JP6158466B2 - Method for producing non-aqueous polymer dispersion and method for producing paint - Google Patents
Method for producing non-aqueous polymer dispersion and method for producing paint Download PDFInfo
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- JP6158466B2 JP6158466B2 JP2011089898A JP2011089898A JP6158466B2 JP 6158466 B2 JP6158466 B2 JP 6158466B2 JP 2011089898 A JP2011089898 A JP 2011089898A JP 2011089898 A JP2011089898 A JP 2011089898A JP 6158466 B2 JP6158466 B2 JP 6158466B2
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- 238000004519 manufacturing process Methods 0.000 title claims 6
- 239000004815 dispersion polymer Substances 0.000 title claims 5
- 239000003973 paint Substances 0.000 title 1
- 239000000203 mixture Substances 0.000 claims 4
- 239000000178 monomer Substances 0.000 claims 3
- 229920006163 vinyl copolymer Polymers 0.000 claims 3
- 239000003960 organic solvent Substances 0.000 claims 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000012674 dispersion polymerization Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
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- Graft Or Block Polymers (AREA)
- Paints Or Removers (AREA)
Description
本発明は、粘性制御剤として塗料に配合する、非水性の重合体分散液の製造方法および塗料の製造方法に関する。 The present invention relates to a method for producing a non-aqueous polymer dispersion and a method for producing a paint, which are blended in a paint as a viscosity control agent.
従来から、塗料中に粘性制御剤として非水性の重合体分散液を添加する技術が知られている。 Conventionally, a technique of adding a non-aqueous polymer dispersion as a viscosity control agent to a paint is known.
例えば、特許文献１にはエチレン性不飽和単量体を共重合した水酸基価４０〜２００の共重合体を分散安定剤として用い、前記分散安定剤の存在下に有機溶剤中で含窒素単量体２〜３０質量％及び他のエチレン性不飽和単量体７０〜９８質量％を共重合せしめてなる非水性の重合体分散液を含む高固形分の塗料が記載されている。
しかし、特許文献１記載の方法では、有機溶剤としてヘキサン、ヘプタン、オクタン等の脂肪族炭化水素系の溶剤と、キシレン、トルエン等の芳香族炭化水素系の溶剤と、アルコ−ル系、エ−テル系、エステル系、ケトン系の溶剤とを組み合わせた極性の低い溶剤中で含窒素モノマ−を含む単量体の共重合を行っている。このため、得られた非水性の重合体分散液を含む組成物を、キシレン、ソルベッソ１００（エクソンケミカル（株）製）等の芳香族炭化水素系溶剤や、メチルエチルケトン等のケトン系溶剤、３−エトキシプロピオン酸エチル（イーストマン（株）製）等のエステル系溶剤といった高極性の溶剤を用いて塗料とした場合に、塗料の貯蔵安定性が不十分となる。 However, in the method described in Patent Document 1, aliphatic hydrocarbon solvents such as hexane, heptane, and octane, aromatic hydrocarbon solvents such as xylene and toluene, alcohol solvents, and alcohols are used as organic solvents. Copolymerization of a monomer containing a nitrogen-containing monomer is carried out in a solvent having a low polarity in combination with a tellurium, ester or ketone solvent. For this reason, the composition containing the obtained non-aqueous polymer dispersion is mixed with an aromatic hydrocarbon solvent such as xylene and Solvesso 100 (manufactured by Exxon Chemical Co.), a ketone solvent such as methyl ethyl ketone, 3- When a paint is made using a highly polar solvent such as an ester solvent such as ethyl ethoxypropionate (Eastman Co., Ltd.), the storage stability of the paint becomes insufficient.
本発明はこれらの問題点を解決することを目的とする。 The present invention aims to solve these problems.
本発明の要旨は、一分子鎖あたり不飽和二重結合を０．２〜１．４個有するビニル系共重合体を重合する工程と、不飽和単量体として少なくとも（メタ）アクリロニトリルを含む単量体混合物を、前記ビニル系共重合体を含み、溶解度パラメ−タ−が８．７（ｃａｌ／ｃｍ ３ ）１／２以上１１．４（ｃａｌ／ｃｍ ３ ） １／２ 以下である有機溶剤中で分散重合する工程を含む非水性の重合体分散液の製造方法にある。
The gist of the present invention is a step of polymerizing a vinyl copolymer having 0.2 to 1.4 unsaturated double bonds per molecular chain, and a single unit containing at least (meth) acrylonitrile as an unsaturated monomer. the dimer mixture comprises said vinyl copolymer, the solubility parameter - data - is 8.7 (cal / cm 3) 1/2 or more 11.4 (cal / cm 3) the organic solvent is less than 1/2 It is in the manufacturing method of the non-aqueous polymer dispersion liquid including the process of carrying out dispersion polymerization in the inside.
本発明の製造法により得られる非水性の重合体分散液は、粘性制御剤として塗料に配合した場合の貯蔵安定性がよく、仕上がり外観の優れた塗膜が得られる。 The non-aqueous polymer dispersion obtained by the production method of the present invention has good storage stability when blended in a coating material as a viscosity control agent, and a coating film having an excellent finished appearance can be obtained.
（ビニル系共重合体を重合する工程）
本発明では、一分子鎖あたり不飽和二重結合を０．２〜１．４個有するビニル系共重合体を製造することが必要である。前記ビニル系共重合体は、分散重合において、不飽和単量体を含む単量体混合物を安定に重合するための分散安定化剤としての機能を果たすものである。
(Process for polymerizing vinyl copolymer)
In the present invention, it is necessary to produce a vinyl copolymer having 0.2 to 1.4 unsaturated double bonds per molecular chain. The vinyl copolymer serves as a dispersion stabilizer for stably polymerizing a monomer mixture containing an unsaturated monomer in dispersion polymerization.
前記ビニル系共重合体が有する一分子鎖あたりの不飽和二重結合の数が、０．２個未満では本発明の重合体分散液を添加した塗料の貯蔵安定性が不良となり、１．４個を超えると、分散重合中に高粘度になりゲル化する。貯蔵安定性の点から０．４〜１．０がより好ましい。 If the number of unsaturated double bonds per molecular chain of the vinyl-based copolymer is less than 0.2, the storage stability of the paint to which the polymer dispersion of the present invention is added becomes poor. When it exceeds the number, it becomes highly viscous and gels during dispersion polymerization. 0.4-1.0 is more preferable from the point of storage stability.
不飽和二重結合のビニル系重合体への導入方法としては、例えば以下の公知の方法で製造できる。
（１）エポキシ基−カルボキシル基等互いに反応する官能基の一方を有する不飽和単量体を含む単量体混合物をラジカル共重合し共重合体を製造し、前記共重合体と、もう一方の官能基をもった不飽和単量体を反応させる方法。
（２）互いに反応する官能基の一方を有する連鎖移動剤や重合開始剤を用いて、重合性単量体混合物を重合し、得られた重合体ともう一方の官能基をもった不飽和単量体を反応させ不飽和二重結合を導入する方法。
（３）触媒的連鎖移動法（ＣＣＴＰ法）よって不飽和単量体を含む単量体混合物を重合する方法。
（４）不飽和二重結合を有するマクロモノマ−を用いて重合する方法。
As a method for introducing an unsaturated double bond into a vinyl polymer, for example, it can be produced by the following known method.
