Room temperature curable resin compositions and articles

Abstract

A room-temperature-curing resin composition, which contains in specific ratios (A) an organic polymer in which molecular chain ends are capped by hydrolyzable silyl groups and / or hydroxysilyl groups and (B) a hydrolyzable organosilane compound represented in general formula (1) below and / or a partially hydrolyzed condensate thereof (where R1 is a monovalent hydrocarbon group having a carbon number of 1-10, n is 1-8, and m is 3 or 4), has equivalent or superior curing properties compared to conventional alcohol-release or oxime-release room-temperature-curing resin compositions even if various catalysts are used, can reduce harmful effects on humans and environmental load, and can provide a cured rubber product after curing having favorable rubber properties, adhesion, and durability.

Description

[Technical Field]

[0001] The present invention relates to a room-temperature curable resin composition of the condensation-curing type, in which the polymer main chain is an organic polymer other than an organopolysiloxane, and the molecular chain ends are sealed with hydrolyzable silyl groups and / or hydroxysilyl groups (silyl or silanol groups having a hydroxyl group bonded to a silicon atom), and the polymer main chain is an organic polymer other than an organopolysiloxane, and the composition undergoes crosslinking (curing) by hydrolysis and condensation reactions in the atmosphere at room temperature (23°C ± 15°C). In particular, the detached compound generated from the crosslinking agent (curing agent) by the hydrolysis and condensation reaction during curing (crosslinking) is a cyclic ketone compound such as cyclobutanone or cyclopentanone, and the composition provides a room-temperature curable resin composition that cures well by the condensation reaction and has excellent adhesion, and provides a rubber cured product other than an organopolysiloxane resin such as silicone rubber, and various articles having the composition or its cured product. [Background technology]

[0002] Polymers having reactive silicon groups (hereinafter referred to as hydrolyzable silyl groups) undergo hydrolysis and condensation in the presence of moisture, and silicon groups having hydroxyl groups on silicon atoms (hereinafter referred to as hydroxysilyl groups or silanol groups) condense with other hydrolyzable silyl groups and silanol groups. Organic polymers whose main chain is not an organopolysiloxane, and whose molecular chain ends are sealed with hydrolyzable silyl groups and / or hydroxysilyl groups, are generally called modified silicone polymers because, although they do not have a repeating organosiloxane structure (silicone structure) in the main chain except for the linker portion (connecting portion) with the silyl group at the molecular chain end, they have reactive silyl groups at the molecular chain ends and form a siloxane structure at the crosslinking points during curing. They crosslink and cure in the presence of moisture and can be used as curable resin compositions. Room-temperature curable resin compositions using organic polymers other than organopolysiloxanes as the base polymer are liquid or paste-like at room temperature (23°C ± 15°C) and have the characteristic of becoming a rubbery elastic material upon curing. These characteristics are utilized in coatings, adhesives, and building sealants.

[0003] Room-temperature curable resin compositions that harden by condensation reactions contain hydrolyzable organosilane compounds having hydrolyzable groups in their molecules as curing agents (crosslinking agents). Widely used curing agents include deoxime-type hydrolyzable organosilane compounds that release oxime compounds such as 2-butanone oxime during curing, and de-alcohol-type hydrolyzable organosilane compounds that release alcohol compounds such as methanol.

[0004] On the other hand, oxime compounds such as 2-butanone oxime, which are generated during the curing of deoxime-type curing agents, are suspected of being carcinogenic and are therefore undesirable. Methanol and other substances generated during the curing of de-alcohol-type curing agents are toxic to humans and are designated as highly toxic substances, making them undesirable from the perspective of human health. Furthermore, in some cases, these compositions use tin catalysts as curing catalysts, which are subject to stricter regulations as environmentally harmful substances. This is undesirable from the perspective of ensuring worker safety and protecting the environment in recent years, and there is a need to replace them with hydrolyzable organosilane compounds (curing agents) that have safer leaving groups (leaving compounds).

[0005] Furthermore, the curing agents (crosslinking agents) used in de-alcoholized, room-temperature curable resin compositions have the disadvantage of being less reactive than the curing agents used in de-oximeized, room-temperature curable resin compositions, resulting in inferior curability compared to the de-oximeized type. From the perspective of environmental protection and the suppression of health damage, there is a particular demand for products that are more environmentally friendly and safe in addition to having improved performance. As a result, there is a growing demand for room-temperature curable organopolysiloxane compositions that have high safety of the detached compounds and excellent performance.

[0006] International Publication No. 2019 / 077942 (Patent Document 1) describes how using a polyoxyalkylene compound having a hydrolyzable silyl group with a thioether bond at the β-position at its terminus achieves higher curability than conventional modified silicone compositions. Furthermore, Japanese Patent Application Publication No. 2018-87348 (Patent Document 2) reports that by using a polyoxyalkylene compound having a silanol group at its terminus, compositions with excellent curability can be obtained by using crosslinking agents other than conventional de-alcohol type crosslinking agents, such as de-oxime type or acetic acid type. However, in these reported examples, the leaving groups are the same as conventional methods, such as methanol and oxime, which are highly toxic, and acetic acid, which is highly corrosive to metals, and there is a need for the development of compositions with safer leaving groups. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2019 / 077942 [Patent Document 2] Japanese Patent Publication No. 2018-87348 [Patent Document 3] Patent No. 6565787 [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention has been made in view of the above circumstances, and in a room-temperature curable resin composition using, as a base polymer, an organic polymer other than organopolysiloxane (modified silicone polymer) whose molecular chain terminals are blocked with a hydrolyzable silyl group and / or a hydroxysilyl group (a silyl group or a silanol group having a hydroxyl group bonded to a silicon atom), there are no reported cases of health hazards such as carcinogenicity and reproductive toxicity to humans, and environmental hazards such as aquatic organism toxicity, and by using, as a curing agent, a hydrolyzable organosilane compound having a cyclic ketone compound such as cyclobutanone or cyclopentanone as a leaving group (leaving compound) with a relatively high flash point, even when using various catalysts, it has curability equal to or higher than that of conventional de-alcohol type and de-oxime type room-temperature curable resin compositions, and moreover, it reduces the harmfulness to humans and the environmental load, and can provide a rubber cured product having good rubber physical properties, adhesiveness and durability after curing. The purpose is to provide a room-temperature curable resin composition, and various articles having this composition or a cured product obtained by curing this composition.

Means for Solving the Problems

[0009] As a result of intensive studies to achieve the above object, the present inventor has found that in a room-temperature curable resin composition using, as a base polymer, an organic polymer other than organopolysiloxane (modified silicone polymer), a hydrolyzable organosilane compound that eliminates and releases a cyclic ketone compound such as cyclobutanone or cyclopentanone as a leaving group (leaving compound) represented by the following general formula (1) and / or its partial hydrolysis condensate as a curing agent (crosslinking agent) solves the problems of harmfulness and safety to the above-mentioned human body and environment. Furthermore, it has been found that even when an organic compound containing titanium, guanidine, etc. is added as a curing catalyst to this composition, it exhibits curability and cured product performance equivalent to those when a tin catalyst is added, and thus the present invention has been completed.

