of photoradical initiator Omnirad 1173, and photoradical initiator 0.01 part by mass of the agent Omnirad 819 was added, mixed well with a medicine spoon, and defoamed to prepare an animal repellent composition.
After filling the obtained animal repellent composition into a polystyrene container (reagent bottle) with a capacity of 30 mL (diameter Φ 33 mm x height 65 mm), it was irradiated with UV light with a cumulative light intensity of 3000 mJ/cm ² using a high-pressure mercury lamp, and the animals were The repellent composition was cured.

(2) Preparation of animal repellent device Thereafter, as shown in Fig. 7, a polyethylene wrap (New Poly Wrap, 30 cm x 50 cm, manufactured by Ube Film Co., Ltd.) is pasted as a membrane member on the top of the head of the gap, and the surrounding area is covered. An animal repellent device containing the cured product of the animal repellent composition of Example 6 was produced by fixing with vinyl tape.

(3) Physical property evaluation Regarding the cured product of the animal repellent composition of Example 6, the water vapor permeability at 25°C specified by JIS Z0208:1976 (moisture permeability test method for moisture-proof packaging materials (cup method)) was 37 g/ ( ^m2・24 hours).
In addition, regarding the cured product of the animal repellent composition of Example 6, the breaking strength of No. 3 dumbbell specified in JIS K6251:2017 "Vulcanized rubber and thermoplastic rubber - How to determine tensile properties" was 0.28 MPa, and the breaking strength at break was 0.28 MPa. The elongation was 110%, and the hardness was 25 as measured by a type E durometer specified in JIS K6253-3:2012 "Vulcanized rubber and thermoplastic rubber - How to determine hardness." The loss tangent tan δ at the glass transition point during dynamic viscoelasticity measurement measured in the same manner as above was 1.9. The above results showed that the cured product of Example 6 had rubber elasticity.

(4) Repellent effect The repellent effect of the animal repellent composition of Example 6 was evaluated in the same manner as (4) Repellent effect of Comparative Example 1. In the animal repellent device containing the cured product of the animal repellent composition of Example 6, the repellent effect against rats was not only observed at the initial stage of installation, but also after one year had passed from the installation of the device. . Therefore, it was found that the cured product of the animal repellent composition of Example 6 could diffuse the animal repellent over a long period of time without impairing the activity of the animal repellent and maintain the repellent effect.

<Example 7>
(1) Preparation and curing of animal repellent composition, production of animal repellent device In Example 6, 60 parts by mass of crosslinked polymer RC100C, 40 parts by mass of crosslinked polymer MM100C, and 2MT of animal repellent 4E2MT were used. An animal repellent device containing a cured product of the animal repellent composition of Example 7 was produced in the same manner as in Example 6 except for the changes.

(2) Physical property evaluation Regarding the cured product of the animal repellent composition of Example 7, the water vapor permeability at 25°C specified by JIS Z0208:1976 (moisture permeability test method for moisture-proof packaging materials (cup method)) was 35 g/ ( ^m2・24 hours).
Furthermore, regarding the cured product of the animal repellent composition of Example 7, the breaking strength of a No. 3 dumbbell specified in JIS K6251:2017 "Vulcanized rubber and thermoplastic rubber - How to determine tensile properties" was 0.15 MPa, and the breaking strength at break was 0.15 MPa. The elongation was 170%, and the hardness was 13 as measured by a type E durometer specified in JIS K6253-3:2012 "Vulcanized rubber and thermoplastic rubber - How to determine hardness." The loss tangent tan δ at the glass transition point during dynamic viscoelasticity measurement measured in the same manner as above was 2.1. The above results showed that the cured product of Example 7 had rubber elasticity.

(3) Repellent effect The repellent effect of the animal repellent composition of Example 7 was evaluated in the same manner as (4) Repellent effect of Comparative Example 1. In the animal repellent device containing the cured product of the animal repellent composition of Example 7, the repellent effect against rats was not only observed at the initial stage of installation, but also after one year had passed from the installation of the device. . Therefore, it was found that the cured product of the animal repellent composition of Example 7 could diffuse the animal repellent over a long period of time without impairing the activity of the animal repellent and maintain the repellent effect.

<Example 8>
(1) Preparation and curing of animal repellent composition, production of animal repellent device An animal repellent device containing a cured product of the repellent composition was produced.

