JP5068488B2 - Method for preparing reactive silicon group-containing polymer composition and room temperature curable silicon group-containing polymer composition - Google Patents

Description

  The present invention relates to a method for preparing a reactive silicon group-containing polymer composition useful as a main component of a room temperature curable silicon group-containing polymer composition useful as an elastic adhesive, a sealing material or a coating material, and room temperature curable silicon. Group-containing polymer composition

  Of the reactive silicon group-containing organic polymers that are liquid at room temperature, those that cure by contact with moisture (humidity) in the air and produce a rubbery elastic body use a base polymer, a crosslinking agent, a catalyst, etc. There is no complication of weighing or mixing immediately before, no mistakes in formulation occur, and excellent adhesiveness, so it is an elastic adhesive and coating material in the electrical and electronic industries, etc. Widely used as a sealing material. Conventionally, a one-pack type room temperature curable polymer composition in which amino group-substituted silanes (amino group-containing silane compounds) are blended as an adhesion improving component has been proposed (see, for example, Patent Document 1). This room temperature curable polymer composition is mainly composed of a reactive silicon group-containing polymer obtained by urethanation reaction of polyoxypropylene polyol and alkoxysilane having isocyanate, and has low flammability and harmfulness. In addition, since the curing is not too fast, there is an advantage that the on-site workability is good.

Conventionally, organic lead compounds and organic zinc compounds have been used as catalysts for the urethanization reaction to obtain the reactive silicon group-containing polymer as the main component. Recently, however, from the viewpoint of environmental protection, organotin compounds have been used. Is used.
Japanese Patent No. 3343604

  However, when an organotin compound is used as a catalyst for the urethanization reaction, the reaction time is shortened and it is economically advantageous, but the viscosity of the reactive silicon group-containing polymer obtained by the urethanization reaction is increased. The storage (storage) stability was not good. In addition, there are problems such as not only the handling when preparing a room temperature-curable polymer composition using the obtained polymer is difficult, but also poor workability such as dischargeability of the composition.

  Furthermore, due to the high catalytic activity of organotin compounds, the reaction between active hydrogen and isocyanate groups tends to occur after urethane bond formation. For this reason, there has been a problem that desired characteristics cannot be obtained due to branching or the fact that the terminal hydroxyl group cannot be sufficiently blocked due to the occurrence of branching.

  The present invention has been made to solve these problems, and an object of the present invention is to provide a reactive silicon group-containing polymer composition that is excellent in storage stability and easy to handle. Another object of the present invention is to provide a room temperature-curable silicon group-containing polymer composition having such a reactive silicon group-containing polymer composition as a main component and excellent workability such as dischargeability.

  As a result of diligent research to solve the above problems, the present inventor added a silane compound containing a mercapto group to a reactive silicon group-containing polymer prepared using an organotin compound as a catalyst for the urethanization reaction. As a result, it was found that the catalyst activity of the organotin compound is suppressed, and a composition that is less prone to thickening and excellent in storage stability can be obtained, thereby completing the present invention.

That is, the method for preparing the reactive silicon group-containing polymer composition of the first invention comprises (a1) a polyoxyalkylene polyol having a number average molecular weight of 500 to 50,000, and (a2) a general formula: R ¹ _m SiX _{3- m—} R ² NCO (wherein R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ² is a C 1-17 divalent hydrocarbon group, and X is hydrolyzable) Each represents a group, m is an integer of 0 to 2), and a process of urethanizing an isocyanate group-containing silicon compound represented by the presence of a tin-based catalyst, and the reactivity obtained in the above process. (B) A step of adding 0.001 to 10 parts by weight of a silane having a mercapto group is added to 100 parts by weight of a silicon group-containing polymer.

The method for preparing the reactive silicon group-containing polymer composition of the second invention comprises: (a1) a polyoxyalkylene polyol having a number average molecular weight of 500 to 50,000, and a polyisocyanate compound having two or more isocyanate groups in the molecule Is subjected to a urethanization reaction in the presence of a tin-based catalyst to obtain a polyoxyalkylene polymer having an isocyanate group at the terminal, and then the resulting isocyanate group-containing polyoxyalkylene polymer is converted into (a3) general formula: R ¹ _m SiX _3-m —R ² W (wherein R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ² is a C 1-17 divalent hydrocarbon group) , X is a hydrolyzable group, W is an active hydrogen group selected from a hydroxyl group, a carboxyl group, a mercapto group, an amino group, and an imino group, and m is 0-2. And (b) a silane having a mercapto group in an amount of 100 parts by weight of the reactive silicon group-containing polymer obtained in the above step. A step of adding 001 to 10 parts by weight is provided.

（式中、Ｒ^３は同一または相異なる炭素数１〜４のアルキル基を示す。）で表される反応性ケイ素基を有する反応性ケイ素基含有ポリマーを生成する工程と、前記工程で得られた反応性ケイ素基含有ポリマー１００重量部に対して、（ｂ）メルカプト基を有するシラン０．００１〜１０重量部を添加する工程を備えることを特徴とする。 The method for preparing the reactive silicon group-containing polymer composition of the third invention comprises: (a1) polyoxypropylene polyol having a number average molecular weight of 500 to 50,000, and (a4) γ-isocyanatopropyltrialkoxysilane. The urethanization reaction is carried out in the presence of a system catalyst, the main chain consists essentially of polyoxypropylene, and the formula:

(Wherein R ³ represents the same or different alkyl groups having 1 to 4 carbon atoms) and a reactive silicon group-containing polymer having a reactive silicon group represented by (B) A step of adding 0.001 to 10 parts by weight of a silane having a mercapto group to 100 parts by weight of the reactive silicon group-containing polymer is provided.