Chemical Formula

[0010] In other words, the present invention provides the following room-temperature curable resin compositions, and various articles (automotive parts, automotive oil seals, electrical and electronic components, building structures, civil engineering structures, adhesives, sealants, potting agents, coating agents, etc.) having the composition or its cured product. [1] (A) Organic polymers other than organopolysiloxanes, in which the molecular chain ends are sealed with hydrolyzable silyl groups and / or hydroxysilyl groups: 100 parts by mass, (B) Hydrolyzable organosilane compounds represented by the following general formula (1) and / or partially hydrolyzed condensates thereof: 1 to 40 parts by mass 、 [ka] (In the formula, R 1 (where n is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer from 1 to 8, and m is 3 or 4.) (C) Curing catalyst: 0.01~10 parts by mass A room-temperature curable resin composition containing [the specified ingredient]. [2] The room-temperature curable resin composition according to [1], wherein the hydrolyzable organosilane compound of component (B) and / or a partially hydrolyzed condensate thereof eliminates a cyclic ketone compound by hydrolysis. [3] The room-temperature curable resin composition according to [2], wherein the cyclic ketone compound to be eliminated is cyclobutanone or cyclopentanone. [4] (A) A room-temperature curable resin composition according to any one of [1] to [3], wherein the number-average molecular weight of the organic polymer of component (A) is 2,000 to 50,000. [ 5 ] (C) The curing catalyst is at least one selected from tin catalysts, titanium catalysts, organic strong base catalysts, and organic bismuth catalysts. 1 The room-temperature curable resin composition described in [ ]. [6 ] It does not contain a tin catalyst. [1] ~ [ 5 A room-temperature curable resin composition as described in any of the following: [ 7 ] Furthermore, (D) contains 0.01 to 5 parts by mass of a silane coupling agent and / or a partially hydrolyzed condensate thereof represented by the following general formula (2) per 100 parts by mass of component (A) [1] to [ 6 A room-temperature curable resin composition as described in any of the following: R 2 R 3 a SiX 3-a (2) (In the formula, R 2 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms and having at least one functional group (excluding the guanidyl group) containing one or more heteroatoms selected from nitrogen, sulfur, and oxygen atoms. 3 (where a is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and X is a hydrolyzable group; a is 0, 1, or 2.) [ 8 ] Furthermore, (E) inorganic filler is contained in an amount of 1 to 500 parts by mass per 100 parts by mass of component (A) [1] to [ 7 A room-temperature curable resin composition as described in any of the following: [ 9 ] (E) Component is one or more inorganic fillers selected from calcium carbonate, aerosolized silica, precipitated silica, carbon black, and aluminum oxide. 8 The room-temperature curable resin composition described in [ ]. [ 10 ] [1] ~ [ 9 Automotive parts having a cured product of a room-temperature curable resin composition as described in any of the following. [ 11 ] [1] ~ [ 9 An automotive oil seal having a cured product of a room-temperature curable resin composition as described in any of the following. [ 12 ] [1] ~ [9 An electrical or electronic component having a cured product of a room-temperature curable resin composition as described in any of the following. [ 13 ] [1] ~ [ 9 A building structure having a cured product of a room-temperature curable resin composition as described in any of the following. [ 14 ] [1] ~ [ 9 A civil engineering structure having a cured product of a room-temperature curable resin composition as described in any of the ]. [ 15 ] [1] ~ [ 9 An adhesive containing a room-temperature curable resin composition as described in any of the following: [ 16 ] [1] ~ [ 9 A sealing material containing a room-temperature curable resin composition as described in any of the following. [ 17 ] [1] ~ [ 9 A potting agent containing a room-temperature curable resin composition as described in any of the following: [ 18 ] [1] ~ [ 9 A coating agent containing a room-temperature curable resin composition as described in any of the following. [Effects of the Invention]

[0011] The room-temperature curable resin composition of the present invention generates compounds (eliminated compounds) from the curing agent (crosslinking agent) through hydrolysis and condensation reactions during curing, which are highly safe cyclic ketone compounds such as cyclobutanone and cyclopentanone. This provides a rubber cured product (elastomer-like cured product) with excellent curability and adhesion after curing, making it suitable for use as various adhesives, sealants, potting agents, coatings, etc., while considering human health and safety. Furthermore, even when organic compounds containing titanium, bismuth, guanidine, etc. are added as curing catalysts, the room-temperature curable resin composition of the present invention exhibits the same curability and cured product performance as when a tin catalyst is added, making it suitable for use as various adhesives, sealants, potting agents, coatings, etc., while considering environmental protection (reducing environmental impact). [Modes for carrying out the invention]

[0012] The present invention will be described in further detail below. [(A) component] Component (A) used in the present invention is an organic polymer other than an organopolysiloxane (modified silicone polymer) whose polymer main chain is sealed with hydrolyzable silyl groups and / or hydroxysilyl groups (silyl or silanol groups having a hydroxyl group bonded to a silicon atom), and acts as a base polymer in the room-temperature curable resin composition of the present invention. The modified silicone polymer of component (A) may have short-chain siloxane structures (preferably diorganosiloxane units with a repeating number of about 1 to 5) in the linking portion (linker portion) that connects the silyl group at the end of the molecular chain to the main chain.

[0013] Such base polymers can be suitably used without limiting the main chain structure, as long as the polymer main chain is an organic polymer other than an organopolysiloxane, with the molecular chain ends sealed with hydrolyzable silyl groups (e.g., alkoxysilyl groups) and / or hydroxysilyl groups (silanol groups). In particular, due to their availability, the polymer main chain is preferably a polymer structure such as polyoxyalkylenes such as polypropylene oxide, polyethylene oxide, polyisobutylene oxide, propylene oxide-ethylene oxide copolymer, polyalkylenes such as polyisobutylene, polyacrylate, or polymethacrylate. These main chain structures may also have a urethane structure (-NHC(=O)O-) or an ester structure (-C(=O)O-) in part.

[0014] (A) The molecular chain ends of component (A) are sealed with hydrolyzable silyl groups and / or hydroxysilyl groups (silanol groups). The polymer main chain is preferably an organic polymer other than an organopolysiloxane (modified silicone polymer), such as a silylated oxyalkylene polymer, a silylated urethane polymer, a silylated acrylate polymer, or a silylated alkylene polymer.

[0015] Examples of silylated oxyalkylene polymers include polymers (polyether-modified silicone polymers) in which the main chain consists of a polyoxyalkylene structure such as polypropylene oxide, polyethylene oxide, or propylene oxide-ethylene oxide copolymer, and the molecular chain ends, particularly both ends of the molecular chain, are sealed with hydrolyzable silyl groups and / or silanol groups.

[0016] Specifically, examples of silylated urethane polymers include polymers (urethane-modified silicone polymers) in which the main chain consists of a polyoxyalkylene structure such as polypropylene oxide, polyethylene oxide, or propylene oxide-ethylene oxide copolymer, has a urethane bond structure (-NHC(=O)O-) with an isocyanate as part of the main chain structure, and has a structure in which the molecular chain ends, particularly both ends of the molecular chain, are sealed with hydrolyzable silyl groups and / or silanol groups.