(2) Physical property evaluation Regarding the cured product of the animal repellent composition of Example 8, the water vapor permeability at 25°C specified by JIS Z0208:1976 (moisture permeability test method for moisture-proof packaging materials (cup method)) was 15 g/ ( ^m2・24 hours).
Furthermore, regarding the cured product of the animal repellent composition of Example 8, the breaking strength of No. 3 dumbbell specified in JIS K6251:2017 "Vulcanized rubber and thermoplastic rubber - How to determine tensile properties" was 3.3 MPa, and the breaking strength at break was 3.3 MPa. The elongation was 300%, and the hardness was 5 as measured by a type E durometer specified in JIS K6253-3:2012 "Vulcanized rubber and thermoplastic rubber - How to determine hardness." The loss tangent tan δ at the glass transition point during dynamic viscoelasticity measurement measured in the same manner as above was 2.2. The above results showed that the cured product of Example 8 had rubber elasticity.

(3) Repellent effect The repellent effect of the animal repellent composition of Example 8 was evaluated in the same manner as (4) Repellent effect of Comparative Example 1. In the animal repellent device containing the cured product of the animal repellent composition of Example 8, the repellent effect against rats was not only observed at the initial stage of installation, but also after one year had passed from the installation of the device. . Therefore, it was found that the cured product of the animal repellent composition of Example 8 could diffuse the animal repellent over a long period of time without impairing the activity of the animal repellent and maintain the repellent effect.

<Example 9>
(1) Preparation and curing of animal repellent composition, production of animal repellent device The same procedure as in Example 5 was repeated except that the animal repellent 4E2MT in Example 5 was changed to animal repellent 2MT. An animal repellent device containing a cured animal repellent composition was produced.

(2) Physical property evaluation Regarding the cured product of the animal repellent composition of Example 9, the water vapor permeability at 25°C specified by JIS Z0208:1976 (moisture permeability test method for moisture-proof packaging materials (cup method)) was 45 g/ ( ^m2・24 hours).
In addition, regarding the cured product of the animal repellent composition of Example 9, the breaking strength of No. 3 dumbbell specified in JIS K6251:2017 "Vulcanized rubber and thermoplastic rubber - How to determine tensile properties" was 0.24 MPa, and the breaking strength at break was 0.24 MPa. The elongation was 95%, and the hardness was 25 as measured by a type E durometer specified in JIS K6253-3:2012 "Vulcanized rubber and thermoplastic rubber - How to determine hardness." The loss tangent tan δ at the glass transition point during dynamic viscoelasticity measurement measured in the same manner as above was 2.0. The above results showed that the cured product of Example 9 had rubber elasticity.

(3) Repellent effect The repellent effect of the animal repellent composition of Example 9 was evaluated in the same manner as in (4) Repellent effect of Comparative Example 1. In the animal repellent device containing the cured product of the animal repellent composition of Example 9, the repellent effect against rats was not only observed at the initial stage of installation, but also after one year had passed from the installation of the device. . Therefore, it was found that the cured product of the animal repellent composition of Example 9 could diffuse the animal repellent over a long period of time without impairing the activity of the animal repellent and maintain the repellent effect.
The components and curing conditions of the cured products in Comparative Examples 1 to 2 and Examples 5 to 9 are shown in Table 7 below.

The contents of each component in Table 7 are as follows.
(polymer)
S203H is an MS polymer (manufactured by Kaneka Corporation, S203H, number average molecular weight (Mn) 11,000, D terminal) composed of an oxyalkylene polymer, and forms a siloxane crosslinked oxyalkylene polymer.
SA100S is an XMAP resin (SA100S, number average molecular weight (Mn) 22,000, D terminal, manufactured by Kaneka Corporation) composed of a (meth)acrylic polymer, and is a siloxane crosslinked (meth)acrylic polymer. form a union.
RC100C is an XMAP resin (manufactured by Kaneka Corporation, RC100C, number average molecular weight (Mn) 28,000, acryloyl terminal) composed of a (meth)acrylic polymer, and MM100C (manufactured by Kaneka Corporation, MM100C, A radically crosslinked (meth)acrylic polymer is formed by combining it with a number average molecular weight (Mn) of 14,000 and acryloyl one end).
jER® 828 (manufactured by Mitsubishi Chemical Corporation) forms an epoxy resin.

(Reactive diluent)
Isobornyl acrylate (trade name: IBXA, manufactured by Kyoeisha Chemical Co., Ltd.) was used as a reactive diluent.

