Two-component room temperature fast curing resin composition and article

Abstract

The present invention is characterized by containing (A) an organic polymer which has a molecular chain terminal terminated with a hydrolyzable silyl group and / or a hydroxysilyl group and does not contain an organopolysiloxane structure in the main polymer chain, and (B) a hydrolyzable organosilane compound represented by formula (1) and / or a partial hydrolysis-condensation product thereof at a specific ratio: (1) (R1 is a monovalent hydrocarbon group, n is 1-8, and m is 3 or 4). (C) a first agent of a curing catalyst; the two-component type room-temperature fast-curing resin composition, which is composed of a specific ratio of a component A, a component B and a component C, and a second agent containing (A ') an organic polymer in which the molecular chain end is blocked by a hydrolyzable silyl group and / or a hydroxysilyl group and which does not contain an organopolysiloxane structure in the main polymer chain, has excellent fast curability and deep curability, and also has good workability. Furthermore, during curing, as a release group (release compound), cyclic ketone compounds such as cyclobutanone, cyclopentanone and the like are released and released, so that the problems of harmfulness to a human body and the environment and safety are solved. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a condensation-curable two-component room temperature rapid curing resin composition, which is composed of two-component compositions stored separately and crosslinked (cured) by hydrolysis and condensation reaction using moisture (water) in the atmosphere at room temperature (23°C±15°C) by mixing the two components, and which has as its base polymer an organic polymer whose molecular chain ends are blocked with hydrolyzable silyl groups and / or hydroxysilyl groups (silyl groups or silanol groups having hydroxyl groups bonded to silicon atoms) and does not contain an organopolysiloxane structure in the polymer main chain, and in particular to a two-component room temperature rapid curing resin composition, which is separated from a crosslinking agent (curing agent) by hydrolysis and condensation reaction during curing (crosslinking), and the generated separated compound is a cyclic ketone compound such as cyclobutanone and cyclopentanone, and which is cured well by condensation reaction to form a rubber cured product other than an organopolysiloxane resin such as silicone rubber having excellent adhesiveness, and various articles having the composition or its cured product. Background Art

[0002] The polymer having a reactive silicon group (hereinafter referred to as a hydrolyzable silyl group) hydrolyzes and condenses in the presence of water, and the silicon group having a hydroxyl group on the silicon atom (hereinafter referred to as a hydroxysilyl group or a silanol group) condenses with the hydrolyzate of the hydrolyzable silyl group or the silanol group. The organic polymer having the molecular chain end blocked with a hydrolyzable silyl group and / or a hydroxysilyl group and not containing an organopolysiloxane structure in the polymer main chain has a reactive silyl group at the molecular chain end, and forms a siloxane structure only at the crosslinking point during curing. Therefore, it is generally called a modified (modified) organosilicon polymer, and crosslinks and cures in the presence of moisture, and can be used as a curable resin composition. The room temperature curable resin composition having the above-mentioned organic polymer not containing an organopolysiloxane structure in the polymer main chain as a base polymer is in liquid or paste form at room temperature (23°C±15°C) and has the characteristic of becoming a rubber elastic body upon curing. Utilizing this characteristic, it is widely used in adhesives, sealants, potting agents, coating agents, etc. used in automotive parts, electrical and electronic parts, building structures, civil engineering structures, etc.

[0003] Compositions that cure by condensation reaction have hydrolyzable groups in the curing agent (crosslinking agent), and widely used curing agents include deoxime-type curing agents that release oxime compounds such as 2-butanone oxime and dealcohol-type curing agents that release alcohol compounds such as methanol during curing.

[0004] On the other hand, oxime compounds such as 2-butanone oxime generated by deoxime-type curing agents during curing are suspected to be carcinogenic, and methanol and the like generated by dealcohol-type curing agents during curing are toxic to the human body and designated as highly toxic substances, and are therefore not preferred from the perspective of human health. Furthermore, in these compositions, tin catalysts, which are subject to strict regulation as environmental load substances, are sometimes used as curing catalysts, which are not preferred from the perspective of environmental protection.

[0005] Among these, the one-component room-temperature curable resin composition that initiates a curing reaction by contact with moisture in the air does not have the trouble of weighing or mixing the base polymer and the crosslinking agent, catalyst, etc. before use, and is easy to handle, but has disadvantages such as a slow curing speed and poor deep curing properties.