[0017] Examples of the silylated acrylate polymer include polymers (acrylate-modified silicone polymers) in which the main chain has a structure such as polyacrylate or polymethacrylate and the molecular chain ends, particularly both ends of the molecular chain, are blocked with a hydrolyzable silyl group and / or a silanol group.

[0018] Examples of the silylated alkylene polymer include polymers (alkylene-modified silicone polymers) in which the main chain has a polyalkylene structure such as a polymer of an isobutylene monomer and the molecular chain ends, particularly both ends of the molecular chain, are blocked with a hydrolyzable silyl group and / or a silanol group.

[0019] Among these, from the viewpoint of easy availability, silylated oxypropylene polymers having a polypropylene oxide blocked at both ends of the molecular chain with a hydrolyzable silyl group and / or a silanol group and silylated acrylate polymers having a polyacrylate blocked at both ends of the molecular chain with a hydrolyzable silyl group and / or a silanol group are preferred. In addition, since polymers having a molecular chain end blocked with a silanol group are preferred from the viewpoints of fast curing property and deep curing property, particularly, silylated oxypropylene polymers having a polypropylene oxide blocked at both ends of the molecular chain with a silanol group are preferred.

[0020] As the organic polymer of component (A), an organic polymer represented by the following general formula (3) or (4) and blocked at both ends of the molecular chain with a hydrolyzable silyl group or a hydroxysilyl group (a silyl group or a silanol group having a hydroxyl group bonded to a silicon atom) is more preferred. [Chemical formula] (In the formula, R 4 and R 6 may be the same or different and are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R 5Each of these is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Each of these is independently an integer of 2 or more, each of the bonded silicon atoms is independently 0, 1, or 2, and each of these is independently an integer from 1 to 5. Y is a divalent organic group that does not contain a siloxane structure.

[0021] In the above equations (3) and (4), R 4 and R 6 R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. 5 R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or a hydrogen atom. 4 , R 5 , R 6 Examples of unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, and octyl groups; cycloalkyl groups such as cyclopentyl and cyclohexyl groups; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, and hexenyl groups; aryl groups such as phenyl, tolyl, xylyl, and α-,β-naphthyl groups; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl groups; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl, and Br, or cyano groups, such as 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl groups. 4 and R 6 As for the group, a methyl group and a phenyl group are preferred, and a methyl group is particularly preferred. 5 As for these, methyl groups, ethyl groups, and hydrogen atoms are preferred, and methyl groups and hydrogen atoms are particularly preferred. 4 , R 5 , R 6 These may be the same group or different groups.

[0022] Furthermore, in formulas (3) and (4), b is an integer of 2 or more, preferably an integer between 2 and 8, more preferably 2, 3, or 4, and particularly preferably 3. In formula (3), c is independently 0, 1, or 2 for each silicon atom to which it is bonded, preferably 0 or 1, and particularly preferably 1. In equation (4), d is an independent integer between 1 and 5, preferably between 1 and 4.

[0023] In the above general formulas (3) and (4), Y is a divalent organic group that does not contain a siloxane structure. Specifically, this includes polyoxyalkylene groups such as polyoxyethylene groups, polyoxypropylene groups, and polyoxybutylene groups, polyalkylene groups such as polyisobutylene groups, polymers of methyl methacrylate represented by the following formula, or a polymer in which one or more of alkylene groups, ether-bonded oxygen atoms, amide bonds, urethane bonds, carbonyl bonds, ester bonds, etc. are interposed on these groups. [ka] (In the formula, R' is a hydrogen atom or a methyl group, R'' is a C1-C10 alkyl group such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, or hexyl group, and z indicates the degree of polymerization of the repeating unit constituting the main chain, and is an integer from 20 to 800.)

[0024] Specific examples of the organic polymer of component (A) include the following structures. [ka] [ka] [ka] [ka] [ka] (In the formula, z represents the degree of polymerization of the repeating units constituting the main chain, and is an integer between 20 and 800. Me represents a methyl group.)

[0025] In each of the above example formulas, the methoxy group (MeO-) at the end of the molecular chain may be substituted with other lower alkoxy groups such as an ethoxy group, and the hydroxydimethylsilyl group (-SiMe2OH) at the end of the molecular chain may be substituted with a terminally hydroxydimethylsilyl-bound polydimethylsiloxanyl group (-[Si(Me)2O] d It may also be a substitution of -H (where d is an integer between 1 and 5).

[0026] The number-average molecular weight of the organic polymer in component (A) is preferably 2,000 to 50,000, more preferably 5,000 to 40,000, and even more preferably 10,000 to 35,000. If the number-average molecular weight is too small, the rubber properties such as elongation and strength of the resulting cured product may deteriorate, and if it is too large, the viscosity of the composition may increase rapidly, which may be disadvantageous in terms of handling. In this invention, the molecular weight (or degree of polymerization) can be determined, for example, by using tetrahydrofuran (THF), toluene, etc., as the developing solvent, and calculating the number-average molecular weight (or number-average degree of polymerization) or weight-average molecular weight (or weight-average degree of polymerization) in terms of polystyrene in gel permeation chromatography (GPC) analysis (the same applies hereinafter).

[0027] These polymers, in which the molecular chain ends are sealed with hydrolyzable silyl groups and / or hydroxysilyl groups (silanol groups), can be obtained by known methods, such as those described in Japanese Patent Publication No. 6565787 (Patent Document 3). Specifically, a method for producing a silylated oxypropylene polymer having polypropylene oxide as the main chain, in which both molecular chain ends are sealed with silanol groups, involves hydrosilylation of an organosilicon compound, such as an organosilane or organosiloxane oligomer having a silanol group (SiOH group) and a hydrosilyl group (SiH group), with a platinum catalyst in a polyoxyalkylene polymer, such as a polyoxypropylene polymer, in which the molecular chain ends are sealed with alkenyl groups having a CH2=CH- structure such as an allyl group. Another method of production involves hydrosilylation of an organosilicon compound, such as an organosilane or organosiloxane oligomer having chlorosilyl groups (SiCl groups) and hydrosilyl groups (SiH groups), onto a polyoxyalkylene polymer, such as a polyoxypropylene polymer, whose molecular chain ends are sealed with alkenyl groups having a CH2=CH- structure such as an allyl group, in the presence of a platinum catalyst, followed by hydrolysis of the chlorosilyl groups to silanols (SiOH).

[0028] Furthermore, for the organic polymer (modified silicone polymer) whose polymer main chain is not an organopolysiloxane, and in which the molecular chain ends of component (A) are sealed with hydrolyzable silyl groups and / or silanol groups, commercially available products may be used. For example, as a polyether-modified silicone polymer, Kaneka Corporation's "MS Polymer" or Wacker GmbH's "GENIOSIL (STP-E)" may be used, and as a urethane-modified silicone polymer, Wacker GmbH's "GENIOSIL (SPUR / STP-U)" may be used.

[0029] (A) Organic polymers in which the molecular chain ends of component (A) are sealed with hydrolyzable silyl groups and / or silanol groups can be used alone or in combination of two or more polymers with different structures and degrees of polymerization as needed.