(1) Radical copolymerization of a monomer mixture containing an unsaturated monomer having one of functional groups that react with each other, such as an epoxy group-carboxyl group, to produce a copolymer, and the copolymer and the other A method of reacting an unsaturated monomer having a functional group.
(2) A polymerizable monomer mixture is polymerized using a chain transfer agent or a polymerization initiator having one of functional groups that react with each other, and the resulting polymer and an unsaturated monomer having the other functional group are polymerized. A method of introducing an unsaturated double bond by reacting a monomer.
(3) A method of polymerizing a monomer mixture containing an unsaturated monomer by a catalytic chain transfer method (CCTP method).
(4) A method of polymerizing using a macromonomer having an unsaturated double bond.
例えば、前記（１）、（２）の方法の場合、あらかじめ、任意の単量組成、重合条件で、互いに反応する官能基の一方を有する不飽和単量体を含む単量体混合物を共重合し共重合体Ａを製造し、ＧＰＣ（ゲル・パ−ミエ−ション・クロマトグラフィ）によって数平均分子量を測定し、数平均分子量をビニル系重合体を構成する単量体のモル平均分子量で割ることにより、1分子鎖あたりのビニル系共重合体を構成する単量体の個数を求める。得られた単量体の個数と不飽和単量体の共重合体Ａを構成する単量体全体に対するモル分率をかけたものを、共重合体Ａ中の官能基の個数ａとする。次にもう一方の官能基をもった不飽和単量体を反応させ反応率をもとめ、前記官能基の個数ａに反応率をかけたものを、本発明のビニル系共重合体の一分子鎖あたりの不飽和二重結合の数とする。互いに反応する官能基を有する不飽和単量体の比率を調整することで、不飽和二重結合の数を調整する。 For example, in the case of the methods (1) and (2), a monomer mixture containing an unsaturated monomer having one of functional groups that react with each other is previously copolymerized under an arbitrary monomer composition and polymerization conditions. Copolymer A is prepared, the number average molecular weight is measured by GPC (gel permeation chromatography), and the number average molecular weight is divided by the molar average molecular weight of the monomer constituting the vinyl polymer. Thus, the number of monomers constituting the vinyl copolymer per molecular chain is determined. The product obtained by multiplying the number of monomers obtained and the molar fraction of the unsaturated monomer copolymer A with respect to the whole monomers is defined as the number a of functional groups in the copolymer A. Next, the unsaturated monomer having the other functional group is reacted to determine the reaction rate, and the number of functional groups a is multiplied by the reaction rate to obtain one molecular chain of the vinyl copolymer of the present invention. The number of unsaturated double bonds per unit. The number of unsaturated double bonds is adjusted by adjusting the ratio of unsaturated monomers having functional groups that react with each other.
なお反応率は、例えばエポキシ基とカルボキシル基の反応であれば酸価の減少量、イソシアネート基とヒドロキシル基の反応であればイソシアネ−ト価の減少量から求めることができる。 The reaction rate can be determined from, for example, an acid value decrease amount in the case of an epoxy group-carboxyl group reaction, and an isocyanate value decrease amount in the case of an isocyanate group-hydroxyl group reaction.
官能基を有する不飽和単量体としては、(メタ)アクリル酸グリシジル等のエポキシ基を有する単量体；メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、メタクリル酸２−サクシノロイルオキシエチル、メタクリル酸２−マレイノイルオキシエチル、メタクリル酸２−フタロイルオキシエチル、メタクリル酸２−ヘキサヒドロフタロイルオキシエチル等のカルボキシル基を有する単量体；２−イソシアネートエチル（メタ）アクリレ−ト等のイソシアネート基を有する単量体；２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、４−ヒドロキシブチル（メタ）アクリレ−ト等の（メタ）アクリル酸ヒドロキシアルキルエステル；２−ヒドロキシエチル（メタ）アクリレ−トのε−カプロラクトン付加物（市販品としては「プラクセルＦＭ１」、「プラクセルＦＡ１」、「プラクセルＦＭ２Ｄ」、「プラクセルＦＡ２Ｄ」、「プラクセルＦＭ３」、「プラクセルＦＭ５（以上、ダイセル化学工業製）」等）、（メタ）アクリル酸ヒドロキシアルキルのポリエチレングリコ−ル付加物、（メタ）アクリル酸ヒドロキシアルキルポリプロピレングリコ−ル付加物（市販品としては「ブレンマ−ＡＰ４００」「ブレンマ−ＰＰ１０００（以上、日本油脂（株）製）」）等のヒドロキシル基を有する単量体が挙げられる。 As the unsaturated monomer having a functional group, a monomer having an epoxy group such as glycidyl (meth) acrylate; meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-succinic methacrylate Monomers having a carboxyl group such as noroyloxyethyl, 2-malenoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate; 2-isocyanatoethyl (meth) Monomers having an isocyanate group such as acrylate; (meth) such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Hydroxyalkyl ester of acrylic acid; ε- of 2-hydroxyethyl (meth) acrylate Caprolactone adducts (commercially available products such as “Placcel FM1”, “Plaxel FA1”, “Plaxel FM2D”, “Plaxel FA2D”, “Plaxel FM3”, “Plaxel FM5 (above, manufactured by Daicel Chemical Industries)”, etc.) ) Polyethylene glycol adduct of hydroxyalkyl acrylate, hydroxyalkyl polypropylene glycol adduct of (meth) acrylate ("Blemma-AP400" and "Blemma-PP1000" (commercially available from Nippon Oil & Fats Co., Ltd.) And a monomer having a hydroxyl group such as “)”.
互いに反応する官能基の組み合わせとして、例えば、カルボキシ基とエポキシ基、イソシアネート基と水酸基を好適に使用することができる。 As a combination of functional groups that react with each other, for example, a carboxy group and an epoxy group, and an isocyanate group and a hydroxyl group can be preferably used.
なお、共重合可能な不飽和単量体の選択の広範さから、エポキシ基含有不飽和単量体とカルボキシル基含有不飽和単量体の組み合わせが好ましい。エポキシ基含有不飽和単量体と、カルボキシル基含有不飽和単量体は、どちらをラジカル共重合で共重合体に導入してもよいが、カルボキシル基含有不飽和単量体の重合性の高さから、カルボキシル基含有不飽和単量体を含む単量体混合物をラジカル重合し、エポキシ基含有不飽和単量体を反応させるのが好ましい。 A combination of an epoxy group-containing unsaturated monomer and a carboxyl group-containing unsaturated monomer is preferred because of the wide selection of copolymerizable unsaturated monomers. Either an epoxy group-containing unsaturated monomer or a carboxyl group-containing unsaturated monomer may be introduced into the copolymer by radical copolymerization, but the carboxyl group-containing unsaturated monomer has high polymerizability. In view of this, it is preferable to radically polymerize a monomer mixture containing a carboxyl group-containing unsaturated monomer and react the epoxy group-containing unsaturated monomer.