  The room temperature-curable silicon group-containing polymer composition of the fourth invention of the present invention is obtained by adding 100 parts by weight of (A) the reactive silicon group-containing polymer composition obtained by the preparation method of the first to third inventions described above. (B) 0.01-10 parts by weight of a curing catalyst and (C) 0.05-25 parts by weight of an amino group-substituted alkoxysilane, respectively.

  According to the preparation method of the present invention, it is possible to obtain a reactive silicon group-containing polymer composition that is less prone to thickening, has excellent storage stability, and is easy to handle. Further, by using such a reactive silicon group-containing polymer composition as a main component, a room temperature-curable silicon group-containing polymer composition having excellent workability such as dischargeability can be obtained.

Embodiments of the present invention will be described below. A method for preparing a reactive silicon group-containing polymer composition according to the first embodiment includes (a1) a polyoxyalkylene polyol having a number average molecular weight of 500 to 50,000, (a2) a general formula: R ¹ _m SiX _{3- m—} R ² NCO (wherein R ¹ is the same or different substituted or unsubstituted monovalent hydrocarbon group, R ² is a C 1-17 divalent hydrocarbon group, and X is hydrolyzable) Wherein m is an integer of 0 to 2), and a process of urethanizing an isocyanate group-containing silane represented by a tin-based reaction catalyst, and the resulting reactive silicon group (B) The process of adding the silane which has a mercapto group with respect to a containing polymer is provided.

The method for preparing the reactive silicon group-containing polymer composition according to the second embodiment includes (a1) a polyoxyalkylene polyol having a number average molecular weight of 500 to 50,000 and a polyoxyalkylene polyol having two or more isocyanate groups in the molecule. An isocyanate compound is subjected to a urethanization reaction in the presence of a tin-based reaction catalyst to obtain a polyoxyalkylene polymer having an isocyanate group at the terminal, and the obtained isocyanate group-containing polyoxyalkylene polymer is subjected to (a3 ) general ^{formula: _{R 1 m SiX 3-m -R}} 2 W ( wherein, monovalent hydrocarbon group of ^{R 1} are different from each other identical or different substituted or unsubstituted, ^{R 2} is a divalent 1 to 17 carbon atoms X represents a hydrolyzable group, W represents an active hydrogen group selected from a hydroxyl group, a carboxyl group, a mercapto group, an amino group and an imino group. m is an integer of 0 to 2.) The active hydrogen group-containing silicon compound represented by (2) is reacted, and (b) a silane having a mercapto group is added to the resulting reactive silicon group-containing polymer. The process to do is provided.

（式中、Ｒ^３は同一または相異なる炭素数１〜４のアルキル基を示す。）で表される反応性ケイ素基を有するポリマーを生成する工程と、得られた反応性ケイ素基含有ポリマーに対して、（ｂ）メルカプト基を有するシランを添加する工程を備えている。 The method for preparing the reactive silicon group-containing polymer composition of the third embodiment comprises (a1) a polyoxypropylene polyol having a number average molecular weight of 500 to 50,000, and (a4) γ-isocyanatopropyltrialkoxysilane. Urethane reaction in the presence of a tin-based reaction catalyst, the main chain consists essentially of polyoxypropylene, and the formula:

(Wherein R ³ represents the same or different alkyl group having 1 to 4 carbon atoms), and a process for producing a polymer having a reactive silicon group represented by In contrast, (b) a step of adding a silane having a mercapto group is provided.

  In the first and second embodiments, the (a1) polyoxyalkylene polyol which is one component for preparing the reactive silicon group-containing polymer is a polyol having a plurality of oxyalkylene units, and a polyoxypropylene polyol Is preferred. Therefore, in the first to third embodiments, polyoxypropylene polyol having a number average molecular weight of 500 to 50,000 is used from commercially available products widely used as urethane raw materials.

  Specifically, polyoxypropylene polyols such as polyoxypropylene diol, polyoxypropylene triol, polyoxypropylene tetraol, and other polyoxypropylenes such as polyoxy (propylene / ethylene) copolymerization type polyols and other alkylenes are co-polymerized. Examples of the polymerization type polyol include polyols having an oxypropylene unit exceeding 50 mol%, and substantial polyoxypropylene polyols obtained by polymerizing a polyoxypropylene polyol by jumping with a diisocyanate or the like. In addition, in the copolymerization type polyol of polyoxypropylene and other alkylene, even if it is a block type polymer, what added other alkylene oxide to polyoxypropylene polyol may be sufficient.

  In the first to third embodiments, the polyoxypropylene polyol needs to have a hydroxyl group at the molecular end. Among these, those excellent in fast curability and storage stability are polyoxypropylene diols having a number average molecular weight of 5000 to 30000, specifically, preminol 4010 and preminol 4019 (both are products of Asahi Glass Co., Ltd.). Name). A polyoxypropylene diol having a molecular weight in the above range by causing a jumping reaction using a diisocyanate to a low molecular weight polyoxypropylene diol can also be suitably used.

In a first embodiment, the other components for preparing a reactive silicon group-containing polymer, (a2) the general _{^{formula: R 1 m SiX 3-m}} -R isocyanate group-containing silane compound represented by the 2 NCO It is. In the second embodiment, first, the (a1) polyoxypropylene polyol and a polyisocyanate compound having two or more isocyanate groups in the molecule are urethanated in the presence of a tin-based catalyst. Thus, an isocyanate group-containing polyoxyalkylene polymer is obtained, and the obtained isocyanate group-containing polyoxyalkylene polymer is converted into an activity represented by (a3) general formula: R ¹ _m SiX _3-m -R ² W. A reactive silicon group-containing polymer is prepared by reacting a hydrogen group-containing silicon compound. In the second embodiment, tolylene diisocyanate or diphenylmethane diisocyanate is used as the polyisocyanate compound.