[0030] [(B) Component: Hydrolyzable organosilane compound and / or partially hydrolyzed condensate thereof] The component (B) used in the room-temperature curable resin composition of the present invention is a hydrolyzable organosilane compound represented by the following general formula (1) and / or a partially hydrolyzed condensate thereof, which is used as a crosslinking agent (curing agent) and is characterized by releasing cyclic ketone compounds such as cyclobutanone and cyclopentanone as leaving groups (leaving substances) upon hydrolysis. In this invention, "partially hydrolyzed condensate" means an organosiloxane oligomer having three or more, preferably four or more, residual hydrolyzable groups in the molecule, which is produced by partially hydrolyzing and condensing the hydrolyzable organosilane compound. [ka] (In the formula, R 1 (where n is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer from 1 to 8, and m is 3 or 4.)

[0031] In the above general formula (1), R 1 R is a monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. 1 Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, and decyl groups; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, and hexenyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenylethyl groups. Among these, methyl, ethyl, vinyl, and phenyl groups are preferred, and methyl, vinyl, and phenyl groups are particularly preferred.

[0032] In the above general formula (1), n ​​is an integer from 1 to 8, preferably an integer from 2 to 6, more preferably an integer from 2 to 4, and even more preferably 2 or 3. When n is 0, a cyclic structure is not formed. When n is an integer of 9 or more, the molecular weight of the hydrolyzable organosilane increases, making purification by distillation difficult, increasing the amount of additive required to ensure shelf life, and resulting in cost disadvantages.

[0033] Furthermore, as mentioned above, m is either 3 or 4. If this number is less than 3 (i.e., m is 0, 1, or 2), rubber curing by crosslinking reaction does not occur, and the compound is unsuitable as a crosslinking agent for room-temperature curable resin compositions.

[0034] Furthermore, the leaving group (leaving compound) produced by the hydrolysis of the hydrolyzable organosilane compound represented by the general formula (1) above is a cyclic ketone compound such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, or cyclodecanone, preferably cyclobutanone or cyclopentanone, and more preferably cyclopentanone. There are no reported cases of health hazards such as carcinogenicity or reproductive toxicity to humans, or environmental hazards such as aquatic toxicity, for cyclobutanone or cyclopentanone. In addition, cyclopentanone is industrially mass-produced, readily available, and highly cost-competitive, making it advantageous for the production of the hydrolyzable organosilane compound of component (B), as will be described later.

[0035] The hydrolyzable organosilane compound of component (B) can be produced, for example, by reacting a chlorosilane compound corresponding to the hydrolyzable organosilane compound represented by general formula (1) with a cyclic ketone compound in the presence of a catalyst and a basic substance (e.g., a dehydrochlorination reaction). This reaction is represented, for example, by the following formula [1]. [ka] (In the formula, R 1 n and m are as described above.

[0036] Examples of chlorosilane compounds are listed below. Note that Me represents a methyl group. [ka]

[0037] Examples of cyclic ketone compounds include those listed below. [ka]

[0038] The amount of cyclic ketone compound added to react with the chlorosilane compound is preferably 0.95 to 3.0 moles, more preferably 0.99 to 2.5 moles, and even more preferably 1.0 to 2.0 moles, per mole of chlorine atoms in the chlorosilane compound. If the amount of cyclic ketone compound added is too small, the reaction may not complete, and if the amount added is too large, the purification process may take longer, increasing the manufacturing time.

[0039] Examples of catalysts used in the reaction include monovalent or divalent metallic copper compounds, such as copper chloride, copper bromide, copper iodide, copper sulfate, copper nitrate, copper carbonate, basic copper carbonate, copper formate, copper acetate, and copper butyrate, but are not limited to these. The amount of catalyst (metallic copper compound) to be added is preferably 0.001 to 0.5 moles, more preferably 0.002 to 0.2 moles, and even more preferably 0.003 to 0.1 moles per mole of chlorosilane compound. If the amount of catalyst added is too small, the reaction may not terminate, and if the amount of catalyst added is too large, it will be cost-ineffective.

[0040] As basic substances used in the reaction, low nucleophilic basic substances such as trimethylamine, triethylamine, tripropylamine, tributylamine, urea, diazabicycloundecene, and diazabicyclononene can be used. Among these, trimethylamine, triethylamine, and tributylamine are preferred, and triethylamine is particularly preferred. The amount of basic substance to be added is preferably 0.95 to 2.5 moles, more preferably 0.99 to 2.0 moles, and even more preferably 1.0 to 1.5 moles, per mole of chlorine atoms in the chlorosilane compound. If the amount of basic substance added is too small, the reaction may not terminate, and if the amount of basic substance added is too large, it is economically disadvantageous.

[0041] For the production of the hydrolyzable organosilane compound of component (B), commonly used solvents may be used. Examples of solvents include aromatic hydrocarbons such as toluene, xylene, and benzene; aliphatic hydrocarbons such as pentane, hexane, heptane, nonane, octane, and decane; ethers such as dimethyl ether, methyl ethyl ether, tetrahydrofuran, and dioxane; halogenated hydrocarbons such as perchloroethane, perchloroethylene, trichloroethane, chloroform, and carbon tetrachloride; amides such as dimethylformamide; and organic solvents such as ethyl acetate, methyl acetate, and butyl acetate. The amount of solvent used is not particularly limited, but is typically in the range of 10 to 500 parts by mass, preferably 30 to 400 parts by mass, and more preferably 50 to 300 parts by mass, per 100 parts by mass of the cyclic ketone compound used.

[0042] The reaction conditions for a chlorosilane compound and a cyclic ketone compound are typically such that the chlorosilane compound is added dropwise to the cyclic ketone compound at a temperature of 0 to 120°C, preferably 0 to 100°C, and the reaction is carried out at 50 to 120°C, preferably 60 to 100°C, for 1 to 48 hours, and more preferably 3 to 30 hours. If the reaction temperature is too low, the reaction may not be completed, and if the reaction temperature is too high, the product may become too discolored. Also, if the reaction time is too short, the reaction may not be completed, and if the reaction time is too long, it will negatively impact productivity. Furthermore, purification after the reaction can be performed by distilling the target product under reduced pressure, preferably at a pressure of 1 × 10⁻⁶. -5 ~3,000 Pa, u-u-1 × 10 -5The pressure is approximately 2,000 Pa, and the purification temperature is preferably 100-250°C, more preferably 120-230°C. If the pressure (degree of reduced pressure) is too high, distillation may become difficult. Also, if the purification temperature is too low, distillation may become difficult, and if it is too high, it may lead to discoloration or decomposition of the reactants.