また、前記官能基を有する不飽和単量体と共重合可能な不飽和単量体としては、スチレン、α−メチルスチレン等のビニル系不飽和単量体；メチル（メタ）アクリレ−ト、エチル（メタ）アクリレ−ト、ｎ−ブチル（メタ）アクリレ−ト、ｉ−ブチル（メタ）アクリレ−ト、ｔ−ブチル（メタ）アクリレ−ト等の（メタ）アクリル酸アルキルエステル；フェニル（メタ）アクリレ−ト、ベンジル（メタ）アクリレ−ト等の（メタ）アクリル酸アラルキルエステル；２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、４−ヒドロキシブチル（メタ）アクリレ−ト等の（メタ）アクリル酸ヒドロキシアルキルエステル；２−ヒドロキシエチル（メタ）アクリレ−トのε−カプロラクトン付加物（市販品としては「プラクセルＦＭ１」、「プラクセルＦＡ１」、「プラクセルＦＭ２Ｄ」、「プラクセルＦＡ２Ｄ」、「プラクセルＦＭ３、「プラクセルＦＭ５（以上、ダイセル化学工業製）」等」；（メタ）アクリル酸ヒドロキシアルキルのポリエチレングリコ−ル付加物、（メタ）アクリル酸ヒドロキシアルキルポリプロピレングリコ−ル付加物（市販品としては「ブレンマ−ＡＰ４００」「ブレンマ−ＰＰ１０００（以上、日油製）」）等の水酸基含有不飽和単量体；（メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、メタクリル酸２−サクシノロイルオキシエチル、メタクリル酸２−マレイノイルオキシエチル、メタクリル酸２−フタロイルオキシエチル、メタクリル酸２−ヘキサヒドロフタロイルオキシエチル等のカルボキシル基含有不飽和単量体；（メタ）アクリル酸グリシジル等のエポキシ基含有不飽和単量体などを挙げることができる。 Examples of the unsaturated monomer copolymerizable with the unsaturated monomer having a functional group include vinyl unsaturated monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (Meth) acrylic acid alkyl esters such as (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate; phenyl (meth) (Meth) acrylic acid aralkyl esters such as acrylate and benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) (Meth) acrylic acid hydroxyalkyl ester such as acrylate; ε-caprolactone adduct of 2-hydroxyethyl (meth) acrylate (commercially available product and "Plaxel FM1", "Plaxel FA1", "Plaxel FM2D", "Plaxel FA2D", "Plaxel FM3," Plaxel FM5 (above, manufactured by Daicel Chemical Industries) "etc." Hydroxyl-containing unsaturated units such as polyethylene glycol adducts, (meth) acrylic acid hydroxyalkyl polypropylene glycol adducts (commercially available products are “Blemma-AP400” and “Blemma-PP1000” (above, NOF Corporation)). (Meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 2-succinoloyloxyethyl methacrylate, 2-maleinoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, methacryl Acids such as 2-hexahydrophthaloyloxyethyl acid Bokishiru group-containing unsaturated monomers; (meth) and the like epoxy-containing unsaturated monomers glycidyl acrylate.
なお、分散重合時の分散安定性の点から、エステルのアルキル部分の炭素数が４以上の（メタ）アクリル酸アルキルエステル及び／または、（メタ）アクリル酸シクロアルキルエステル等の単量体を４０質量％以上含むことが好ましい。 From the viewpoint of dispersion stability at the time of dispersion polymerization, a monomer such as (meth) acrylic acid alkyl ester and / or (meth) acrylic acid cycloalkyl ester in which the alkyl portion of the ester has 4 or more carbon atoms is used. It is preferable to contain at least mass%.
また、水酸基含有アクリル樹脂とポリイソシアネートからなる２液型塗料に配合した際、ポリイソシアネートと反応して塗膜成分となることから、ビニル系共重合体の水酸基価は、１０〜１５０ｍｇＫＯＨ／ｇ，より好ましくは２０〜１００ｍｇＫＯＨ／ｇの範囲が好適である。 Moreover, when it mix | blends with the two-component paint which consists of a hydroxyl-containing acrylic resin and polyisocyanate, since it reacts with polyisocyanate and becomes a coating-film component, the hydroxyl value of a vinyl-type copolymer is 10-150 mgKOH / g, More preferably, the range of 20-100 mgKOH / g is suitable.
なお、前記官能基を有する不飽和単量体を含む単量体混合物の共重合は、溶液重合や懸濁重合等の公知の重合方法によって行うことができる。例えば、有機溶剤中にて、ラジカル重合開始剤の存在下で行う溶液重合法によって好適に得ることができる。 In addition, the copolymerization of the monomer mixture containing the unsaturated monomer having the functional group can be performed by a known polymerization method such as solution polymerization or suspension polymerization. For example, it can be suitably obtained by a solution polymerization method carried out in an organic solvent in the presence of a radical polymerization initiator.
（分散重合工程）
次に本発明では、不飽和単量体を含む単量体混合物を、前記ビニル系共重合体を含み溶解度パラメ−タ−が８．５（ｃａｌ／ｃｍ３）1／２以上である有機溶剤中で分散重合する。
分散重合法とは、分散安定化剤の存在下で、単量体の状態では有機溶剤に可溶であるが、重合により生成する重合体は、その有機溶剤に不溶となるような単量体と有機溶剤の組み合わせにおいて重合を行う方法である。前記ビニル系重合体は、溶液重合で得られた重合体溶液を用いても良く、懸濁重合で得られた重合体粒子を有機溶剤に溶解して用いても良い。なお本発明では、前記ビニル系共重合体が分散安定化剤となる。
(Dispersion polymerization process)
Next, in the present invention, the monomer mixture containing an unsaturated monomer is converted into an organic solvent containing the vinyl copolymer and having a solubility parameter of 8.5 (cal / cm 3 ) 1/2 or more. Disperse polymerization in.
A dispersion polymerization method is a monomer that is soluble in an organic solvent in the state of a monomer in the presence of a dispersion stabilizer, but the polymer produced by polymerization is insoluble in the organic solvent. This is a method of carrying out polymerization in a combination of organic solvent. As the vinyl polymer, a polymer solution obtained by solution polymerization may be used, or polymer particles obtained by suspension polymerization may be dissolved in an organic solvent. In the present invention, the vinyl copolymer serves as a dispersion stabilizer.