(animal repellent)
As an animal repellent, 2MT (2-methyl-2-thiazoline, manufactured by Tokyo Chemical Industry Co., Ltd.) or 4E2MT (4-ethyl-2-methylthiazoline, manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

(curing catalyst)
VA (neodecanoic acid, manufactured by Yasu Pharmaceutical Co., Ltd.) and DEAPA (3-diethylaminopropylamine, manufactured by Koei Kagaku Kogyo Co., Ltd.) are used as curing catalysts (acid/amine combination catalysts), or ethylenediamine (as a curing agent for epoxy resins) is used. (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was used.

(Photoradical initiator)
As photo-radical initiators, Omnirad 1173 (α-hydroxyacetophenone, manufactured by BASF Japan Ltd.) and Omnirad 819 (bis(2,4,6-trimethylbenzoyl), manufactured by BASF Japan Ltd.) were used.

The experimental results for Comparative Examples 1 to 2 and Examples 5 to 9 are shown in Table 8 below.

In the cured products produced in Comparative Examples 1 to 2 and Examples 5 to 9, whitening of the surface of the cured products as observed in Example 1 (3) was not observed.

<Comparative Example 3, Examples 10 to 11>
A specified amount of resin (XMAP, etc.), repellent component, and curing catalyst (Versatic/DEAPA) are placed in a container (300 cc capacity) dedicated to the planetary stirring deaerator (foam remover Rentaro ARE-310 (manufactured by Shinky Co., Ltd.)). etc.), and set it in the same stirring/defoaming machine, and first stirred and mixed (a combination of rotation and revolution) at a rotation speed of 1600 rpm for 1.5 minutes.Next, centrifugal defoaming was performed at 2200 rpm for 2 minutes. A mixture was prepared.

Pour 25 g of the obtained mixture into a 30 cc polystyrene vial below without bubbles, remove the top lid, cover with polyethylene wrap, and store at 23°C x 55% RH for a predetermined period (7 days). ) A repellent-containing cured product was obtained by curing.

A container filled with the cured product containing the repellent was exposed to a predetermined location outdoors or indoors with the top covered with polyethylene wrap to confirm the repellent effect and sustained release properties on target animals.

The experimental procedures of Comparative Example 3 and Examples 10 to 11 are shown in the flowchart of FIG. The results of Comparative Example 3 and Examples 10 to 11 are shown in Table 9 below. Note that in the cured products produced in Comparative Example 3 and Examples 10 to 11, whitening of the surface of the cured product as observed in Example 1 (3) was not observed.

From the results of Examples 10 and 11, it was found that the animal repellent was active due to the crosslinked polymer formed by radical crosslinking of a (meth)acrylic polymer and the crosslinked polymer formed by urethane crosslinking of a polyolefin polymer. It has been shown that the repellent effect can be maintained over a long period of time without any damage.
All publications, patents, and patent applications cited herein are incorporated by reference in their entirety.

Claims (23)

A sustained release mammalian repellent composition comprising:
including a mammalian repellent and a cross-linked polymer;
The mammalian repellent has the following formulas (I) to (VI):