[0043] Specific examples of hydrolyzable organosilane compounds of component (B) include those represented by the following formula, where Me represents a methyl group. [ka]

[0044] (B) Component may be used alone or in combination of two or more components. The amount of component (B) is 1 to 40 parts by mass, preferably 3 to 30 parts by mass, and more preferably 5 to 20 parts by mass, per 100 parts by mass of component (A). If the amount of component (B) is less than the lower limit of 1 part by mass, the shelf life when stored in a sealed container may deteriorate. Furthermore, if the amount of component (B) exceeds the upper limit of 40 parts by mass, the curability of the room-temperature curable resin composition may decrease significantly, and the adhesiveness may also deteriorate. Furthermore, the hydrolyzable organosilane compound of component (B) and / or its partially hydrolyzed condensate are clearly distinguishable from the silane coupling agent of component (D), which is described later as an optional component, in that they do not contain a monovalent hydrocarbon group in their molecule that has at least one functional group containing one or more atoms selected from nitrogen, sulfur, and oxygen atoms.

[0045] [(C) component curing catalyst] The room-temperature curable resin composition of the present invention may optionally contain a curing catalyst of component (C) as an optional component. As the curing catalyst of component (C), a metal-based or non-metal-based condensation catalyst that has been commonly used as a curing accelerator for room-temperature curable resin compositions can be used. Examples include organotin compounds (tin catalysts) such as dibutyltin methoxide, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dioctate, dimethyltin dimethyltin diacetate, and other organotin compounds (titanium catalysts) such as tetrapropyl titanate, tetrabutyl titanate, tetra-2-ethylhexyl titanate, dimethoxytitanium diacetylacetonate, and titanium diisopropoxybis(ethylacetoacetate), as well as amine compounds such as triethylamine, hexylamine, tetramethylguanidine, and γ-tetramethylguanidylpropyltrimethoxysilane, and their salts (organic strong base catalysts), and organobismuth compounds such as bismastris (2-ethylhexanoate) and bismastris (neodecanoate), and mixtures thereof (organobismuth catalysts). At least one of these, i.e., one type alone or two or more types in combination, can be used. Furthermore, in this invention, regardless of whether a titanium catalyst, organic strong base catalyst, or organic bismuth catalyst is used, the curing properties and cured product performance are equivalent to those when a tin catalyst is used. Therefore, from an environmental protection standpoint, it is preferable to use a titanium catalyst, organic strong base catalyst, or organic bismuth catalyst without using a tin catalyst.

[0046] (C) When component (C) is included, the amount included is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of component (A). If the amount of component (E) is less than the lower limit of 0.01 parts by mass, the catalytic effect may not be obtained, and if it exceeds the upper limit of 10 parts by mass, the storage stability of the composition may be poor.

[0047] [(D) Component: Silane coupling agent and / or partially hydrolyzed condensate thereof] The room-temperature curable resin composition of the present invention may optionally contain a silane coupling agent of component (D) and / or a partially hydrolyzed condensate thereof as an optional component. Component (D) is a silane coupling agent represented by the following general formula (2) (i.e., a hydrolyzable organosilane compound or carbon functional silane having a functional group-containing monovalent hydrocarbon group) and / or a partially hydrolyzed condensate thereof, and is a component for exhibiting good adhesion to the cured product of the room-temperature curable resin composition of the present invention. R 2 R 3 a SiX 3-a (2) (In the formula, R 2 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms and having at least one functional group (excluding the guanidyl group) containing one or more heteroatoms selected from nitrogen, sulfur, and oxygen atoms. 3 (where a is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and X is a hydrolyzable group; a is 0, 1, or 2.)

[0048] In equation (2) above, R 2 This refers to a monovalent hydrocarbon group having 1 to 20 carbon atoms that has at least one functional group containing one or more heteroatoms selected from nitrogen, sulfur, and oxygen atoms (for example, an unsubstituted or substituted amino group, an unsubstituted or substituted imino group, an amide group, a ureido group, a mercapto group, an epoxy group, a (meth)acryloxy group, etc., but excluding the guanidyl group). Specifically, this includes β-(2,3-epoxycyclohexyl)ethyl group, β-(3,4-epoxycyclohexyl)ethyl group, γ-glycidoxypropyl group, γ-methacrylate Examples include monovalent hydrocarbon groups having 3 to 20 carbon atoms, more preferably 3 to 14 carbon atoms, which contain at least one heteroatom selected from nitrogen atoms, sulfur atoms, and oxygen atoms, such as oxypropyl group, γ-acryloxypropyl group, N-β-(aminoethyl)-γ-aminopropyl group [also known as: N-2-(aminoethyl)-3-aminopropyl group], γ-aminopropyl group, N-phenyl-γ-aminopropyl group, γ-ureidopropyl group, γ-mercaptopropyl group, and γ-isocyanatetopropyl group. 2Of these, γ-glycidoxypropyl group, γ-aminopropyl group, and N-β-(aminoethyl)-γ-aminopropyl group are particularly preferred.

[0049] Also, in equation (2) above, R 3 This refers to an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, and decyl groups, cycloalkyl groups such as cyclohexyl groups, alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, and hexenyl groups, aryl groups such as phenyl and tolyl groups, and aralkyl groups such as benzyl and phenylethyl groups. Alternatively, these hydrocarbon groups may be partially substituted with halogen atoms such as chlorine, fluorine, or bromine, such as trifluoropropyl groups. Among these, methyl, ethyl, propyl, and isopropyl groups are preferred. 3 These may be the same group or different groups.

[0050] In formula (2) above, examples of the hydrolyzable group X include ketoxime groups, alkoxy groups, alkoxyalkoxy groups, acyloxy groups, alkenyloxy groups, etc. Specifically, examples include ketoxime groups having 3 to 8 carbon atoms such as dimethylketoxime group, diethylketoxime group, methylethylketoxime group, and methylisobutylketoxime group; alkoxy groups having 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms, such as methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group; alkoxyalkoxy groups having 2 to 4 carbon atoms such as methoxymethoxy group and methoxyethoxy group; acyloxy groups having 2 to 4 carbon atoms such as acetoxy group and propionoxy group; and alkenyloxy groups having 2 to 4 carbon atoms such as vinyloxy group, allyloxy group, propenoxy group, and isopropenoxy group. X is preferably a methoxy group. Note that the hydrolyzable group X may be the same group or different groups.

[0051] Component (D) is a silane coupling agent represented by formula (2). Specifically, examples include aminosilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and 3-2-(aminoethylamino)propyltrimethoxysilane [also known as N-2-(aminoethyl)-3-aminopropyltrimethoxysilane], epoxysilanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (meth)acryloxypropyltrimethoxysilanes such as γ-(meth)acryloxypropyltrimethoxysilane and γ-(meth)acryloxypropyltriethoxysilane, mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, and isocyanatesilanes such as γ-isocyanatepropyltrimethoxysilane.

[0052] The silane coupling agent and / or its partially hydrolyzed condensate of component (D) may be used alone or in combination of two or more.

[0053] When component (D) is added, the amount added is preferably 0.01 to 5 parts by mass, and more preferably 0.1 to 3 parts by mass, per 100 parts by mass of component (A). If it is less than 0.01 parts by mass, the cured product may not exhibit sufficient adhesive performance, and if it is added in excess of 5 parts by mass, the rubber strength after curing may decrease or the curability may decrease.