In the formula representing the isocyanate group-containing silane compound as the component (a2) and the formula representing the active hydrogen group-containing silicon compound as the component (a3), R ¹ is the same or different substituted or unsubstituted monovalent carbonization. Indicates a hydrogen group. R ² represents a divalent hydrocarbon group having 1 to 17 carbon atoms, preferably an alkylene group or phenylene group having 8 or less carbon atoms. Particularly preferred as R ² are a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, and a hexamethylene group. X represents a hydrolyzable group. Examples of the hydrolyzable group include an alkoxyl group such as a methoxy group and an ethoxy group, a carbamato group, an enoxy group, and an acetoxy group. m is an integer of 0-2. Further, in the formula representing the active hydrogen group-containing silicon compound, W is an activity selected from a hydroxyl group, a carboxyl group, a mercapto group, an amino group (primary amino group), and an imino group (secondary amino group). Indicates a hydrogen group.

  In the third embodiment, the other component for preparing the reactive silicon group-containing polymer is (a4) γ-isocyanatopropyltrialkoxysilane. In particular, γ-isocyanatopropyltrimethoxysilane is preferably used.

  In the first to third embodiments, the mixing ratio of both components for performing the urethanization reaction is not particularly limited, but the isocyanate group-containing silane compound or (a4) γ-isocyanate as the component (a2). The ratio of the number of isocyanate groups (NCO) such as propyltrialkoxysilane and the number of hydroxyl groups (OH) of (a1) polyoxypropylene polyol (hereinafter referred to as NCO / OH ratio) is 0.6 to 1. .2, preferably in a range of 0.8 to 1.0.

  The remaining hydroxyl groups tend to cause deterioration of the curability of the uncured product and a decrease in the weather resistance and water resistance of the cured product. More desirable. However, if the NCO / OH ratio exceeds 1.0, (a1) the reaction with the terminal hydroxyl group of the polyoxypropylene polyol and the reaction of the isocyanate group to the terminal urethane bonding site occur, and the reactive groups are the same. Since it exists in a branched state at the end, problems such as failure to obtain desired physical properties arise. Moreover, since an isocyanate group-containing compound is not inexpensive, there is an economic disadvantage. Therefore, the NCO / OH ratio is most preferably in the range of 0.9 to 0.99.

  Specifically, if it is one kind of polyoxypropylene polyol, the hydroxyl value of this polyol is calculated, and if it is two or more kinds of polyoxypropylene polyol, the hydroxyl value of the mixed polyol by weighted average is calculated. The amount of γ-isocyanatopropyltrialkoxysilane to be reacted is calculated so that the NCO / OH ratio is in the above range per part by weight.

  In determining the blending amount of γ-isocyanatopropyltrialkoxysilane with respect to the polyol, if the NCO / OH ratio is less than 0.6, the resulting silicon group-containing polymer has a reduced fast curability and is due to residual hydroxyl groups. Since water resistance falls, it is not preferable. On the other hand, when the NCO / OH ratio is greater than 1.2, γ-isocyanatopropyltrialkoxysilane remains, so that the storage stability is lowered. When the (a1) polyoxypropylene polyol and (a4) an isocyanate group-containing compound such as γ-isocyanatopropyltrialkoxysilane are blended so that the NCO / OH ratio is in the range of 0.8 to 1.0. Can obtain a room temperature-curable silicon group-containing polymer composition having excellent properties such as fast curability, storage stability, and water resistance.

  In carrying out the urethanization reaction, (a1) polyoxypropylene polyol and (a4) isocyanate group-containing compounds such as γ-isocyanatopropyltrialkoxysilane are mixed in predetermined amounts, respectively, in the presence of a tin-based reaction catalyst, for example, Stir for several hours while heating to a temperature of 60-100 ° C. This reaction is desirably performed in an inert gas such as nitrogen gas.

  Examples of tin catalysts that are catalysts for urethanization include organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, and dibutyltin diacetate; carboxylic acids such as tin octylate, tin naphthenate, tin laurate, and tin ferzatic acid Tin salts can be mentioned. These tin compounds may be added at the beginning of the urethanization reaction or during the urethanization reaction. Completion of the reaction can be judged by taking the point at which a value approximated to the theoretical NCO amount or theoretical hydroxyl value calculated from the NCO / OH ratio is obtained as the reaction end point.

  (A1) When a mixture of polyoxypropylene diol having a specific molecular weight and a polyoxypropylene polyol other than this diol is used as the polyoxypropylene polyol, this mixture is urethanated with (a4) γ-isocyanatopropyltrialkoxysilane. A reactive silicon group-containing polymer may be reacted, or a polyoxypropylene diol having a specific molecular weight and a polyoxypropylene polyol other than the diol are individually (a4) γ-isocyanatopropyltrialkoxysilane and urethane. It is good also as a reactive silicon group containing polymer by making it react, and mixing the urethanide obtained.

  The mixing ratio of the polyoxypropylene diol having a specific molecular weight and the polyoxypropylene polyol other than the diol is preferably 5 to 200 parts by weight of the latter per 100 parts by weight of the former. If it is this range, properties, such as storage stability of a reactive silicon group containing polymer obtained and rapid-hardening property, will not be impaired.

  The reactive silicon group-containing polymer thus obtained has a main chain substantially composed of polyoxypropylene and has a trialkoxysilyl group as the reactive silicon-containing group. Examples include those having a methylene bond and one urethane bond in the chemical bond portion of the chain.