[0006] And the curing speed of the room temperature curing resin composition of two-component type is fast, and deep curing property is also excellent.Said composition is divided into the main component and crosslinking component comprising the polymer and inorganic filler etc. that the molecular chain end is blocked by silanol group and / or hydrolyzable silyl group and prepared.And, separately preserve in separate containers, mix and use (with reference to patent documentation 1,2 (Japanese Patent Laid-Open No. 11-246780 Gazette, Japanese Patent Laid-Open No. 2013-204020 Gazette)) during use, therefore can reduce the crosslinking amount added in large quantities in order to ensure preservation property for the room temperature curing resin composition of one-component type, the elongation physical property of cured product is also good.

[0007] However, the gas generated during curing is methanol as in the conventional art, and a tin catalyst is sometimes used, so that the toxicity of the leaving group and the catalyst and the environmental load cannot be reduced.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Laid-Open No. 11-246780

[0011] Patent Document 2: Japanese Patent Application Publication No. 2013-204020

[0012] Patent Document 3: Japanese Patent Application Publication No. 2017-203065 Summary of the invention

[0013] Problems to be solved by the invention

[0014] The present invention has been completed in view of the above-mentioned actual situation, and its purpose is to provide a room temperature curable resin composition using an organic polymer whose molecular chain ends are blocked with hydrolyzable silyl groups and / or hydroxysilyl groups and does not contain an organic polysiloxane structure in the polymer main chain as a base polymer, that is, a two-component type, fast curing property, excellent deep curing property, using cyclic ketone compounds such as cyclobutanone and cyclopentanone with relatively high flash points as a crosslinking agent with no reported health hazards such as carcinogenicity and reproductive toxicity to humans and environmental hazards such as aquatic toxicity, various articles having the composition, and elastomer molded products obtained by curing the two-component type room temperature fast curing resin composition.

[0015] Means for solving problems

[0016] The present inventors have repeatedly conducted in-depth studies to achieve the above-mentioned purpose, and as a result, found that a two-component room temperature fast curing resin composition consisting of a first component and a second component has excellent curing properties compared to a one-component room temperature curing resin composition, and cyclic ketone compounds such as cyclobutanone and cyclopentanone are released as leaving groups (leaving compounds) during curing, thereby solving the problems of harmfulness and safety to the human body and the environment. The first component contains (A) an organic polymer having a molecular chain terminal blocked with a hydrolyzable silyl group and / or a hydroxysilyl group and having no organopolysiloxane structure in the polymer main chain, (B) a hydrolyzable organosilane compound represented by the following general formula (1) and / or its partial hydrolysis condensate, and (C) a curing catalyst in a specific ratio, and the second component contains a specific amount of (A') an organic polymer having a molecular chain terminal blocked with a hydrolyzable silyl group and / or a hydroxysilyl group and having no organopolysiloxane structure in the polymer main chain.

[0017] [Chemistry 1]

[0018]

[0019] (Where R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 8, and m is 3 or 4.

[0020] As for the two-component room temperature fast curing resin composition of the present invention, it is believed that when the two components are separated into the first and second components and stored, by making the crosslinking agent of the (B) component coexist only with the (A) component in the first component of the base polymer as a whole, the amount of the crosslinking agent required to ensure storage stability can be reduced to the vicinity of the minimum amount sufficient for crosslinking of the base polymer as a whole (i.e., the total amount of the base polymer after mixing the two components) compared to the one-component room temperature curing resin composition, so that the curing reaction proceeds relatively quickly compared to the one-component room temperature curing resin composition, that is, the curing property (fast curing property, deep curing property) is improved. More preferably, by adding an organic compound having a primary amino group as a curing accelerator, after the two components are mixed, the cyclic ketone compound generated by the hydrolysis of the (B) component in the initial stage of curing reacts with the organic compound having a primary amino group of the (D) component to generate water in the system, thereby further promoting the hydrolysis and condensation reaction, so it is presumed that the curing property (fast curing property, deep curing property) is improved in the same manner as the one-component room temperature curing resin composition.