[0054] [(E) Component: Inorganic filler] The room-temperature curable resin composition of the present invention may optionally contain an inorganic filler of component (E) as an optional component. The inorganic filler of component (E) is a reinforcing or non-reinforcing filler for imparting rubber properties to the room-temperature curable resin composition of the present invention. Examples of the inorganic filler of component (E) include dry silica such as calcined silica, fused silica, crushed silica, and fumed silica, wet silica such as precipitated silica and sol-gel silica, crystalline silica (fine powdered quartz), diatomaceous earth, carbon black, talc, bentonite, calcium carbonate, zinc carbonate, magnesium carbonate, calcium oxide, zinc oxide, magnesium oxide, aluminum oxide, aluminum hydroxide, etc. Among these, calcium carbonate, fumed silica, precipitated silica, carbon black, and aluminum oxide are preferred, and more preferably, calcium carbonate, fumed silica, precipitated silica, carbon black, and aluminum oxide have been hydrophobically treated on their surfaces. In this case, it is preferable that these inorganic fillers have a low moisture content. There are no particular restrictions on the type, quantity, or method of the surface treatment agent (hydrophobic treatment agent), but typically, organosilicon compounds such as chlorosilanes, alkoxysilanes, and organosilazanes, as well as fatty acids, paraffins, silane coupling agents, and titanium coupling agents can be used. The inorganic filler of component (E) may be used alone or in combination of two or more types.

[0055] When component (E) is included, the amount included is preferably 1 to 500 parts by mass, more preferably 20 to 500 parts by mass, even more preferably 20 to 300 parts by mass, and particularly preferably 50 to 300 parts by mass, per 100 parts by mass of component (A). If the amount is less than 1 part by mass, sufficient rubber strength cannot be obtained, which may result in problems as the product is unsuitable for the intended use. If the amount exceeds 500 parts by mass, the dispensing performance from the cartridge deteriorates, storage stability decreases, and the mechanical properties of the resulting rubber may also decrease.

[0056] [Other ingredients] Furthermore, the room-temperature curable resin composition of the present invention may also contain generally known additives other than those listed above, as long as they do not impair the objectives of the present invention. Among the additives, plasticizers include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), tetrahydrophthalates, and dioctyl adipate. Chil (DOA), Diisononyl adipate (DINA), Diisodecyl adipate (DIDA), Di-n-alkyl adipate, Dibutyl diglycol adipate (BXA), Bis(2-ethylhexyl) azelaate (DOZ), Dibutyl sebacate (DBS), Dioctyl sebacate (DOS), Dibutyl maleate (DBM), Di-2-ethylhexyl maleate (DOM), Dibutyl fumarate (DBF), Tricresyl phosphate (TCP), Examples include triethyl phosphate (TEP), tributyl phosphate (TBP), tris(2-ethylhexyl) phosphate (TOP), tri(chloroethyl) phosphate (TCEP), trisdichloropropyl phosphate (CPP), tributoxyethyl phosphate (TBXP), tris(β-chloropropyl) phosphate (TMCPP), triphenyl phosphate (TPP), octyldiphenyl phosphate (ODP), acetyltriethyl citrate, tributyl acetylcitrate, etc. Other examples include trimellitic acid-based plasticizers, polyester-based plasticizers, chlorinated paraffins, stearic acid-based plasticizers, as well as silicone oils such as dimethylpolysiloxane (non-functional organopolysiloxanes), and more recently, petroleum-based high-boiling point solvents such as polyoxypropylene glycol-based, acrylic resin-based, acrylic polymer-based, paraffin-based, naphthenic, and high-boiling point isoparaffin-based. If necessary, colorants such as pigments, dyes, and fluorescent whitening agents, physiologically active additives such as antifungal agents, antibacterial agents, and marine organism repellents, surface modifiers such as organic liquids like phenyl silicone oil and fluorosilicone oil as bleed oils, and solvents such as solvent volatile oils and low-boiling point isoparaffins can also be added.

[0057] The room-temperature curable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components, and furthermore, predetermined amounts of the above-mentioned additives, in a dry atmosphere. Furthermore, the room-temperature curable resin composition of the present invention hardens by being left at room temperature, but the molding method, curing conditions, etc., can be those of known methods and conditions depending on the type of composition.

[0058] The room-temperature curable resin composition of the present invention, particularly the one-component composition, is stored in the absence of moisture, i.e., in a sealed container that blocks moisture, and readily hardens at room temperature (23°C ± 15°C) when exposed to moisture in the air at the time of use.

[0059] The room-temperature curable resin composition of the present invention generates compounds from the crosslinking agent through hydrolysis during curing that are highly safe cyclic ketone compounds such as cyclopentanone, thus being considerate of human health and the environment. Furthermore, cyclopentanone has a flash point of 35°C, which is higher than that of de-alcoholized resins that release alcohol compounds such as methanol during curing, making it highly safe. The room-temperature curable resin composition of the present invention exhibits good curability when using various existing catalysts, and the cured product also has excellent adhesive properties. Moreover, by using catalysts other than tin, it is possible to provide a composition that is even more environmentally friendly.

[0060] Therefore, the room-temperature curable resin composition of the present invention is useful as an adhesive, sealant, potting agent, or coating agent. The method for using the room-temperature curable resin composition of the present invention as an adhesive, sealant, potting agent, or coating agent can be carried out according to conventionally known methods.

[0061] Examples of items covered include automotive parts, automotive oil seals, electrical and electronic components, building structures, and civil engineering structures. [Examples]

[0062] The present invention will be described in more detail below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples. Viscosity is measured using a rotational viscometer at 23°C according to the method specified in JIS Z 8803. Molecular weight is measured as the number-average molecular weight in polystyrene equivalent in GPC analysis using tetrahydrofuran as the developing solvent. Me represents a methyl group. In all examples and comparative examples, a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) was used as the appropriate mixer. Furthermore, in the examples below, unless otherwise specified, physical properties such as viscosity (measured using a rotational viscometer) are shown at 23°C.

[0063] [Synthesis Example 1] <Synthesis of polyoxypropylene containing silanol groups at both ends of the molecular chain> In a 1 L four-necked separable flask equipped with a stirrer, reflux condenser, thermometer, and dropping funnel, 600 g of polyoxypropylene with a number average molecular weight of 23,000 and allyl groups sealed at both ends of the molecular chain (0.058 moles in terms of functional groups of terminal allyl groups), and 2.4 g of platinum catalyst (toluene solution of Karlsted catalyst; platinum concentration 1% by mass) were placed, and the temperature was raised to 90°C while heating and stirring. Next, under stirring, 19.6 g of 1-hydroxy-octamethyltetrasiloxane (i.e., 1-hydroxy-7-hydrogen-1,1,3,3,5,5,7,7-octamethyltetrasiloxane) (with a functional group content of 0.066 moles at the terminal Si-H) was added dropwise, and the reaction system was maintained at a reaction temperature of 90-95°C for 6 hours. After the reaction was complete, it was cooled to room temperature, and a polyoxyalkylene compound containing silanol groups at both ends of the molecular chain (a polyoxyalkylene compound in which both ends of the molecular chain are sealed with -(CH2)3-[Si(Me)2O]4-H and the main chain is polyoxypropylene (in formula (4) above, R 4 =methyl group, R 5 (=hydrogen atom, b=3, d=4, Y=polyoxypropylene group) 570g was obtained (yield 92%, viscosity 24,000 mPa·s, number average molecular weight: 24,000).