また前記不飽和単量体としては、スチレン、α−メチルスチレン等のビニル系不飽和単量体；メチル（メタ）アクリレ−ト、エチル（メタ）アクリレ−ト、ｎ−ブチル（メタ）アクリレ−ト、ｉ−ブチル（メタ）アクリレ−ト、ｔ−ブチル（メタ）アクリレ−ト等の（メタ）アクリル酸アルキルエステル；フェニル（メタ）アクリレ−ト、ベンジル（メタ）アクリレ−ト等の（メタ）アクリル酸アラルキルエステル；２−ヒドロキシエチル（メタ）アクリレ−ト、２−ヒドロキシプロピル（メタ）アクリレ−ト、４−ヒドロキシブチル（メタ）アクリレ−ト等の（メタ）アクリル酸ヒドロキシアルキルエステル；２−ヒドロキシエチル（メタ）アクリレ−トのε−カプロラクトン付加物（市販品としては「プラクセルＦＭ１」、「プラクセルＦＡ１」、「プラクセルＦＭ２Ｄ」、「プラクセルＦＡ２Ｄ」、「プラクセルＦＭ３、「プラクセルＦＭ５（以上、ダイセル化学工業製）」等」；（メタ）アクリル酸ヒドロキシアルキルのポリエチレングリコ−ル付加物、（メタ）アクリル酸ヒドロキシアルキルポリプロピレングリコ−ル付加物（市販品としては「ブレンマ−ＡＰ４００」「ブレンマ−ＰＰ１０００（以上、日油製）」）等の水酸基含有不飽和単量体；（メタ）アクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、メタクリル酸２−サクシノロイルオキシエチル、メタクリル酸２−マレイノイルオキシエチル、メタクリル酸２−フタロイルオキシエチル、メタクリル酸２−ヘキサヒドロフタロイルオキシエチル等のカルボキシル基含有不飽和単量体；（メタ）アクリル酸グリシジル等のエポキシ基含有不飽和単量体；（メタ）アクリロニトリル、（メタ）アクリルアミド、４−アクリロイルモルホリン、（メタ）アクリル酸２−ジメチルアミノエチル、Ｎ−メトキシ（メタ）アクリルアミド、Ｎ−ブトキシ（メタ）アクリルアミド等のＮ−アルコキシ（メタ）アクリルアミド等の含窒素不飽和単量体等が挙げられる。 Examples of the unsaturated monomer include vinyl unsaturated monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, and n-butyl (meth) acrylate. (Meth) acrylic acid alkyl esters such as i-butyl (meth) acrylate and t-butyl (meth) acrylate; phenyl (meth) acrylate, benzyl (meth) acrylate and other (meth ) Acrylic acid aralkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; 2 Ε-caprolactone adducts of hydroxyethyl (meth) acrylate (commercially available products are “PLAXEL FM1”, “PLAXEL F A1 "," Placcel FM2D "," Placcel FA2D "," Placcel FM3 "," Placcel FM5 (manufactured by Daicel Chemical Industries, Ltd.) ", etc."; Hydroxyl-containing unsaturated monomers such as hydroxyalkyl polypropylene glycol adducts (commercially available products such as “Blemma-AP400” and “Blemma-PP1000” (manufactured by NOF Corporation)); (meth) acrylic acid, itacon Acid, crotonic acid, maleic acid, fumaric acid, 2-succinoloyloxyethyl methacrylate, 2-maleinoyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, etc. Carboxyl group-containing unsaturated monomer; Epoxy group-containing unsaturated monomers such as glycidyl phosphate; (meth) acrylonitrile, (meth) acrylamide, 4-acryloylmorpholine, 2-dimethylaminoethyl (meth) acrylate, N-methoxy (meth) acrylamide, N- And nitrogen-containing unsaturated monomers such as N-alkoxy (meth) acrylamide such as butoxy (meth) acrylamide.
さらに本発明では、本発明の分散液を塗料に添加した際の、塗料のタレ性が向上することから、前記単量体混合物が、（メタ）アクリロニトリルを５〜３０質量％含むことが好ましく、１０〜２０質量％がさらに好ましい。 Furthermore, in the present invention, since the sagging property of the coating is improved when the dispersion of the present invention is added to the coating, the monomer mixture preferably contains 5 to 30% by mass of (meth) acrylonitrile. 10-20 mass% is further more preferable.
また、前記単量体混合物は、本発明の分散液を塗料に添加した際の、塗料のタレ防止性を向上させるために、ジ（メタ）アクリル酸エチレングリコ−ル、ジ（メタ）アクリル酸トリエチレングリコ−ル、ジ（メタ）アクリル酸１，３−ブチレングリコ−ル、ジ（メタ）アクリル酸１，６−ヘキサンジオ−ル、トリメタクリル酸トリメチロ−ルプロパン等のジ及びトリ（メタ）アクリル酸エステル；ジビニルベンゼン；メタクリル酸アリル；フタル酸ジアリル、マレイン酸ジアリル、シアヌル酸トリアリル、イソシアヌル酸トリアリル等のジ及びトリアリル化合物等の分子内に２個以上の不飽和二重結合を有する単量体を含むことが好ましい。 In addition, the monomer mixture contains di (meth) acrylic acid ethylene glycol and di (meth) acrylic acid in order to improve the sagging prevention property of the paint when the dispersion of the present invention is added to the paint. Di- and tri (meth) acrylic such as triethylene glycol, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane trimethacrylate Monomers having two or more unsaturated double bonds in the molecule such as di- and triallyl compounds such as acid ester; divinylbenzene; allyl methacrylate; diallyl phthalate, diallyl maleate, triallyl cyanurate, triallyl isocyanurate It is preferable to contain.
さらに本発明では、前記単量体混合物を、前記ビニル系共重合体を含み溶解度パラメ−タ−が８．５（ｃａｌ／ｃｍ３）1／２以上である有機溶剤中で分散重合することが必要である。 Furthermore, in the present invention, the monomer mixture may be subjected to dispersion polymerization in an organic solvent containing the vinyl copolymer and having a solubility parameter of 8.5 (cal / cm 3 ) 1/2 or more. is necessary.
前記有機溶剤の溶解度パラメ−タ−が８．５（ｃａｌ／ｃｍ３）１／２未満では、本発明の分散液を塗料に配合した場合、塗料のシンナ−との極性の違いにより、重合体の過度な膨潤や凝集が起こり、塗料の貯蔵安定性が不良となる。前記溶解度パラメ−タ−は、塗料に配合した場合の安定性の点から、８．８（ｃａｌ／ｃｍ３）1／２以上が好ましい。 When the solubility parameter of the organic solvent is less than 8.5 (cal / cm 3 ) 1/2 , when the dispersion of the present invention is blended in the paint, the polymer may differ due to the difference in polarity from the paint thinner. Excessive swelling and aggregation occur, and the storage stability of the paint becomes poor. The solubility parameter is preferably 8.8 (cal / cm 3 ) 1/2 or more from the viewpoint of stability when blended with a paint.
なお前記有機溶剤には、前記ビニル系共重合体を溶液重合で得られた重合体溶液として使用する場合は、溶液重合に使用した有機溶剤も含まれる。 In addition, when using the said vinyl-type copolymer as a polymer solution obtained by solution polymerization, the organic solvent used for solution polymerization is also contained in the said organic solvent.
また、懸濁重合で得られた前記ビニル系共重合体を有機溶剤に溶解し使用するときは、溶解に使用した有機溶剤も含まれる。 Further, when the vinyl copolymer obtained by suspension polymerization is dissolved in an organic solvent and used, the organic solvent used for dissolution is also included.