(In the formula, R ₁ , R ₂ , and R ₃ each independently represent hydrogen, a halogen atom, a C _1-6 alkyl group, or a C _1-6 alkylthio group.)
Consisting of one or more compounds or salts thereof selected from the compounds shown in
The crosslinked polymer consists of a siloxane crosslinked product of an oxyalkylene polymer, a siloxane crosslinked product of a (meth)acrylic polymer, a radical crosslinked product of a (meth)acrylic polymer, and a urethane crosslinked product of a polyolefin polymer. one or more selected from the group;
The sustained release mammalian repellent composition. A claim in which the compound represented by formula (I) is any compound selected from 2-methylthiazole, 2-ethylthiazole, 2-bromothiazole, 4-methylthiazole, and 2,4-dimethylthiazole. Item 2. The sustained-release mammal repellent composition according to item 1. The compound represented by formula (II) or (III) is 2-methyl-2-thiazoline, 2-methylthio-2-thiazoline, 4-methyl-2-thiazoline, 2,4-dimethyl-2-thiazoline, and The sustained release mammalian repellent composition according to claim 1, which is any compound selected from 2,2-dimethylthiazolidine. The sustained-release mammal repellent composition according to claim 1, wherein the compound represented by formula (IV) is thiomorpholine. The sustained release mammal according to claim 1, wherein the compound represented by formula (V) is any compound selected from 2,5-dimethyl-2-thiazoline and 5-methyl-2-thiazoline. Repellent composition. The sustained-release mammal repellent composition according to any one of claims 1 to 5 , wherein the crosslinked polymer is a siloxane crosslinked product of an oxyalkylene polymer and/or a (meth)acrylic polymer. The oxyalkylene group that is a constituent unit of the polyoxyalkylene structure of the oxyalkylene polymer is an oxyalkylene group having 1 to 6 carbon atoms, and the oxyalkylene polymer has a number average molecular weight of 1,000 to 30,000. 7. The sustained release mammalian repellent composition of claim 6 . The (meth)acrylic polymer contains butyl acrylate as an acrylic acid alkyl ester monomer unit in the main chain, and the (meth)acrylic polymer has a number average molecular weight of 2,000 to 30,000. Item 8. The sustained-release mammal repellent composition according to item 6 or 7 . The sustained release mammal repellent composition according to any one of claims 1 to 8 , further comprising at least one selected from the group consisting of a curing catalyst, an initiator, and a crosslinking agent. 10. The sustained release mammalian repellent composition of claim 9 , wherein the curing catalyst is a carboxylic acid, an amine compound, or an organometallic catalyst. The hardness of the sustained-release mammal repellent composition as measured using a type E durometer according to JIS K6253-3:2012 is 0 or more and less than 50, according to any one of claims 1 to 10 . A sustained release mammalian repellent composition. Claims 1 to 11 , wherein the sustained release mammal repellent composition has a water vapor permeability at 25°C of 0.1 (g/m ² 24 hours) or more and 100 (g/m ² 24 hours) or less. The sustained release mammal repellent composition according to any one of . The sustained-release mammal repellent composition has a breaking strength of 0.01 MPa or more and an elongation at break of 50% or more, as measured by the method described in JIS K6251:2017 using a No. 3 dumbbell. 13. The sustained-release mammal repellent composition according to any one of items 1 to 12 . The loss tangent (tan δ) calculated as the ratio of the loss modulus E'' to the storage modulus E' at the glass transition point during dynamic viscoelasticity measurement of the sustained-release mammal repellent composition is 1.5 or more. , the sustained release mammalian repellent composition according to any one of claims 1 to 13 . A mammal repellent device comprising the sustained release mammal repellent composition according to any one of claims 1 to 14 and a container containing the sustained release mammal repellent composition therein. 16. The mammal repellent device according to claim 15 , wherein the container has one or more openings that are in contact with the outside world. 17. The mammal repellent device according to claim 16 , wherein the opening is a hole or a gap. A method for repelling mammals, the method comprising:
The sustained release mammal repellent composition according to any one of claims 1 to 14 or the mammal repellent device according to any one of claims 15 to 17 is placed in a space where mammals are repelled. The above-mentioned method for avoiding. 1. A method for producing a sustained release mammalian repellent composition, the method comprising:
A mammal repellent, an oxyalkylene polymer and/or (meth)acrylic polymer having a hydrolyzable silyl group , and at least one selected from the group consisting of a curing catalyst, an initiator, and a crosslinking agent are mixed. a mixing step, and a crosslinking step of crosslinking the mixture obtained in the mixing step,
The mammalian repellent has the following formulas (I) to (VI):

(In the formula, R ₁ , R ₂ , and R ₃ each independently represent hydrogen, a halogen atom, a C _1-6 alkyl group, or a C _1-6 alkylthio group.)
The production method comprises one or more compounds selected from the compounds represented by or salts thereof. The oxyalkylene group which is a constituent unit of the polyoxyalkylene structure of the oxyalkylene polymer having a hydrolyzable silyl group is an oxyalkylene group having 1 to 6 carbon atoms, and the oxyalkylene polymer having a hydrolyzable silyl group The manufacturing method according to claim 19 , wherein the number average molecular weight of is 1,000 to 30,000. The (meth)acrylic polymer having a hydrolyzable silyl group contains butyl acrylate as an acrylic acid alkyl ester monomer unit in the main chain, and the number of (meth)acrylic polymers having a hydrolyzable silyl group. The manufacturing method according to claim 19 , wherein the average molecular weight is 2,000 to 30,000. The manufacturing method according to any one of claims 19 to 21 , wherein the curing catalyst is a carboxylic acid, an amine compound, or an organometallic catalyst. 1. A method for producing a sustained release mammalian repellent composition, the method comprising:
A mixing step of mixing a mammal repellent, a polyolefin polymer having a hydroxyl group, and an isocyanate group-containing compound, and
A crosslinking step of crosslinking the mixture obtained in the mixing step,
The mammalian repellent has the following formulas (I) to (VI):

(In the formula, R ₁ ,R ₂ , and R ₃ are each independently hydrogen, halogen atom, C _1-6 Alkyl group or C _1-6 Indicates an alkylthio group. )
The production method comprises one or more compounds selected from the compounds represented by or salts thereof.

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