[0064] [Synthesis Example 2] <Synthesis of hydrolyzable organosilane compound 1> In a 5,000 mL four-neck separable flask equipped with a mechanical stirrer, thermometer, reflux tubing, and dropping funnel, 834 g (9.9 mol) of cyclopentanone, 825 g (8.2 mol) of triethylamine (TEA), 5 g (0.05 mol) of copper(I) chloride, and 1,500 ml of hexane were charged. 400 g (2.47 mol) of vinyltrichlorosilane was added dropwise over approximately 2 hours at a temperature of 40-60°C. After stirring at 80°C for 12 hours, the resulting triethylamine hydrochloride was removed by filtration. Hexane was then removed from the filtrate at 100°C and atmospheric pressure, and the mixture was distilled at 180°C and 300 Pa to obtain hydrolyzable organosilane compound 1 (yield 532 g, yield 69%). The reaction equation is shown in the following formula [2]. [ka]

[0065] [Synthesis Example 3] <Synthesis of hydrolyzable organosilane compound 2> In a 5,000 mL four-neck separable flask equipped with a mechanical stirrer, thermometer, reflux tubing, and dropping funnel, 834 g (9.9 mol) of cyclopentanone, 825 g (8.2 mol) of triethylamine (TEA), 5 g (0.05 mol) of copper(I) chloride, and 1,500 ml of hexane were charged. 368 g (2.47 mol) of methyltrichlorosilane was added dropwise over approximately 2 hours at a temperature of 40-60°C. After stirring at 80°C for 12 hours, the resulting triethylamine hydrochloride was removed by filtration. Hexane was then removed from the filtrate at 100°C and atmospheric pressure, and the mixture was distilled at 170°C and 300 Pa to obtain hydrolyzable organosilane compound 2 (yield 519 g, 71%). The reaction equation is shown in the following formula [3]. [ka]

[0066] [Example 1] (A-1) 100 parts by mass of polyoxypropylene containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 was mixed thoroughly with (E) 10 parts by mass of fumes of silica (product name: MU-215, manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface was treated with dimethyldichlorosilane, and (B-1) 8 parts by mass of the hydrolyzable organosilane compound 1 was added and mixed thoroughly. Finally, (D-1) 1 part by mass of γ-aminopropyltrimethoxysilane (product name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) and (C-1) 0.1 parts by mass of dioctyl tin dilaurate were added and mixed completely under reduced pressure to obtain composition 1.

[0067] [Example 2] (A-1) 100 parts by mass of polyoxypropylene containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 was mixed thoroughly with (E) 10 parts by mass of fuzzy silica (product name: MU-215, manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface was treated with dimethyldichlorosilane, and (B-1) 8 parts by mass of the hydrolyzable organosilane compound 1 was added and mixed thoroughly. Finally, (D-2) 1 part by mass of γ-glycidoxypropyltrimethoxysilane (product name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) and (C-2) 4 parts by mass of titanium diisopropoxybis(ethylacetoacetate) (product name: Orgatics TC750, manufactured by Matsumoto Fine Chemical Co., Ltd.) were added and mixed completely under reduced pressure to obtain composition 2.

[0068] [Example 3] (A-1) 100 parts by mass of polyoxypropylene containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 was mixed thoroughly with (E) 10 parts by mass of fuzzy silica (product name: MU-215, manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface was treated with dimethyldichlorosilane, and (B-1) 8 parts by mass of the hydrolyzable organosilane compound 1 was added and mixed thoroughly. Finally, (D-3) 1 part by mass of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (product name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) and (C-3) 0.6 parts by mass of γ-tetramethylguanidylpropyltrimethoxysilane were added and mixed completely under reduced pressure to obtain composition 3.

[0069] [Example 4] (A-1) 100 parts by mass of polyoxypropylene containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 was mixed thoroughly with (E) 10 parts by mass of fuzzy silica (product name: MU-215, manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface was treated with dimethyldichlorosilane, and (B-1) 8 parts by mass of the hydrolyzable organosilane compound 1 was added and mixed thoroughly. Finally, (D-1) 1 part by mass of γ-aminopropyltrimethoxysilane (product name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) and (C-4) 1 part by mass of an organic bismuth catalyst mainly composed of bismastris (2-ethylhexanoate) (product name: Neostan U-600, manufactured by Nitto Chemical Co., Ltd.) were added and mixed completely under reduced pressure to obtain composition 4.

[0070] [Example 5] (A-1) 100 parts by mass of polyoxypropylene containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 was mixed thoroughly with (E) 10 parts by mass of fuzzy silica (product name: MU-215, manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface was treated with dimethyldichlorosilane, and (B-2) 8 parts by mass of the hydrolyzable organosilane compound 2 was added and mixed thoroughly. Finally, (D-1) 1 part by mass of γ-aminopropyltrimethoxysilane (product name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) and (C-3) 0.6 parts by mass of γ-tetramethylguanidylpropyltrimethoxysilane were added and mixed completely under reduced pressure to obtain composition 5.

[0071] [Example 6] (A-2) Kaneka MS Polymer S303H (polyoxypropylene with dimethoxy(methyl)silylpropyl groups sealed at both ends of the molecular chain (in the above general formula (3), R 4 =R 6 =methyl group, R 5(b=3, c=2, Y=polyoxypropylene group), manufactured by Kaneka Corporation, number average molecular weight: 17,500) 100 parts by mass of (E) fumesine silica whose surface has been treated with dimethyldichlorosilane (product name: MU-215, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and thoroughly mixed, then 8 parts by mass of (B-2) the hydrolyzable organosilane compound 2 was added and thoroughly mixed. Finally, 1 part by mass of (D-2) γ-glycidoxypropyltrimethoxysilane (product name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.6 parts by mass of (C-3) γ-tetramethylguanidylpropyltrimethoxysilane were added and thoroughly mixed under reduced pressure to obtain composition 6.

[0072] [Comparative Example 1] (A-1) 100 parts by mass of polyoxypropylene containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 was mixed thoroughly with (E) 10 parts by mass of fumes of silica (product name: MU-215, manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface was treated with dimethyldichlorosilane, and (B') 8 parts by mass of methyltrimethoxysilane was added and mixed thoroughly. Finally, (D-1) 1 part by mass of γ-aminopropyltrimethoxysilane (product name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) and (C-1) 0.1 parts by mass of dioctyl tin dilaurate were added and mixed completely under reduced pressure to obtain composition 7.

[0073] [Comparative Example 2] (A-1) 100 parts by mass of polyoxypropylene containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 was mixed thoroughly with (E) 10 parts by mass of fuzzy silica (product name: MU-215, manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface was treated with dimethyldichlorosilane, and (B') 8 parts by mass of methyltrimethoxysilane was added and mixed thoroughly. Finally, (D-1) 1 part by mass of γ-aminopropyltrimethoxysilane (product name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) and (C-3) 0.6 parts by mass of γ-tetramethylguanidylpropyltrimethoxysilane were added and mixed completely under reduced pressure to obtain composition 8.