[0021] In addition, it was found that the above-mentioned curing problem can be solved by using a hydrolyzable organosilane compound and / or its partially hydrolyzed condensate (crosslinking agent) with a cyclic ketone compound such as cyclobutanone and cyclopentanone as a leaving group, which has no health hazards such as carcinogenicity and reproductive toxicity to humans, and environmental hazards such as aquatic toxicity, as the (B) component, and an organic compound having a primary amino group as the (D) component, so that after the two components are mixed, the cyclic ketone compound generated by the hydrolysis of the (B) component reacts with the ketimine of the organic compound having a primary amino group in the (D) component to generate water from the inside, thereby obtaining a composition with excellent rapid curing property. It was further found that the two-component room temperature rapid curing resin composition of the present invention can be cured quickly even without using a tin catalyst, as in the case of using a tin catalyst, thereby solving the problems of toxicity and safety to humans and the environment, and completing the present invention.

[0022] That is, the present invention provides the following two-component room temperature fast-curing resin composition, and various articles having the composition or its cured products (automotive parts, electrical and electronic parts, building structures, civil engineering structures, adhesives, sealants, potting agents, coating agents, etc.), etc. [1]

[0024] A two-component room temperature fast curing resin composition, which consists of a first component and a second component, wherein the first component contains:

[0025] (A) an organic polymer having a molecular chain terminal blocked with a hydrolyzable silyl group and / or a hydroxysilyl group and having no organopolysiloxane structure in the polymer main chain: 10 to 90 parts by mass, wherein the total of the component (A) and the component (A') described below is 100 parts by mass,

[0026] (B) a hydrolyzable organosilane compound represented by the following general formula (1) and / or a partially hydrolyzed condensate thereof: 1 to 30 parts by mass based on 100 parts by mass of the total of the components (A) and (A'); and

[0027] [Chemistry 2]

[0028]

[0029] In the formula, R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 8, m is 3 or 4,

[0030] (C) Curing catalyst: 0.01 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (A');

[0031] The second dose contains:

[0032] (A') an organic polymer having a molecular chain terminal blocked with a hydrolyzable silyl group and / or a hydroxysilyl group and containing no organopolysiloxane structure in the polymer main chain: 10 to 90 parts by mass, wherein the total of the components (A) and (A') is 100 parts by mass. [2]

[0034] The two-component room temperature rapid curing resin composition according to [1], wherein the first component and the second component each contain 0 to 5 parts by mass of a curing accelerator (D): an organic compound having a primary amino group, based on 100 parts by mass of the total of the components (A) and (A'), and the curing accelerator is contained in at least 0.1 parts by mass in either the first component or the second component. [3]

[0036] The two-component room temperature rapid curing resin composition according to [1] or [2], wherein the hydrolyzable organosilane compound and / or its partial hydrolysis condensate of the component (B) releases the cyclic ketone compound by hydrolysis. [4]

[0038] The two-component room temperature rapid curing resin composition according to [3], wherein the cyclic ketone compound to be released is cyclobutanone or cyclopentanone. [5]

[0040] The two-component room temperature rapid curing resin composition according to any one of [1] to [4], wherein the number average molecular weight of the organic polymers of the components (A) and (A′) is 2,000 to 50,000. [6]

[0042] The two-component room temperature rapid curing resin composition according to any one of [1] to [5], wherein the curing catalyst (C) does not contain a tin catalyst. [7]

[0044] The two-component room temperature rapid curing resin composition according to any one of [1] to [6], wherein the first component and the second component each further contain 0 to 1000 parts by mass of an (E) inorganic filler relative to 100 parts by mass of the total of the (A) component and the (A′) component, and the (E) inorganic filler is contained in at least 0.1 parts by mass or more in either the first component or the second component. [8]

[0046] The two-component room temperature rapid curing resin composition according to [7], wherein the component (E) is one or more inorganic fillers selected from the group consisting of calcium carbonate, fumed silica, precipitated silica, carbon black and alumina. [9]

[0048] The two-component room temperature rapid curing resin composition according to any one of [1] to [8], wherein the first component and the second component each further contain 0 to 5 parts by mass of an adhesion promoter (F) relative to 100 parts by mass of the total of the components (A) and (A'), and the adhesion promoter is contained in at least 0.1 parts by mass in either the first component or the second component.