（式中、Ｒ^３は同一または相異なる炭素数１〜４のアルキル基を示す。ｒは正の整数であって、８６＜ｒ＜３４４を満足する数である。）で表される。特に、Ｒ^３が全てメチル基であるものが好ましい。この反応性ケイ素基含有ポリマーは、（ａ4）成分であるγ−イソシアネートプロピルトリアルコキシシランとして、γ−イソシアネートプロピルトリメトキシシランを使用することにより得られるものであり、速硬化性が良好で保存安定性に優れている。 That is, the reactive silicon group-containing polymer has the general formula:

(Wherein R ³ represents the same or different alkyl group having 1 to 4 carbon atoms. R is a positive integer and satisfies 86 <r <344). In particular, those in which all R ³ are methyl groups are preferred. This reactive silicon group-containing polymer is obtained by using γ-isocyanatopropyltrimethoxysilane as γ-isocyanatopropyltrialkoxysilane as component (a4), and has fast curing properties and good storage stability. Excellent in properties.

  In addition, when the number average molecular weight is substantially 5000 to 30000 by jumping reaction with low molecular weight polyoxypropylene diol and diisocyanates, the main chain structure portions are ether bonds such as one or more urethane bonds. In some cases, the terminal of the molecule is a hydroxyl group, and finally the reaction of the hydroxyl group of this jumped polyoxypropylene diol with the isocyanate group of γ-isocyanatopropyltrimethoxysilane is performed by trimethoxy. If the polymer which has a silyl group is obtained, this is also included by the reactive silicon group containing polymer of this invention.

  In the first to third embodiments, (b) a silane having a mercapto group (hereinafter referred to as mercaptosilane) added to the reactive silicon group-containing polymer thus obtained is the above-mentioned after the urethanization reaction. It is a component for suppressing the catalytic activity of the tin compound. Mercaptosilane also functions as an adhesion-imparting component depending on the member (for example, mortars and plastics which are porous members). Examples of such mercaptosilane include 3- (γ-) mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-mercaptopropylmethyldimethoxysilane. In particular, use of 3-mercaptopropyltrimethoxysilane is preferable.

  The blending amount of such mercaptosilane is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 5 parts by weight with respect to 100 parts by weight of the reactive silicon group-containing polymer. . If the blending amount of mercaptosilane is too small, the effect of suppressing the catalytic activity of the tin-based compound cannot be obtained sufficiently, and thickening occurs. On the other hand, if the amount is too large, the effect of suppressing the activity of the tin-based catalyst is saturated and not only economically disadvantageous, but also the amount of the curing catalyst compounded when preparing the composition must be increased. No longer get. Preferably, the amount is 0.01 to 1.0, more preferably 0.01 to 0.95 in terms of molar ratio to the tin-based reaction catalyst used for the preparation of the reactive silicon group-containing polymer.

  In the first and third embodiments, the obtained (A) reactive silicon group-containing polymer composition is a compound that reacts with alcohol and / or moisture to suppress hydrolysis of reactive silicon groups in the polymer. (Hereinafter referred to as a silicon group decomposition inhibiting compound) is preferably blended. The latter silicon group decomposition inhibiting compound suppresses hydrolysis of reactive silicon groups in the polymer by reacting with a compound such as alkoxysilane that generates alcohol by hydrolysis or moisture itself. Compounds are included.

  Examples of the compound that reacts with moisture such as moisture to suppress the decomposition of the reactive silicon group include 2- (3-heptyl) -3-butyl-1,3-oxazolidine, 4-butoxycarbonyl-2,2-dimethyl. Examples include oxazolidine compounds such as -1,3-oxazolidine, oxazoline compounds such as 4-methoxymethyl-2-methyl-5-phenyl-2-oxazoline, and silicon compounds such as silazanes.

  Reactive groups due to moisture such as moisture when taking out reactive silicon group-containing polymers from the reaction system or storing them in a container or preparing a composition by blending an alcohol and / or silicon group decomposition inhibiting compound Decomposition can be suppressed. The compounding amount of the alcohol and / or silicon group decomposition inhibiting compound depends on the influence of moisture and the like, but if the compounding amount is too large compared to the amount of the reactive silicon group-containing polymer, it becomes difficult to obtain desired physical properties. . Alcohol and alkoxysilane can be removed to some extent by heating and decompression during the process, but oxazoline and the like are relatively difficult to remove. Therefore, the compounding amount of the silicon group decomposition inhibiting compound such as oxazoline is 10 parts by weight or less, preferably 5 parts by weight or less with respect to 100 parts by weight of the reactive silicon group-containing polymer.

  The alcohol is preferably the same alcohol that may be generated from the reactive silicon group-containing polymer, or an alcohol that does not significantly differ from the alcohol. When an alcohol having a significantly larger number of carbons than the alcohol generated from the reactive silicon group-containing polymer is added, an exchange reaction with the functional group (alkoxy group) of the reactive silicon group-containing polymer occurs during storage, Since the reactivity of a reactive silicon group containing polymer falls, it is not preferable. The same applies to alkoxysilane. That is, when a silane having an alkoxy group having a significantly larger carbon number than the functional group (alkoxy group) of the reactive silicon group-containing polymer is used, the effect of suppressing the decomposition of the reactive group by moisture is low and the reactivity is low. This is not preferable because it reduces the reactivity of the silicon group-containing polymer.

  The blending amount of such alcohol and / or alkoxysilane is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the obtained reactive silicon group-containing polymer. More preferably, it is 0.1-5 weight part.