[0074] [Comparative Example 3] (A-1) 100 parts by mass of polyoxypropylene containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 was mixed thoroughly with (E) 10 parts by mass of fumes of silica (product name: MU-215, manufactured by Shin-Etsu Chemical Co., Ltd.) whose surface was treated with dimethyldichlorosilane, and (B'') 8 parts by mass of vinyltris(methylethylketoxime)silane was added and mixed thoroughly. Finally, (D-3) 1 part by mass of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (product name: KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.) and (C-1) 0.1 parts by mass of dioctyl tin dilaurate were added and mixed completely under reduced pressure to obtain composition 9.

[0075] A list of the obtained compositions is shown in Table 1 below.

[0076] [Table 1]

[0077] [Test Method] The compositions 1 to 9 prepared in the above examples and comparative examples were evaluated as follows.

[0078] Tack Free Time The tack-free time (touch-dry time) was measured using compositions 1 to 9 prepared in the above examples and comparative examples, in accordance with the method specified in JIS A 5758.

[0079] Rubber properties Compositions 1 to 9 prepared in the above examples and comparative examples were each poured into molds with a depth of 2 mm and cured at 23°C and 50% RH for 7 days to obtain 2 mm thick rubber sheets. The rubber properties (Type A durometer hardness, elongation at break, and tensile strength) were measured from the 2 mm thick rubber sheets in accordance with JIS K 6249.

[0080] Shear adhesion strength and cohesive failure rate Compositions 1-9 prepared in the above examples and comparative examples were cured between two aluminum plates measuring 25 mm in width and 100 mm in length at 23°C and 50% RH for 7 days, with an adhesive area of ​​2.5 cm between each of the upper and lower aluminum plates. 2 A 1 mm thick layer of cured rubber was formed to create shear adhesion test specimens as specified in JIS K 6249. The shear adhesion strength and cohesive failure rate to aluminum were measured using each of these specimens in accordance with the method specified in JIS K 6249, and the cohesive failure rates were compared. These results, along with the compounds released during curing in compositions 1 to 9 prepared in the above examples and comparative examples, their health and environmental hazards, the flash point and boiling point of the leaving group, and the catalysts used, are shown in Table 2 below.

[0081] [Table 2] *1) Highly toxic substance, can cause organ damage *2) May cause cancer, harmful to aquatic life

[0082] In Examples 1 to 6, which used a predetermined polyoxyalkylene compound as the base polymer and a decyclic ketone crosslinking agent, all showed good rubber properties and adhesion. From the results of the examples, it was found that the compositions of the present invention can be obtained with good curability even when using various catalysts such as tin catalysts, titanium catalysts, organic strong base catalysts, and organic bismuth catalysts. In particular, in Examples 3 and 5, which used a polyoxyalkylene compound having terminal silanol groups and an organic strong base catalyst, the tack-free time was shortened and the curability was further improved. On the other hand, in the comparative examples, Comparative Examples 1 and 3, which used a tin catalyst, showed physical properties equivalent to those of the examples, but Comparative Example 2, which used an organic strong base catalyst, showed reduced curability.

[0083] Furthermore, the compound released by the composition in the example during curing is cyclopentanone, a highly safe compound with no reported health hazards such as carcinogenicity or reproductive toxicity to humans, or environmental hazards such as aquatic toxicity. On the other hand, the compounds released by the composition in the comparative example during curing all have their health hazards indicated in the SDS (Safety Data Sheet), etc., and include 2-butanone oxime, which may be carcinogenic and toxic to aquatic organisms, and methanol, which is designated as a highly toxic substance and is strongly harmful to humans. Moreover, since methanol has a lower flash point and boiling point compared to cyclopentanone, it can be seen that the room-temperature curable resin composition of the present invention is superior from the viewpoint of human health and environmental protection.

Claims

1. (A) Organic polymers other than organopolysiloxanes, in which the molecular chain ends are sealed with hydrolyzable silyl groups and / or hydroxysilyl groups: 100 parts by mass, (B) Hydrolyzable organosilane compounds represented by the following general formula (1) and / or partially hydrolyzed condensates thereof: 1 to 40 parts by mass, 【Chemistry 1】 (In the formula, R 1 (where n is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer from 1 to 8, and m is 3 or 4.) (C) Curing catalyst: 0.01 to 10 parts by mass A room-temperature curable resin composition containing [the specified ingredient].

2. The room-temperature curable resin composition according to claim 1, wherein the hydrolyzable organosilane compound and / or partially hydrolyzed condensate of component (B) removes a cyclic ketone compound by hydrolysis.

3. The room-temperature curable resin composition according to claim 2, wherein the cyclic ketone compound to be eliminated is cyclobutanone or cyclopentanone.

4. The room-temperature curable resin composition according to claim 1, wherein the number-average molecular weight of the organic polymer of component (A) is 2,000 to 50,000.

5. (C) The room-temperature curable resin composition according to claim 1, wherein the curing catalyst is at least one selected from a tin catalyst, a titanium catalyst, an organic strong base catalyst, and an organic bismuth catalyst.

6. The room-temperature curable resin composition according to claim 1, which does not contain a tin catalyst.

7. Furthermore, the room-temperature curable resin composition according to claim 1, wherein (D) contains 0.01 to 5 parts by mass of a silane coupling agent and / or a partially hydrolyzed condensate thereof represented by the following general formula (2) per 100 parts by mass of component (A). R 2 R 3 a SiX 3-a (2) (In the formula, R 2 R is a monovalent hydrocarbon group having 1 to 20 carbon atoms and having at least one functional group (excluding the guanidyl group) containing one or more heteroatoms selected from nitrogen, sulfur, and oxygen atoms. 3 (where a is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and X is a hydrolyzable group; a is 0, 1, or 2.)

8. Furthermore, the room-temperature curable resin composition according to claim 1, wherein (E) an inorganic filler is contained in an amount of 1 to 500 parts by mass per 100 parts by mass of component (A).

9. The room-temperature curable resin composition according to claim 8, wherein component (E) is one or more inorganic fillers selected from calcium carbonate, aerosolized silica, precipitated silica, carbon black, and aluminum oxide.

10. Automotive part having a cured product of a room-temperature curable resin composition according to any one of claims 1 to 9.

11. An automotive oil seal having a cured product of a room-temperature curable resin composition according to any one of claims 1 to 9.

12. An electrical or electronic component having a cured product of a room-temperature curable resin composition according to any one of claims 1 to 9.

13. A building structure having a cured product of a room-temperature curable resin composition according to any one of claims 1 to 9.

14. A civil engineering structure having a cured product of a room-temperature curable resin composition according to any one of claims 1 to 9.

15. An adhesive containing the room-temperature curable resin composition according to any one of claims 1 to 9.

16. A sealing material containing the room-temperature curable resin composition according to any one of claims 1 to 9.

17. A potting agent containing the room-temperature curable resin composition according to any one of claims 1 to 9.

18. A coating agent containing the room-temperature curable resin composition according to any one of claims 1 to 9.

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