[10]

[0050] The two-component room temperature rapid curing resin composition according to any one of [1] to [9], wherein the mixing ratio of the first component to the second component is 1:1 to 10:1 in terms of mass ratio.

[11]

[0052] An automobile part comprising a cured product of the two-component room temperature rapid curing resin composition according to any one of [1] to

[10] .

[12]

[0054] An electric or electronic component comprising a cured product of the two-component room temperature rapid curing resin composition according to any one of [1] to

[10] .

[13]

[0056] A building structure comprising a cured product of the two-component room temperature rapid curing resin composition according to any one of [1] to

[10] .

[14]

[0058] A civil engineering structure comprising a cured product of the two-component room temperature rapid curing resin composition according to any one of [1] to

[10] .

[15]

[0060] An adhesive comprising the two-component room temperature rapid curing resin composition according to any one of [1] to

[10] .

[16]

[0062] A sealant comprising the two-component room temperature rapid curing resin composition according to any one of [1] to

[10] .

[17]

[0064] A potting agent comprising the two-component room temperature rapid curing resin composition according to any one of [1] to

[10] .

[18]

[0066] A coating agent comprising the two-component room temperature rapid curing resin composition according to any one of [1] to

[10] .

[0067] Effects of the Invention

[0068] The two-component room temperature rapid curing resin composition of the present invention is composed of a first component and a second component. Thus, when the first component and the second component are mixed, rapid curing and deep curing properties are excellent.

[0069] The two-component type room temperature fast curing resin composition of the present invention is particularly excellent in the fast curing property in the air at room temperature, and workability is also good. For the two-component type room temperature fast curing resin composition of the present invention, if the first agent and the second agent are mixed and exposed to the air, then it is cured rapidly, showing excellent physical properties. And then, for the two-component type room temperature fast curing resin composition of the present invention, the cross-linking agent used does not have the reported example of environmental harmfulness such as carcinogenicity, reproductive toxicity, aquatic toxicity, etc. for human body when curing, and the cyclic ketone compounds such as cyclobutanone and cyclopentanone with higher flash point are released as the departure group (departure substance), and even if tin catalyst is not used, it is also cured, so it can be suitable as various adhesives, sealants, potting agents, coating agents, etc. that consider the health, safety, environmental protection (load reduction) of human body. DETAILED DESCRIPTION

[0070] The present invention is described in more detail below.

[0071] <Two-component room temperature fast curing resin composition>

[0072] The two-component room temperature rapid curing resin composition of the present invention comprises a first component containing specific amounts of the components (A), (B) and (C) described below, and a second component containing the component (A'). It should be noted that the second component does not contain the components (B) and (C).

[0073] Each component is described in detail below. It should be noted that in the present invention, the viscosity is a value measured at 23°C using a rotational viscometer according to the method specified in JIS Z-8803. The "room temperature" in the so-called "two-component room temperature fast curing resin composition" refers to a state of temperature 23°C ± 15°C and humidity 50% RH ± 5% RH.

[0074] [Component (A), component (A'): organic polymer]

[0075] The components (A) and (A') used in the present invention are organic polymers (modified silicone polymers) whose molecular chain ends are blocked with hydrolyzable silyl groups and / or hydroxysilyl groups (silyl groups or silanol groups having hydroxyl groups bonded to silicon atoms) and do not contain an organopolysiloxane structure in the polymer main chain. The component (A) is formulated in the first agent, and the component (A') is formulated in the second agent. These components (A) and (A') both function as base polymers in the two-component room temperature rapid curing resin composition of the present invention. It should be noted that the modified silicone polymers of the components (A) and (A') may have a short-chain siloxane structure (preferably, a diorganosiloxane unit having a repeating number of about 2 to 5) in the linking portion (connecting portion) connecting the silyl group at the molecular chain end to the main chain. That is, the modified silicone polymer of the components (A) and (A') preferably does not have a long-chain siloxane structure containing a diorganosiloxane unit having a repetition number of 6 or more in the linking portion (connecting portion) connecting the silyl group at the end of the molecular chain to the main chain (that is, if the organic polymer does not contain an organopolysiloxane structure in the polymer main chain, the linking portion (connecting portion) adjacent to the silyl group at the end of the molecular chain may contain a short-chain siloxane structure containing a diorganosiloxane unit having a repetition number of 2 to 5).