溶解度パラメ−タ−が８．５以上の有機溶剤としては、ベンゼン（９．２）、工業用キシレン（９．０）、ｏ−キシレン（９．０）、ｐ−キシレン（８．８）、トルエン（８．９）、酢酸エチル（９．１）、酢酸ｎ−ブチル（８．５）、３−エトキシプロピオン酸エチル（９．１）、アセトン（９．９）、メチルエチルケトン（９．３）、メタノ−ル（１４．５）、エタノ−ル（１２．７）、ｎ−ブタノ−ル（１１．４）等が挙げられる。 Examples of organic solvents having a solubility parameter of 8.5 or more include benzene (9.2), industrial xylene (9.0), o-xylene (9.0), p-xylene (8.8), Toluene (8.9), ethyl acetate (9.1), n-butyl acetate (8.5), ethyl 3-ethoxypropionate (9.1), acetone (9.9), methyl ethyl ketone (9.3) , Methanol (14.5), ethanol (12.7), n-butanol (11.4) and the like.
また、市販の「ソルベッソ１００（８．６）」、「ソルベッソ１５０（８．５、以上、エクソンケミカル（株）製）」、ＤＢＥ（９．９、二塩基酸エステル混合物、デュポン（株）製）等の混合溶剤を用いても良い。また、２種類以上の有機溶剤を混合して用いても良く、混合した有機溶剤の溶解度パラメ−タ−が８．５以上であれば、溶解度パラメ−タ−が８．５未満の有機溶剤を含んでいても良い。 In addition, commercially available “Solvesso 100 (8.6)”, “Solvesso 150 (8.5, manufactured by Exxon Chemical Co., Ltd.)”, DBE (9.9, dibasic acid ester mixture, manufactured by DuPont Co., Ltd.) ) Etc. may be used. In addition, two or more kinds of organic solvents may be mixed and used. If the solubility parameter of the mixed organic solvent is 8.5 or more, an organic solvent having a solubility parameter of less than 8.5 is used. It may be included.
有機溶剤の溶解度パラメ−タ−は、Ｓｏｌｖｅｎｔ Ｓｅｌｅｃｔｏｒ Ｃｈａｒｔ（Ｐｕｂ．Ｎｏ．Ｍ−１６７−ＡＡ，Ｅａｓｔｍａｎ Ｃｈｅｍｉｃａｌ Ｃｏｍｐａｎｙ，２００６）に記載されている値を用いた。なお、ソルベッソ１００、ソルベッソ１５０の溶解度パラメーターは、ｐｏｌｙｍｅｒ Ｈａｎｄｂｏｏｋ Ｆｏｒｔｈ Ｅｄｉｔｉｏｎ、ＶＩＩ（１９９９、Ｊｏｈｎ Ｗｉｌｅｙ ＆ Ｓｏｎｓ）の値を用いた。
また前記分散重合は公知の方法で行えばよく、ラジカル重合開始剤存在下、重合温度を３０〜１５０℃、好ましくは５０〜１１０℃とし、重合時間を通常２〜５時間とすることが好ましい。
As the solubility parameter of the organic solvent, values described in Solvent Selector Chart (Pub. No. M-167-AA, Eastman Chemical Company, 2006) were used. The solubility parameters of Solvesso 100 and Solvesso 150 used the values of Polymer Handbook Forth Edition, VII (1999, John Wiley & Sons).
The dispersion polymerization may be carried out by a known method. In the presence of a radical polymerization initiator, the polymerization temperature is preferably 30 to 150 ° C., preferably 50 to 110 ° C., and the polymerization time is usually 2 to 5 hours.
ラジカル重合開始剤としては、例えば、過酸化ベンゾイル、過酸化ラウロイル、過酸化カプロイル、ｔ−ブチルパーオクトエート、過酸化ジアセチル等の有機過酸化物；アゾビスイソブチロニトリル、アゾビスジメチルバレロニトリル、ジメチルα，α´−アゾイソブチレート等のアゾ系開始剤；ジイソプロピルペルオキシジカルボネート等のジアルキルペルオキシジカルボネート；及びレドックス開始剤等を挙げることができる。重合開始剤の濃度は、重合性不飽和単量体に対して０．０１〜１０質量％、より好ましくは０．１〜５質量％の範囲内であることが好適である。 Examples of radical polymerization initiators include organic peroxides such as benzoyl peroxide, lauroyl peroxide, caproyl peroxide, t-butyl peroctoate, and diacetyl peroxide; azobisisobutyronitrile and azobisdimethylvaleronitrile. And azo initiators such as dimethyl α, α′-azoisobutyrate; dialkyl peroxydicarbonates such as diisopropylperoxydicarbonate; and redox initiators. The concentration of the polymerization initiator is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass with respect to the polymerizable unsaturated monomer.
さらに本発明では、前記有機溶剤中に含まれる前記ビニル系共重合体と、前記単量体混合物との質量比が２０／８０〜５０／５０であることが好ましい。前記ビニル系共重合体の比率が２０以上であれば分散重合時の分散安定性が良好となりやすく、５０以下であれば、得られる塗膜の外観が向上しやすい。 Furthermore, in this invention, it is preferable that mass ratio of the said vinyl-type copolymer contained in the said organic solvent and the said monomer mixture is 20 / 80-50 / 50. If the ratio of the vinyl copolymer is 20 or more, the dispersion stability during dispersion polymerization tends to be good, and if it is 50 or less, the appearance of the resulting coating film is likely to improve.
本発明で得られた非水性の重合体分散液は、粘性制御剤として塗料に添加して用いることができる。 The non-aqueous polymer dispersion obtained in the present invention can be used by adding to a coating material as a viscosity control agent.
前記塗料は、硬化剤と反応して良好な塗膜を形成できる樹脂を含むものであればよく、例えばエポキシ基、水酸基、カルボキシル基等の官能基を有する樹脂を挙げることができる。該官能基を有する樹脂としては、例えば、ビスフェノール型エポキシ樹脂、ノボラック型エポキシ樹脂、アクリル樹脂、ポリエステル（アルキド樹脂も包含する）、フッ素樹脂等を挙げることができる。 The coating material should just contain resin which can react with a hardening agent and can form a good coat, for example, resin which has functional groups, such as an epoxy group, a hydroxyl group, and a carboxyl group, can be mentioned. Examples of the resin having a functional group include bisphenol type epoxy resin, novolac type epoxy resin, acrylic resin, polyester (including alkyd resin), and fluorine resin.
なかでも、本発明で得られた非水性の重合体分散液を、水酸基含有アクリル樹脂とポリイソシアネ−トからなる２液型塗料に配合した場合に、タレ膜厚が厚く、外観の良い塗膜を得ることができる。 In particular, when the non-aqueous polymer dispersion obtained in the present invention is blended in a two-component paint comprising a hydroxyl group-containing acrylic resin and a polyisocyanate, a coating film having a large sagging film thickness and a good appearance is obtained. Can be obtained.
水酸基含有アクリル樹脂は、特に限定されるものではなく、用途に合わせて適宜選択することができる。が、例えば、ダイヤナ−ルＨＲ−２３０１（三菱レイヨン（株）製；固形分６５％；ＯＨＶ４０のアクリルポリオ−ル）などが挙げられる。 The hydroxyl group-containing acrylic resin is not particularly limited and can be appropriately selected according to the application. However, for example, Dial HR-2301 (manufactured by Mitsubishi Rayon Co., Ltd .; solid content 65%; OHV40 acrylic polyol).