  The room temperature-curable silicon group-containing polymer composition of the fourth embodiment of the present invention is based on 100 parts by weight of the (A) reactive silicon group-containing polymer composition obtained in the first to third embodiments. (B) 0.01 to 10 parts by weight of a curing catalyst and (C) 0.05 to 25 parts by weight of an amino group-substituted alkoxysilane are blended.

  (B) A well-known silanol condensation catalyst can be widely used as a curing catalyst. For example, titanium-based esters such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin dilaurate, dibutyltin maleate and dibutyltin diacetate; tin octylate, tin naphthenate, tin laurate, tin ferzatic acid, etc. Carboxylic acid tin salts; Reaction products of dibutyltin oxide and phthalates; Dibutyltin diacetylacetonate; Organoaluminum compounds such as aluminum triacetylacetonate, aluminum trisethylacetoacetate, di (isopropoxy) aluminum ethylacetoacetate; Chelate compounds such as zirconium tetraacetylacetonate and titanium tetraacetylacetonate; lead octylate; iron naphthenate; bismuth-tri (Neodecanoate), bismuth - it can be exemplified metallic catalysts such as tris (2-ethylhexoate) bismuth compounds such as.

  These metal catalysts may be used alone or in combination of two or more. Further, a known amine catalyst such as laurylamine may be used. In the second embodiment, among the above curing catalysts, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate, tin naphthenate, tin laurate, tin tin felzatic acid, or organotin compounds A reaction product of dibutyltin oxide and phthalate; a tin-based catalyst such as dibutyltin diacetylacetonate is particularly preferred.

  The (B) component curing catalyst is 0.01 to 10 parts by weight, preferably 0.05 to 8.0 parts by weight, more preferably 100 parts by weight of the reactive silicon group-containing polymer composition (A). Is blended in an amount of 0.1 to 5.0 parts by weight.

  The room temperature-curable silicon group-containing polymer composition of the fourth embodiment is blended with (C) amino group-substituted alkoxysilane (hereinafter also referred to as aminosilanes) together with the above-described (B) curing catalyst. Known aminosilanes can be used, and specific examples thereof include monoaminosilanes, diaminosilanes, triaminosilanes, terminal trialkoxysilanes, composite reactive aminosilanes, and the like. Monoaminosilanes can be broadly classified into silanes having a primary amino group, silanes having a secondary amino group, silanes having a tertiary amino group, and quaternary ammonium salts. Examples of diaminosilanes include compounds having one primary amino group and one secondary amino group in the molecule, and compounds having two secondary amino groups in the molecule. Examples of terminal trialkoxyaminosilanes include silanes having an alkoxysilyl structure at both ends and having a secondary amino group in the molecule.

  Preferred examples of the amino group-substituted alkoxysilane as component (C) are as follows. Among monoaminosilanes and diaminosilanes, a compound having a primary amino group at the molecular end and a compound in which the alkoxysilyl group is a trimethoxysilyl group, a methyldimethoxysilyl group or a triethoxysilyl group is rapidly cured. It is preferable at the point which shows property. Particularly preferred amino group-substituted alkoxysilanes are N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane. , Γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane. These compounds have the advantage of providing excellent storage stability as well as fast curability.

  (C) The amino group-substituted alkoxysilane is 0.05 to 25 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 100 parts by weight of the reactive silicon group-containing polymer composition (A). -5 parts by weight is blended. When the compounding amount of the amino group-substituted alkoxysilane as component (C) is less than 0.05 parts by weight, good initial adhesiveness cannot be obtained, and adhesion development particularly at low temperatures decreases. If it exceeds 25 parts by weight, liquid separation may occur in the container during storage.

  In the room temperature-curable silicon group-containing polymer composition according to the fourth embodiment of the present invention, vinyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. are used for further improving adhesiveness and storage stability. The silane coupling agent can be blended. Moreover, an epoxy resin and its hardening | curing agent, a filler, a plasticizer, a viscosity modifier, another additive, etc. can be suitably mix | blended as needed.

  Conventionally known epoxy resins can be widely used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, flame retardant type epoxy resin such as tetrabromobisphenol A glycidyl ether, novolac type epoxy resin, hydrogenated bisphenol A type epoxy resin, glycidyl of bisphenol A propylene oxide adduct Ether type epoxy resin, diglycidyl-p-oxybenzoic acid, phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, etc., phthalic acid diglycidyl ester epoxy resin, m-aminophenol epoxy Resin, diaminodiphenylmethane epoxy resin, urethane-modified epoxy resin, various alicyclic epoxy resins, N, N-diglycidylaniline, N, N-diglycidyl-o-toluic Examples thereof include glycidyl ethers of polyhydric alcohols such as gin, triglycidyl isocyanurate, polyalkylene glycol diglycidyl ether and glycerin, epoxidized products of unsaturated polymers such as hydantoin type epoxy resins and petroleum resins.

  Among these epoxy resins, those containing at least two epoxy groups in the molecule are preferable from the viewpoints of high reactivity during curing and that the cured product can easily form a three-dimensional network. More preferable epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, novolac type epoxy resins and phthalic acid diglycidyl ester type epoxy resins.

  Examples of epoxy resin curing agents include triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, Latent curing agents such as amines such as 2,4,6-tris (dimethylaminomethyl) phenol, tertiary amine salts, polyamide resins, ketimines, aldimines, enamines, imidazoles, dicyandiamides, three Boron fluoride complexes, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride, chlorenic anhydride Emissions acids, alcohols, phenols, such as carboxylic acids can be exemplified.