[0076] As such a base polymer, any organic polymer having a molecular chain terminal blocked with a hydrolyzable silyl group (e.g., an alkoxysilyl group, etc.) and / or a hydroxysilyl group (silanol group) and having no organopolysiloxane structure in the polymer main chain can be preferably used without limitation in terms of the main chain structure. From the perspective of availability, it is particularly preferred that the polymer main chain be a polymer structure such as polyoxyalkylene such as polypropylene oxide, polyethylene oxide, polyisobutylene oxide, and a propylene oxide-ethylene oxide copolymer, a polyolefin such as polyisobutylene, a polyacrylate, or a polymethacrylate. Part of these main chain structures may have a carbamate structure (-NHC(=O)O-), an ester structure (-C(=O)O-), or the like.

[0077] The organic polymer (modified silicone polymer) having the molecular chain ends blocked with a hydrolyzable silyl group and / or a hydroxysilyl group (silanol group) as the components (A) and (A') and having no organopolysiloxane structure in the polymer main chain is preferably a silylated oxyalkylene polymer, a silylated urethane polymer, a silylated acrylate polymer or a silylated olefin polymer.

[0078] Specific examples of silylated oxyalkylene polymers include polymers having a structure in which the main chain includes a polyoxyalkylene structure such as polypropylene oxide, polyethylene oxide, or a propylene oxide-ethylene oxide copolymer, and the molecular chain ends, particularly both molecular chain ends, are blocked with a hydrolyzable silyl group and / or a silanol group (polyether-modified silicone polymer).

[0079] Specific examples of silylated urethane polymers include polymers having a structure in which the main chain includes a polyoxyalkylene structure such as polypropylene oxide, polyethylene oxide, or a propylene oxide-ethylene oxide copolymer, a urethane bond structure (-NHC(=O)O-) with isocyanate in a part of the main chain structure, and the molecular chain ends, particularly both molecular chain ends, are blocked with a hydrolyzable silyl group and / or a silanol group (urethane-modified silicone polymer).

[0080] Specific examples of silylated acrylate polymers include polymers having a structure including polyacrylate, polymethacrylate or the like in the main chain and having a structure in which the molecular chain ends, particularly both molecular chain ends, are capped with hydrolyzable silyl groups and / or silanol groups (acrylate-modified silicone polymers).

[0081] Specific examples of silylated olefin polymers include polymers having a polyolefin structure such as a polymer containing an isobutylene monomer in the main chain and having a structure in which the molecular chain ends, particularly both molecular chain ends, are blocked with a hydrolyzable silyl group and / or a silanol group (olefin-modified silicone polymer).

[0082] Among these, from the viewpoint of availability, preferred are silylated propylene oxide polymers having a polypropylene oxide as the main chain and having both ends of the molecular chain blocked with hydrolyzable silyl groups and / or silanol groups, and silylated acrylate polymers having a polyacrylate as the main chain and having both ends of the molecular chain blocked with hydrolyzable silyl groups and / or silanol groups. More preferred are silylated propylene oxide polymers having a polypropylene oxide as the main chain and having both ends of the molecular chain blocked with hydrolyzable silyl groups and / or silanol groups.

[0083] In addition, since polymers having molecular chain terminals blocked with silanol groups are preferred from the viewpoint of rapid curability and deep curability, silylated propylene oxide polymers having polypropylene oxide as the main chain and having both molecular chain terminals blocked with silanol groups are particularly preferred.

[0084] The organic polymers of the components (A) and (A') are more preferably organic polymers represented by the following general formula (2) or (3) and having both ends of the molecular chain blocked with hydrolyzable silyl groups or hydroxysilyl groups (silyl groups or silanol groups having hydroxyl groups bonded to silicon atoms).

[0085] [Chemistry 3]

[0086]

[0087] (Where R 2 and R 4 They may be the same or different and are unsubstituted or substituted monovalent hydrocarbon groups having 1 to 10 carbon atoms. 3 Each is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. a is independently an integer greater than 2, b is independently 0, 1 or 2 for each bonded silicon atom, and c is independently an integer from 1 to 5. Y is a divalent organic group that does not contain a siloxane structure.