ポリイソシアネート硬化剤は、特に限定されるものではなく、用途に合わせて適宜選択することができるが、例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチルヘキサンジイソシアネート等の脂肪族ジイソシアネート類、イソホロンジイソシアネート、４，４’−メチレンビス（シクロヘキシルイソシアネート）等の脂環族ジイソシアネート類、キシリレンジイソシアネート、トリレンジイソシアネート等の芳香族ジイソシアネート類等が挙げられる。 The polyisocyanate curing agent is not particularly limited and can be appropriately selected depending on the application. For example, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate, isophorone diisocyanate, 4 Alicyclic diisocyanates such as 4,4'-methylenebis (cyclohexyl isocyanate), and aromatic diisocyanates such as xylylene diisocyanate and tolylene diisocyanate.
ポリイソシアネート硬化剤と共に、エチレングリコール、プロピレングリコール、ネオペンチルグリコール、トリメチロールプロパン等の多価アルコールやイソシアネート基と反応する官能基を有する低分子量のポリエステル樹脂または水等の付加物またはビュレット体、ジイソシアネート同士の重合体、さらにこれらと低級一価アルコール、メチルエチルケトオキシム等公知のブロック化剤でブロックしたもの等を併用することができる。 Polyisocyanate curing agents, polyhydric alcohols such as ethylene glycol, propylene glycol, neopentyl glycol, trimethylolpropane, etc., low molecular weight polyester resins having functional groups that react with isocyanate groups, or adducts or burettes such as water, diisocyanates These polymers can be used in combination with those blocked with a known blocking agent such as a lower monohydric alcohol or methyl ethyl ketoxime.
必要に応じて、ジブチル錫ジラウレート等に代表される硬化促進剤や、硬化触媒（アミン系等）を使用することができる。また、本発明の重合体を含む非水性の分散液を含む塗料を調製する際には、酸化チタン等の無機系顔料やシアニンブルー等の有機系顔料、表面調製剤、紫外線吸収剤、光安定剤、酸化防止剤、等の添加剤を、必要に応じて公知の手段を用いて配合することができる。 If necessary, a curing accelerator represented by dibutyltin dilaurate or the like, or a curing catalyst (such as an amine) can be used. In preparing a coating containing a non-aqueous dispersion containing the polymer of the present invention, an inorganic pigment such as titanium oxide, an organic pigment such as cyanine blue, a surface preparation agent, an ultraviolet absorber, a light stabilizer Additives such as additives and antioxidants can be blended using known means as necessary.
また、塗料化の際にはシンナーで適当な粘度となるように希釈調整する。シンナーに用いられる有機溶剤の具体例としては、キシレン、ソルベッソ１００（エクソンケミカル製）等の芳香族炭化水素系溶剤や、メチルエチルケトン等のケトン系溶剤、３−エトキシプロピオン酸エチル（イーストマン社製）等のエステル系溶剤、プロピレングリコールモノメチルエーテルアセテート等が挙げられる。 In the case of coating, dilution adjustment is performed with a thinner so as to obtain an appropriate viscosity. Specific examples of the organic solvent used in the thinner include aromatic hydrocarbon solvents such as xylene and Solvesso 100 (manufactured by Exxon Chemical), ketone solvents such as methyl ethyl ketone, and ethyl 3-ethoxypropionate (manufactured by Eastman). And ester solvents such as propylene glycol monomethyl ether acetate.
本発明で得られた、重合体を含む非水性の分散液は、上記のＳＰ８．５以上の高極性のシンナーを含む塗料において、貯蔵安定性が良く、チキソ性を有するためタレ防止性に優れた塗料となる。
なお本発明で得られた非水性の重合体分散液は、塗料組成物の全樹脂固形分（非水性の重合体分散液の樹脂固形分も含む）１００質量部に対して、通常、固形分重量で１〜２０質量部、さらに好ましくは３〜１０質量部の範囲内であることが塗料へのチキソ性の付与によるタレ防止性の向上、塗膜の仕上がり外観などの点から好適である。
The non-aqueous dispersion containing the polymer obtained in the present invention is excellent in anti-sagging because it has good storage stability and thixotropy in the above-mentioned paint containing high-polarity thinner than SP8.5. Paint.
The non-aqueous polymer dispersion obtained in the present invention is usually a solid content with respect to 100 parts by mass of the total resin solid content of the coating composition (including the resin solid content of the non-aqueous polymer dispersion). The weight is preferably in the range of 1 to 20 parts by mass, more preferably 3 to 10 parts by mass, from the viewpoints of improvement of sagging prevention by imparting thixotropy to the paint and the finished appearance of the coating film.
本発明の非水性の分散液を含む塗料は、スプレー塗装、刷毛塗り塗装、浸漬塗装、ロール塗装、流し塗装等により塗装することができ、木、金属、ガラス、布、プラスチック、発砲体等、特にプラスチック及び金属表面（例えば、スチール、アルミニウムおよびこれら合金）に用いることができ、なかでも自動車用上塗り塗料として好適に使用することができる。 The paint containing the non-aqueous dispersion of the present invention can be applied by spray coating, brush coating, dip coating, roll coating, flow coating, etc., such as wood, metal, glass, cloth, plastic, foam, etc. In particular, it can be used for plastic and metal surfaces (for example, steel, aluminum, and alloys thereof), and among them, it can be suitably used as a top coating for automobiles.
以下に本発明の実施例を示す。また、評価は以下に示す方法で行った。
なお、「部」は「質量部」を意味する。
Examples of the present invention are shown below. Moreover, evaluation was performed by the method shown below.
“Part” means “part by mass”.
（ビニル系共重合体の数平均分子量（Ｍｎ））
ビニル系共重合体をテトラヒドロフランにて溶液濃度が０．４質量％になるよう調整した後、ＴＯＳＯ社製カラム（ＧＥ４０００ＨＸＬおよびＧ２０００ＨＸＬ）を用いＴＯＳＯ社製ゲルパ−ミエ−ションクロマトグラフィ装置に注入し（注入量１００μｌ）、流量１ｍｌ／分（溶離液テトラヒドロフラン）、カラム温度４０℃にてポリスチレンを基準とし測定した。
(Number average molecular weight (Mn) of vinyl copolymer)
After adjusting the vinyl copolymer with tetrahydrofuran so that the solution concentration becomes 0.4% by mass, the solution is injected into a gel permeation chromatography apparatus manufactured by TOSO using an TOSO column (GE4000HXL and G2000HXL) (injection). The amount was measured based on polystyrene at an amount of 100 μl), a flow rate of 1 ml / min (eluent tetrahydrofuran) and a column temperature of 40 ° C.
（貯蔵安定性）
得られた分散液を６０℃の恒温水槽に1週間浸漬後、粒ゲ−ジ（０〜１００μｍ；大平理化工業製）を用いて５ｍｍ幅に３個以上の粒状痕が見られた膜厚で評価した。
(Storage stability)
After immersing the obtained dispersion in a constant temperature water bath at 60 ° C. for 1 week, using a particle gauge (0 to 100 μm; manufactured by Ohira Rika Kogyo Co., Ltd.), the film thickness was such that 3 or more granular marks were observed in a width of 5 mm. evaluated.