  As the filler, conventionally known fillers can be widely used. Specifically, reinforcing fillers such as fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid and carbon black, calcium carbonate Non-reinforcing fillers such as magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, and glass balloons, asbestos, glass fiber and Examples thereof include fibrous fillers such as filaments.

  Examples of the plasticizer include phthalic acid esters such as dioctyl phthalate, dibutyl phthalate, and butyl benzyl phthalate; aliphatic carboxylic acid esters such as dioctyl adipate, isodecyl succinate, dibutyl sebacate, and butyl oleate; penta Glycol esters such as erythritol ester; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; They can be used in combination. Further, polyoxypropylene monool, polyoxypropylene diol and terminal-modified products thereof can also be used. Examples of the terminal modified product include a compound in which the terminal hydroxyl group is modified to an alkoxy group or an alkenyloxy group, or a compound blocked with a hydrocarbon group via a urethane bond, an ester bond, a urea bond, or a carbonate bond. .

  Examples of the viscosity improver include gelling agents such as hydrogenated castor oil, dibenzylidene sorbitol and tribenzylidene sorbitol, and fatty acid amidated products such as amide wax. Examples of other additives include pigments, various antiaging agents, and ultraviolet absorbers.

  The blending ratio of each of the above components to be blended in the room temperature curable silicon group-containing polymer composition of the present invention is not particularly limited, but usually 1 epoxy resin per 100 parts by weight of the silicon group-containing polymer composition. To 100 parts by weight (preferably 10 to 100 parts by weight), 1 to 200 parts by weight (preferably 50 to 100 parts by weight) of epoxy resin curing agent per 100 parts by weight of epoxy resin, and 0.1 to 200 parts by weight of filler. 1 to 50 parts by weight of a plasticizer and about 0.1 to 10 parts by weight of a viscosity improver are preferably blended.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not limited to a following example. In the examples, “parts” means “parts by weight” and “%” means “% by weight”. All physical property values such as viscosity are measured values at 25 ° C. and relative humidity (RH) 50%.

Example 1
A polyoxy having a number average molecular weight (hereinafter abbreviated as Mn) of 16000 in a 3 liter four-necked separable flask equipped with a stirrer, a dropping funnel, a reflux tube, a thermometer, a nitrogen gas flow device, and a decompression device. Propylene diol (trade name: Preminol 4016: manufactured by Asahi Glass Co., Ltd.) was charged in 2000 parts, and dehydrated by vacuum distillation at 100 ° C. and 10-20 mmHg for 1 hour. Next, after cooling to 50 ° C. or lower, 0.2 parts (100 ppm) of dibutyltin dilaurate (trade name Neostan U-100: manufactured by Nitto Kasei Co., Ltd.) and the NCO / OH ratio become 1.0. Was charged with 44.8 parts of γ-isocyanatopropyltrimethoxysilane (trade name Silquest A-link35: manufactured by GE Toshiba Silicone Co., Ltd.), heated in a nitrogen stream, and stirred at a temperature of 60 to 70 ° C. Continued for hours. The NCO content was measured and decreased to 0.04% (theoretical value: 0%). After cooling to 50 ° C., 0.1 part of 3-mercaptopropyltrimethoxysilane was added, stirred for 1 hour, and then removed. It was. In this way, a reactive silicon group-containing polypropylene polymer composition A was obtained. The viscosity of this polymer composition was 20200 mPa · s.

Example 2
The same operation was performed using the same apparatus as in Example 1, and when the NCO content reached 0.05%, the mixture was cooled to 50 ° C., and 0.05 part of 3-mercaptopropyltrimethoxysilane was added. Then, after stirring for 1 hour, it was taken out. Thus, a reactive silicon group-containing polypropylene polymer composition B was obtained. The viscosity of this polymer composition was 21200 mPa · s.

Example 3
In place of the polyoxypropylene diol used in Example 1, polyoxypropylene diol having a Mn of 10,000 (trade name: Preminol 4010, manufactured by Asahi Glass Co., Ltd.) was used for dehydration in the same manner as in Example 1, and then dibutyltin. 0.2 part (100 ppm) of dilaurate and 6.7 parts of 2,4-toluene diisocyanate were added so that the NCO / OH ratio was 0.48, and the mixture was stirred while stirring at a temperature of 70 to 80 ° C. in a nitrogen stream. By reacting for a period of time, an isocyanate-terminated urethane prepolymer was synthesized.

  Next, after this prepolymer was once cooled to 40 ° C., 28 parts of γ-isocyanatopropyltrimethoxysilane (trade name: Silquest A-link35) was added and reacted for 10 hours with stirring. And when NCO content rate became 0.1%, it cooled to 50 degreeC, 4-mercaptopropyltrimethoxysilane 4 parts was added, and it took out, after stirring for 1 hour. Thus, a reactive silicon group-containing polypropylene polymer composition C having a viscosity of 30130 mPa · s was obtained.

Example 4
300 parts (0.1 mol) of polyoxypropylene diol having a Mn of 3000 (trade name ADEKA Polyether P-3000: manufactured by Asahi Denka Kogyo Co., Ltd.) and 48 parts (0.192 mol) of 4,4′-diphenylmethane diisocyanate And 0.03 part (100 ppm) of dibutyltin dilaurate and 0.033 part of benzoyl chloride as a retarder are respectively added to the mixture (with an NCO / OH ratio of 1.4) and stirred at 60 to 70 ° C. for 4 hours. The NCO content was reduced to about 0.67%.