[0088] In the above formulas (2) and (3), R 2 and R 4 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, R 3 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. 2 , R 3 , R 4The unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, includes, for example, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, and octyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, and hexenyl; aryl groups such as phenyl, tolyl, xylyl, α-, β-naphthyl; aralkyl groups such as benzyl, 2-phenylethyl, and 3-phenylpropyl; and groups in which a part or all of the hydrogen atoms of these groups are substituted with halogen atoms such as F, Cl, and Br, cyano, and the like, for example, 3-chloropropyl, 3,3,3-trifluoropropyl, and 2-cyanoethyl. As R 2 and R 4 , preferably methyl or phenyl, and particularly preferably methyl. 3 , preferably a methyl group, an ethyl group, or a hydrogen atom, and particularly preferably a methyl group or a hydrogen atom. 2 , R 3 , R 4 They may be the same group or different groups.

[0089] In formulae (2) and (3), a is each independently an integer of 2 or more, preferably an integer of 2 to 8, more preferably 2, 3 or 4, and particularly preferably 3.

[0090] In formula (2), b is independently 0, 1 or 2, preferably 0 or 1, and particularly preferably 1 for each bonded silicon atom.

[0091] In formula (3), c is independently an integer of 1-5, preferably an integer of 1-4.

[0092] In the above general formulae (2) and (3), Y is a divalent organic group not containing a siloxane structure, and specifically includes polyoxyalkylene groups such as polyoxyethylene, polyoxypropylene, and polyoxybutylene, polyalkylene groups such as polyisobutylene, and polymers of methyl methacrylate represented by the following formula, or groups in which one or more groups selected from an alkylene group, an ether bond oxygen atom, an amide bond, a carbamate bond, a carbonyl bond, an ester bond, etc. exist.

[0093] [Chemistry 4]

[0094]

[0095] (In the formula, R' is a hydrogen atom or a methyl group, R" is an alkyl group having 1 to 10 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, etc., and z represents the degree of polymerization of the repeating units constituting the main chain, which is an integer of 20 to 800.)

[0096] Specific examples of the organic polymers of the components (A) and (A′) include the following structures.

[0097] [Chemistry 5]

[0098]

[0099] [Chemistry 6]

[0100]

[0101] [Chemistry 7]

[0102]

[0103] [Chemistry 8]

[0104]

[0105] [Chemistry 9]

[0106]

[0107] (In the formula, z represents the degree of polymerization of the repeating unit constituting the main chain, and is an integer of 20 to 800. Me represents a methyl group.)

[0108] It should be noted that in the above-mentioned exemplary formulas, the methoxy group (MeO-) at the end of the molecular chain may be substituted by other lower alkoxy groups such as ethoxy groups, and the hydroxydimethylsilyl group (-SiMe2OH) at the end of the molecular chain may be substituted by a polydimethylsiloxane group (-[Si(Me)2O] c’ -H, c'=an integer from 2 to 5).

[0109] The number average molecular weight of the organic polymers of the components (A) and (A') is preferably 2000 to 50000, more preferably 5000 to 40000, and even more preferably 10000 to 35000. If the number average molecular weight is too small, the rubber properties such as elongation and strength of the obtained cured product may deteriorate, while if it is too large, the viscosity of the composition increases sharply, which may be disadvantageous in terms of handling.

[0110] It should be noted that in the present invention, the molecular weight (or degree of polymerization) can be obtained, for example, by using tetrahydrofuran (THF), toluene, etc. as an elution solvent, as the number average molecular weight (or number average degree of polymerization) or weight average molecular weight (or weight average degree of polymerization) converted to polystyrene in gel permeation chromatography (GPC) analysis (the same below).