（シンナ−中での貯蔵安定性）
得られた分散液をソルベッソ１００と３−エトキシプロピオン酸エチルの重量比を１：１に調整したシンナ−で２倍に希釈したものを、恒温水槽にて２５℃に保温した後、Ｂ型粘度計を用いて、回転数６０ｒｐｍにおいて１分後の粘度（初期の粘度）を測定した。その後４０℃の恒温水槽に1週間浸けた後、同様に粘度（貯蔵後の粘度）を測定し、増粘率を以下のようにして計算した。
増粘率＝貯蔵後の粘度／初期の粘度×１００質（％）
なお、沈殿や凝集が目視で確認できたものは×とした。
(Storage stability in thinner)
A dispersion obtained by diluting the obtained dispersion twice with a thinner adjusted to a weight ratio of Solvesso 100 and ethyl 3-ethoxypropionate to 1: 1 is kept at 25 ° C. in a constant temperature water bath, and then the B type viscosity is obtained. Using a meter, the viscosity after 1 minute (initial viscosity) was measured at a rotational speed of 60 rpm. Then, after being immersed in a constant temperature water bath at 40 ° C. for 1 week, the viscosity (viscosity after storage) was measured in the same manner, and the thickening rate was calculated as follows.
Thickening rate = viscosity after storage / initial viscosity × 100 quality (%)
In addition, what was able to confirm precipitation and aggregation visually was set to x.
（タレ性試験）
ダイヤナ−ルＨＲ−２３０１（三菱レイヨン（株）製；固形分６５質量％；ＯＨＶ４０のアクリルポリオ−ル）１５３．８部に、得られた分散液を固形分重量で１０部、デュラネ−トＴＰＡ−１００（旭化成ケミカルズ（株）製；固形分１００質量％；ＮＣＯ含有量２３．１質量％のヘキサメチレンジイソシアネ−トのイソシアヌレ−ト型）４５．３部を加えたものを、ソルベッソ１００と３−エトキシプロピオン酸エチルの重量比を１：１に調整したシンナ−で、フォ−ドカップ＃４で２５秒に粘度を調整し、塗料用組成物を得た。
(Sag test)
153.8 parts of dial HR-2301 (manufactured by Mitsubishi Rayon Co., Ltd .; solid content 65% by mass; acrylic polyol of OHV40) 10 parts by weight of the obtained dispersion, duranet TPA Solvesso 100 was prepared by adding 45.3 parts of -100 (manufactured by Asahi Kasei Chemicals Corporation; solid content: 100% by mass; hexamethylene diisocyanate isocyanurate type having NCO content of 23.1% by mass). With a thinner in which the weight ratio of ethyl 3-ethoxypropionate was adjusted to 1: 1, the viscosity was adjusted to 25 seconds with Ford Cup # 4 to obtain a coating composition.
石油ベンジンを含浸させたガ−ゼで拭き脱脂した穴あきダル鋼板（孔径５ミリ；三木コ−ティング（株）製）に、得られた塗料用組成物を、塗装スプレ−ガンを用いて乾燥塗膜が４０μｍとなるように塗装し、塗板を垂直にした状態で室温で１０分間静置した後のタレ長さを測定した。 The obtained coating composition was dried on a perforated dull steel plate (hole diameter: 5 mm; manufactured by Miki Coating Co., Ltd.), which was wiped with gaze impregnated with petroleum benzine and degreased using a paint spray gun. The sagging length was measured after applying the coating film to 40 μm and allowing it to stand at room temperature for 10 minutes with the coated plate vertical.
なお、得られた分散液を加えずに調製した塗料用組成物のタレ長さは３５ｍｍであった。
［実施例１］
The sagging length of the coating composition prepared without adding the obtained dispersion was 35 mm.
[Example 1]
窒素導入管、撹拌機、温度計、還流冷却器、滴下ポンプを備えた反応容器に３−エトキシプロピオン酸エチル４０部を仕込み、窒素を吹き込みながら、１５０℃まで昇温した。同温度を保持しながら、後記表１に示す単量体及びジ−ｔ−アミルパ−オキサイド１部の混合物を3時間かけて滴下した。同温度を１時間保持した後、１３０℃まで冷却し、ｔ−ブチルパ−オキシ−２−エチルヘキサノエ−ト０．５部と３−エトキシプロピオン酸エチル５部の混合物を３０分かけて滴下し、同温度を１時間保持し共重合体を得た。 A reaction vessel equipped with a nitrogen introduction tube, a stirrer, a thermometer, a reflux condenser and a dropping pump was charged with 40 parts of ethyl 3-ethoxypropionate and heated to 150 ° C. while blowing nitrogen. While maintaining the same temperature, a mixture of a monomer and 1 part of di-t-amyl peroxide shown in Table 1 below was added dropwise over 3 hours. After maintaining the same temperature for 1 hour, the mixture was cooled to 130 ° C., and a mixture of 0.5 parts of t-butyl peroxy-2-ethylhexanoate and 5 parts of ethyl 3-ethoxypropionate was added dropwise over 30 minutes. The same temperature was maintained for 1 hour to obtain a copolymer.
得られた共重合体は、数平均分子量が３８００、固形酸価が３．９ｍｇＫＯＨ／ｇであった。前記重合体を構成する単量体のモル平均分子量が１３８．４、アクリル酸のモル分率は１ｍｏｌ％であることから、前記共重合体は、一分子鎖当りの構成単位は２７．５個、一分子鎖当りのアクリル酸由来の構成単位は０．３個であった。 次いで、９０℃に冷却し、ヒドロキノンモノメチルエ−テル０．０５部、テトラブチルアンモニウムブロマイド０．５部、メタクリル酸グリシジル１部を投入し、９０℃でアクリル酸とメタクリル酸グルシジルの反応率が固形酸価から計算し９０質量％以上になるまで同温度を保持した。３−エトキシプロピオン酸エチル２１．７部を投入後冷却し、ビニル系共重合体１を得た。
得られたビニル共重合体１は、固形酸価が０．２ｍｇＫＯＨ／ｇでカルボキシ基とエポキシ基の反応率は９５質量％であり、ビニル系共重合体１の一分子鎖あたりの二重結合数は０．３個であった。
The obtained copolymer had a number average molecular weight of 3800 and a solid acid value of 3.9 mgKOH / g. Since the molar average molecular weight of the monomer constituting the polymer is 138.4 and the molar fraction of acrylic acid is 1 mol%, the copolymer has 27.5 structural units per molecular chain. The number of structural units derived from acrylic acid per molecular chain was 0.3. Next, the mixture was cooled to 90 ° C., 0.05 part of hydroquinone monomethyl ether, 0.5 part of tetrabutylammonium bromide, and 1 part of glycidyl methacrylate were added, and the reaction rate of acrylic acid and glycidyl methacrylate was solid at 90 ° C. The same temperature was maintained until it was 90% by mass or more calculated from the acid value. After charging 21.7 parts of ethyl 3-ethoxypropionate, the mixture was cooled to obtain vinyl copolymer 1.