  Next, 28.5 parts (0.112 mol) of N-phenyl-γ-aminopropyltriethoxysilane (trade name Silquest Y-9669: manufactured by GE Toshiba Silicones Co., Ltd.) was added to the resulting isocyanate-terminated polyurethane prepolymer. The reaction was continued at a temperature of 70 to 75 ° C. until the NCO content became zero, and then cooled to 50 ° C. Thereafter, 0.05 part of 3-mercaptopropyltrimethoxysilane was added and stirred for 1 hour, and then taken out. Thus, a reactive silicon group-containing polypropylene polymer composition D having a viscosity of 27650 mPa · s was obtained.

Comparative Example 1
A reactive silicon group-containing polypropylene polymer E having a viscosity of 21000 mPa · s was used except that 3-mercaptopropyltrimethoxysilane was added, and the same apparatus as in Example 1 was used. Got.

Comparative Example 2
A reactive silicon group-containing polypropylene polymer F having a viscosity of 33200 mPa · s was used except that 3-mercaptopropyltrimethoxysilane was added and the same apparatus as in Example 3 was used. Got.

Comparative Example 3
A reactive silicon group-containing polypropylene polymer G having a viscosity of 30050 mPa · s was used except that 3-mercaptopropyltrimethoxysilane was finally added and the same apparatus as in Comparative Example 1 was used. Got.

Next, the reactive silicon group-containing polypropylene polymers (compositions) A to G obtained in Examples 1 to 4 and Comparative Examples 1 to 3, respectively, were stored in a thermostatic bath at 60 ° C. for 14 days and 30 days. It was left to stand at a room temperature of 23 ° C. for 1 day and returned to 23 ° C., and the viscosity (mPa · s) was measured. And the thickening rate was calculated | required with the following formula | equation. These values are shown in Table 1 together with the measured values of the initial viscosity (mPa · s).
Thickening rate (%) = (viscosity after storage at 60 ° C.−initial viscosity) / initial viscosity × 100

Examples 5-7
In Example 5, 100 parts of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1 was mixed with 2 parts of methanol and stirred and mixed uniformly to obtain a reactive silicon group-containing polypropylene polymer solution I. Obtained. In Example 6, 100 parts of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1 was mixed with 3 parts of vinyltrimethoxysilane and stirred and mixed uniformly. Solution J was obtained. Further, in Example 7, 3 parts of 3-butyl-2- (3-heptyl) -1,3-oxazolidine was added to 100 parts of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1. Then, the mixture was uniformly stirred and mixed to obtain a reactive silicon group-containing polypropylene polymer solution K.

  Next, for each of the reactive silicon group-containing polypropylene polymer solutions I to K obtained in Examples 5 to 7, the viscosity (mPa · s) after storage at 60 ° C. for 14 days and 30 days was measured, respectively, and the viscosity increase rate Asked. These values are shown in Table 2 together with the measured values of the initial viscosity (mPa · s).

Example 8
To 100 parts of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1, 3.0 parts of vinyltrimethoxysilane (trade name Silquest A-171: manufactured by GE Toshiba Silicone Co., Ltd.) was added, and 20 parts at room temperature. After mixing uniformly for 1 minute, 100 parts of synthetic calcium carbonate treated with fatty acid (trade name: Shirahana CCR: manufactured by Shiraishi Kogyo Co., Ltd.) and heavy calcium carbonate (trade name: Whiten SB: manufactured by Bihoku Flour Industries Co., Ltd.) 50 parts of each was added and mixed uniformly.

  Next, 60 parts of dioctyl phthalate was added as a plasticizer, heated and mixed at 100 ° C. for 3 hours under reduced pressure, and then cooled to 50 ° C. or lower. Then, 2.0 parts of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (trade name Silquest A-1120: manufactured by GE Toshiba Silicone Co., Ltd.), vinyltrimethoxysilane (trade name Silquest A-171 ) 2.0 parts and dibutyltin dilaurate 0.3 parts were added and mixed uniformly to obtain a silicon group-containing polymer composition.

Examples 9-11
In Example 9, in place of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1, the reactive silicon group-containing polypropylene polymer composition B obtained in Example 2 was used. The same operation as in No. 8 was performed to obtain a silicon group-containing polymer composition. Further, in Example 10, instead of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1, the reactive silicon group-containing polypropylene polymer composition C obtained in Example 3 was used. The same operation as in Example 8 was performed to obtain a silicon group-containing polymer composition. Furthermore, in Example 11, instead of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1, the reactive silicon group-containing polypropylene polymer composition D obtained in Example 4 was used. The same operation as in Example 8 was performed to obtain a silicon group-containing polymer composition.

Comparative Examples 4-6
In Comparative Example 4, the reactive silicon group-containing polypropylene polymer composition E obtained in Comparative Example 1 was used in place of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1. The same operation as in No. 7 was performed to obtain a silicon group-containing polymer composition. In Comparative Examples 5 and 6, instead of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1, the reactive silicon group-containing polypropylene polymers F and G obtained in Comparative Examples 2 and 3 were used. Were used in the same manner as in Example 7 to obtain silicon group-containing polymer compositions.

  Next, for the silicon group-containing polymer compositions obtained in Examples 8 to 11 and Comparative Examples 4 to 6, respectively, initial physical properties (hardness, 100% modulus, tensile strength and elongation) were measured, The initial dischargeability and the dischargeability after storage at 60 ° C. for 14 days and 30 days were examined. The physical characteristics and the discharge properties were measured as follows.

[Physical properties]
The composition was extruded into a sheet having a thickness of 2 mm, and the obtained sheet was allowed to stand at 23 ° C. and 50% RH for 168 hours to be cured by moisture in the air, and the hardness, 100% modulus, and tensile strength of the cured product. And elongation were measured according to JIS K6301 respectively.