[0111] These polymers whose molecular chain ends are blocked by hydrolyzable silyl groups and / or hydroxysilyl groups (silanol groups) can be obtained, for example, by using known methods such as Japanese Patent Application Laid-Open No. 2017-203065 (Patent Document 3). Specifically, as a method for producing a silylated oxypropylene polymer with polypropylene oxide as the main chain and whose molecular chain ends are blocked by silanol groups, a polyoxyalkylene polymer such as a polyoxypropylene polymer whose molecular chain ends are blocked by alkenyl groups having a CH2=CH- structure such as an allyl group at the end and an organosilicon compound such as an organosilane having a silanol group (SiOH group) and a hydrosilyl group (SiH group), an organosiloxane oligomer, etc. can be produced by hydrosilylation in the presence of a platinum catalyst. In addition, as another manufacturing method, a polyoxyalkylene polymer such as a polyoxypropylene polymer whose molecular chain ends are capped with alkenyl groups having a CH2=CH- structure such as an allyl group at the end is subjected to hydrosilylation with an organic silicon compound such as an organic silane and an organic siloxane oligomer having a chlorosilyl group (SiCl group) and a hydrosilyl group (SiH group) in the presence of a platinum catalyst, and then the chlorosilyl group is subjected to silanol (SiOH) conversion by a hydrolysis reaction.

[0112] It should be noted that the organic polymer (modified silicone polymer) in which the molecular chain ends of the components (A) and (A') are blocked with hydrolyzable silyl groups and / or silanol groups and which does not contain an organopolysiloxane structure in the polymer main chain can be a commercially available product. For example, as a polyether-modified silicone polymer, "MS polymer" manufactured by Kaneka Co., Ltd., "GENIOSIL (registered trademark) (STP-E)) manufactured by Wacker Co., Ltd. (Germany) can be used, and as a urethane-modified silicone polymer, "GENIOSIL (registered trademark) (SPUR / STP-U)" manufactured by Wacker Co., Ltd. (Germany) can be used.

[0113] The organic polymers of the components (A) and (A') whose molecular chain ends are blocked with hydrolyzable silyl groups and / or silanol groups may be used alone or in combination of two or more of them having different structures and polymerization degrees as required. In addition, the organopolysiloxanes of the components (A) and (A') may be the same or different.

[0114] [Component (B): Hydrolyzable organosilane compound and / or its partially hydrolyzed condensate]

[0115] The component (B) used in the two-component room temperature rapid curing resin composition of the present invention is a hydrolyzable organosilane compound represented by the following general formula (1) and / or its partial hydrolysis condensate, which is characterized in that it is used as a crosslinking agent (curing agent) and releases cyclic ketone compounds such as cyclobutanone and cyclopentanone as a leaving group (leaving substance) through hydrolysis.

[0116] In the present invention, the "partial hydrolysis condensate" refers to an organosiloxane oligomer having three or more, preferably four or more, residual hydrolyzable groups in the molecule, which is produced by partial hydrolysis and condensation of the hydrolyzable organosilane compound.

[0117] [Chemistry 10]

[0118]

[0119] (Where R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 8, and m is 3 or 4.

[0120] In the above general formula (1), R 1 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, and R 1 Examples include alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2-ethylhexyl, nonyl, and decyl, alkenyl groups such as vinyl, allyl, propenyl, isopropenyl, butenyl, and hexenyl, aryl groups such as phenyl and tolyl, and aralkyl groups such as benzyl and phenylethyl. Among these, methyl, ethyl, vinyl, and phenyl are preferred, and methyl, vinyl, and phenyl are particularly preferred.

[0121] In the above general formula (1), n ​​is an integer of 1 to 8, preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and even more preferably 2 or 3. When n is 0, a cyclic structure is not formed. If n is an integer of 9 or more, the molecular weight of the hydrolyzable organosilane becomes large, and purification by distillation becomes difficult, or the amount of addition required to ensure storage stability increases, which becomes disadvantageous in terms of cost.

[0122] As described above, m is 3 or 4. When the number is less than 3, rubber curing by a crosslinking reaction does not occur, and the crosslinking agent is not suitable as a crosslinking agent for a two-component type room temperature rapid curing resin composition.

[0123] In addition, the leaving group (leaving compound) generated by the hydrolysis of the hydrolyzable organosilane compound represented by the above general formula (1) is a cyclic ketone compound such as cyclopropanone, cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, and cyclodecanone, preferably cyclobutanone and cyclopentanone, and more preferably cyclopentanone. As for cyclobutanone and cyclopentanone, there are no reported examples of health hazards such as carcinogenicity and reproductive toxicity to humans, and environmental hazards such as toxicity to aquatic organisms. In addition, cyclopentanone is mass-produced industrially, is easy to obtain, and has high cost competitiveness, so as described later, it is also advantageous for the production of the hydrolyzable organosilane compound of component (B).