The obtained vinyl copolymer 1 has a solid acid value of 0.2 mg KOH / g and a reaction rate of carboxy group and epoxy group of 95% by mass. The vinyl copolymer 1 has a double bond per one molecular chain. The number was 0.3.
なおビニル系共重合体１を構成する単量体の混合物の合計を１００部として計算した。 The total of the monomer mixture constituting the vinyl copolymer 1 was calculated as 100 parts.
次に、窒素導入管、撹拌機、温度計、還流冷却器、滴下ポンプを備えた反応容器にビニル系共重合体１を７１．４部とソルベッソ１００（溶解度パラメ−タ−は８．６；エクソンケミカル製）１１４．４部を仕込み、窒素を吹き込みながら、９０℃まで昇温した。同温度を保持しながら、表１に示す不飽和単量体とｔ−ブチルパ−オキシ−２−エチルヘキサノエ−ト４部の混合物を３時間かけて滴下した。同温度を1時間保持した後、ｔ−ブチルパ−オキシ−２−エチルヘキサノエ−ト０．５部とソルベッソ１００ １４．６部の混合物を３０分かけて滴下し、更に1時間保持し分散重合を行い、非水性の重合体分散液を得た。なお、分散重合の工程の各原料は分散重合の工程で使用する不飽和単量体を含む単量体混合物の合計を１００部として計算した。評価結果を表１に示す。 Next, 71.4 parts of vinyl copolymer 1 and Solvesso 100 (solubility parameter is 8.6; in a reaction vessel equipped with a nitrogen introduction tube, a stirrer, a thermometer, a reflux condenser, and a dropping pump. 114.4 parts (manufactured by Exxon Chemical) was charged, and the temperature was raised to 90 ° C. while blowing nitrogen. While maintaining the same temperature, a mixture of the unsaturated monomer shown in Table 1 and 4 parts of t-butyl peroxy-2-ethylhexanoate was added dropwise over 3 hours. After maintaining the same temperature for 1 hour, a mixture of 0.5 part of t-butyl peroxy-2-ethylhexanoate and 14.6 parts of Solvesso 100 is added dropwise over 30 minutes, and further maintained for 1 hour for dispersion polymerization. To obtain a non-aqueous polymer dispersion. In addition, each raw material of the process of dispersion polymerization calculated the total of the monomer mixture containing the unsaturated monomer used at the process of dispersion polymerization as 100 parts. The evaluation results are shown in Table 1.
実施例１において、ビニル系共重合体の組成およびメタクリル酸グリシジルの部数を表１に示すように変えた以外はすべて実施例１と同様にして行い、非水性の重合体分散液を得た。
［実施例４］
A non-aqueous polymer dispersion was obtained in the same manner as in Example 1, except that the composition of the vinyl copolymer and the number of parts of glycidyl methacrylate were changed as shown in Table 1.
[Example 4]
実施例１において、有機溶剤の比率を表１に示すように変えた以外はすべて実施例１と同様にして行い、非水性の重合体分散液を得た。
［実施例５、６］
In Example 1, everything was carried out in the same manner as in Example 1 except that the ratio of the organic solvent was changed as shown in Table 1 to obtain a non-aqueous polymer dispersion.
[Examples 5 and 6]
実施例１において、ビニル系共重合体と単量体混合物の比率を表１に示すように変えた以外はすべて実施例１と同様にして行い、非水性の重合体分散液を得た。
［実施例７、８］
A non-aqueous polymer dispersion was obtained in the same manner as in Example 1 except that the ratio of the vinyl copolymer and the monomer mixture in Example 1 was changed as shown in Table 1.
[Examples 7 and 8]
実施例１において、単量体混合物の組成を表１に示すように変えた以外はすべて実施例１と同様にして行い、非水性の重合体分散液を得た。
［比較例１］
In Example 1, everything was carried out in the same manner as in Example 1 except that the composition of the monomer mixture was changed as shown in Table 1 to obtain a non-aqueous polymer dispersion.
[Comparative Example 1]
窒素導入管、撹拌機、温度計、還流冷却器、滴下ポンプを備えた反応容器に３−エトキシプロピオン酸エチル４０部を仕込み、窒素を吹き込みながら、１５０℃まで昇温した。同温度を保持しながら、後記表１に示す重合性単量体及び重合開始剤の混合物を３時間かけて滴下した。同温度を１時間保持した後、１３０℃まで冷却し、ｔ−ブチルパ−オキシ−２−エチルヘキサノエ−ト０．５部と３−エトキシプロピオン酸エチル５部の混合物を３０分かけて滴下し、同温度を１時間保持した。３−エトキシプロピオン酸エチル２１．７部を投入後冷却し、ビニル系共重合体２を得た。 A reaction vessel equipped with a nitrogen introduction tube, a stirrer, a thermometer, a reflux condenser and a dropping pump was charged with 40 parts of ethyl 3-ethoxypropionate and heated to 150 ° C. while blowing nitrogen. While maintaining the same temperature, a mixture of a polymerizable monomer and a polymerization initiator shown in Table 1 below was dropped over 3 hours. After maintaining the same temperature for 1 hour, the mixture was cooled to 130 ° C., and a mixture of 0.5 parts of t-butyl peroxy-2-ethylhexanoate and 5 parts of ethyl 3-ethoxypropionate was added dropwise over 30 minutes. The same temperature was maintained for 1 hour. After charging 21.7 parts of ethyl 3-ethoxypropionate, the mixture was cooled to obtain vinyl copolymer 2.
得られたビニル系共重合体２を用いた以外は、すべて実施例１と同様にして行い、非水性の重合体分散液を得た。ビニル系共重合体２が不飽和二重結合を有していないため、得られた分散液は貯蔵安定性も悪く、シンナー中での貯蔵安定性試験において沈降した。
［比較例２］
A non-aqueous polymer dispersion was obtained in the same manner as in Example 1 except that the obtained vinyl copolymer 2 was used. Since the vinyl copolymer 2 does not have an unsaturated double bond, the obtained dispersion was poor in storage stability and settled in a storage stability test in thinner.
[Comparative Example 2]
実施例１において、ビニル系共重合体の組成およびメタクリル酸グリシジルの部数を表１に示すように変えた以外は全て同様に行った。しかし、ビニル系共重合体の不飽和二重結合量が多いため、分散重合中にゲル化してしまい、非水性の重合体分散液は得られなかった。
［比較例３］
The same procedure as in Example 1 was carried out except that the composition of the vinyl copolymer and the number of parts of glycidyl methacrylate were changed as shown in Table 1. However, since the vinyl copolymer has a large amount of unsaturated double bonds, gelation occurred during dispersion polymerization, and a non-aqueous polymer dispersion could not be obtained.
[Comparative Example 3]
実施例１において、有機溶剤の種類と比率を表１に示すように変えた以外は全て同様に行い、非水性の重合体分散液を得た。有機溶剤の溶解度パラメ−タ−を８．０と低いため、得られた分散液は貯蔵安定性が不十分であった。 In Example 1, it carried out similarly except having changed the kind and ratio of the organic solvent as shown in Table 1, and obtained the non-aqueous polymer dispersion liquid. Since the solubility parameter of the organic solvent was as low as 8.0, the obtained dispersion had insufficient storage stability.
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