[Dischargeability]
The composition was filled in an aluminum foil wrapping paper cartridge manufactured by Showa Marutsu Co., Ltd. having a volume of 333 ml, and left at the initial stage and 70 ° C. for 5 days, and then a nozzle attached to the tip of the cartridge (the inner diameter of the tip was 6.2 mm). The composition was extruded from At this time, the plunger at the bottom of the cartridge was pushed, and the force for pushing out the composition (discharge force) was measured with an autograph manufactured by Shimadzu Corporation. These measurement results are shown in Table 3.

Examples 12-14
In Example 12, instead of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1, the reactive silicon group-containing polypropylene polymer solution I obtained in Example 5 was used and The same operation was performed to obtain a silicon group-containing polymer composition. In Example 13, the reactive silicon group-containing polypropylene polymer solution J obtained in Example 6 was used in place of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1. The same operation as in No. 8 was performed to obtain a silicon group-containing polymer composition. Furthermore, in Example 14, instead of the reactive silicon group-containing polypropylene polymer composition A obtained in Example 1, the reactive silicon group-containing polypropylene polymer solution K obtained in Example 7 was used. The same operation as in No. 8 was performed to obtain a silicon group-containing polymer composition.

  Next, with respect to the silicon group-containing polymer compositions obtained in Examples 12 to 14, the initial physical properties (hardness, 100% modulus, tensile strength and elongation) were measured in the same manner as described above. And the discharge properties after storage at 60 ° C. for 14 days and 30 days were examined. These measurement results are shown in Table 4.

  As is clear from Tables 1 to 4, the reactive silicon group-containing polymer compositions and polymer solutions obtained in Examples 1 to 7 have a low viscosity increase rate after storage and excellent storage (storage) stability. Yes. In addition, the room temperature curable silicon group-containing polymer compositions of Examples 8 to 14 blended with these reactive silicon group-containing polymers as main components have a good physical property and a low ejection force. Excellent workability such as discharge performance.

  According to the preparation method of the present invention, it is possible to obtain a reactive silicon group-containing polymer composition that is less prone to thickening, has excellent storage stability, and is easy to handle. Further, by using such a reactive silicon group-containing polymer composition as a main component, a room temperature-curable silicon group-containing polymer composition having excellent workability such as dischargeability can be obtained. This room temperature curable silicon group-containing polymer composition is suitable as an elastic adhesive and coating material in the electrical and electronic industries, and as a building sealing material.

Claims (6)

(A1) a polyoxyalkylene polyol number average molecular weight of 500 to 50,000, (a2) the general _{^{formula: R 1 m SiX 3-m}} -R 2 NCO
(Wherein R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group that is the same or different from each other, R ² represents a C 1-17 divalent hydrocarbon group, and X represents a hydrolyzable group. m is an integer of 0 to 2), and a step of urethanizing an isocyanate group-containing silicon compound represented by the following formula:
Reactive silicon group-containing, comprising (b) adding 0.001 to 10 parts by weight of a silane having a mercapto group to 100 parts by weight of the reactive silicon group-containing polymer obtained in the step A method for preparing a polymer composition. (A1) A polyoxyalkylene polyol having a number average molecular weight of 500 to 50,000 and a polyisocyanate compound having two or more isocyanate groups in the molecule are subjected to a urethanation reaction in the presence of a tin-based catalyst, and isocyanate is terminated at the terminal. After obtaining the polyoxyalkylene polymer having a group, the obtained isocyanate group-containing polyoxyalkylene polymer is added to (a3) general formula: R ¹ _m SiX _3-m -R ² W
Wherein R ¹ is a substituted or unsubstituted monovalent hydrocarbon group that is the same or different from each other, R ² is a divalent hydrocarbon group having 1 to 17 carbon atoms, X is a hydrolyzable group, and W is a hydroxyl group. An active hydrogen group selected from a carboxyl group, a mercapto group, an amino group, and an imino group, and m is an integer of 0 to 2).
Reactive silicon group-containing, comprising (b) adding 0.001 to 10 parts by weight of a silane having a mercapto group to 100 parts by weight of the reactive silicon group-containing polymer obtained in the step A method for preparing a polymer composition. (A1) A polyoxypropylene polyol having a number average molecular weight of 500 to 50,000 and (a4) γ-isocyanatopropyltrialkoxysilane are urethanated in the presence of a tin-based catalyst, so that the main chain is substantially poly Consists of oxypropylene at the end of the main chain:

(Wherein R ³ represents the same or different alkyl group having 1 to 4 carbon atoms), and a step of producing a reactive silicon group-containing polymer having a reactive silicon group represented by:
Reactive silicon group-containing, comprising (b) adding 0.001 to 10 parts by weight of a silane having a mercapto group to 100 parts by weight of the reactive silicon group-containing polymer obtained in the step A method for preparing a polymer composition. At least one compound selected from alcohol, alkoxysilane, oxazolidine compound, oxazoline compound, and silazanes is added to the reactive silicon group-containing polymer composition obtained by the preparation method according to any one of claims 1 to 3. A method for preparing a reactive silicon group-containing polymer. To 100 parts by weight of the (A) reactive silicon group-containing polymer composition obtained by the preparation method according to any one of claims 1 to 4,
(B) 0.01 to 10 parts by weight of a curing catalyst;
(C) A room temperature-curable silicon group-containing polymer composition comprising 0.05 to 25 parts by weight of an amino group-substituted alkoxysilane.   6. The room temperature-curable silicon group-containing polymer composition according to claim 5, wherein the (C) amino group-substituted alkoxysilane is N- (β-aminoethyl) -aminopropyltrimethoxysilane.