[0124] The hydrolyzable organosilane compound of the component (B) can be produced, for example, by reacting a chlorosilane compound corresponding to the hydrolyzable organosilane compound represented by the general formula (1) as a product with a cyclic ketone compound in the presence of a catalyst and an alkaline substance (for example, a dehydrochlorination reaction). The reaction formula is represented, for example, by the following formula [1].

[0125] [Chemistry 11]

[0126]

[0127] (Where R 1 , n, m are as described above.)

[0128] Among them, examples of the chlorosilane compound include the following compounds.

[0129] [Chemistry 12]

[0130]

[0131] In addition, examples of the cyclic ketone compound include the following compounds.

[0132] [Chemistry 13]

[0133]

[0134] The amount of the cyclic ketone compound to be reacted with the chlorosilane compound is preferably 0.95 to 3.0 mol, more preferably 0.99 to 2.5 mol, and even more preferably 1.0 to 2.0 mol relative to 1 mol of the number of chlorine atoms in the chlorosilane compound. If the amount of the cyclic ketone compound added is too small, the reaction may not be completed, and if the amount of the cyclic ketone compound added is too large, purification takes time and the production time may increase.

[0135] The catalyst used in the reaction includes 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, copper butyrate, etc., but is not limited to these.

[0136] The amount of the catalyst (metal copper compound) added is preferably 0.001 to 0.5 mol, more preferably 0.002 to 0.2 mol, and further preferably 0.003 to 0.1 mol relative to 1 mol of the chlorosilane compound. If the amount of the catalyst added is too small, the reaction may not be completed, and if the amount of the catalyst added is too large, it becomes disadvantageous in terms of cost.

[0137] As the alkaline substance used in the reaction, a low nucleophilic alkaline substance such as trimethylamine, triethylamine, tripropylamine, tributylamine, urea, diazabicycloundecene, diazabicyclononene, etc. can be used. Among them, trimethylamine, triethylamine, and tributylamine are preferred, and triethylamine is particularly preferred.

[0138] The amount of the alkaline substance added is preferably 0.95 to 2.5 mol, more preferably 0.99 to 2.0 mol, and further preferably 1.0 to 1.5 mol, relative to 1 mol of the number of chlorine atoms in the chlorosilane compound. If the amount of the alkaline substance added is too small, the reaction may not be completed, and if the amount of the alkaline substance added is too large, it is economically disadvantageous.

[0139] In the production of the hydrolyzable organosilane compound of the component (B), a generally used solvent can be used. Examples of the solvent 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 esters such as ethyl acetate, methyl acetate, and butyl acetate.

[0140] The amount of the solvent used is not particularly limited, but is usually 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, based on 100 parts by mass of the cyclic ketone compound used.

[0141] As the reaction conditions of the chlorosilane compound and the cyclic ketone compound, it is preferred to drop the chlorosilane compound into the cyclic ketone compound at a temperature of usually 0 to 120° C., preferably 0 to 100° C., and react at 50 to 120° C., preferably 60 to 100° C. for 1 to 48 hours, more preferably about 3 to 30 hours. If the temperature during the reaction is too low, the reaction may not be completed, and if the temperature during the reaction is too high, the coloring of the product may become greater. In addition, if the reaction time is too short, the reaction may not be completed, and if the reaction time is too long, it will be disadvantageous to productivity.

[0142] In addition, purification after the reaction can be carried out by distilling the target product under reduced pressure, and the degree of reduced pressure is preferably 1×10 -5 ~3000Pa, more preferably 1×10-5 The temperature during purification is preferably 100 to 250° C., more preferably 120 to 230° C. If the pressure (degree of reduced pressure) during decompression is too high, distillation may become difficult. In addition, if the temperature during purification is too low, purification by distillation may become difficult, and if it is too high, it may cause coloration or decomposition of the reactant.

[0143] Specific examples of the hydrolyzable organosilane compound of the component (B) include compounds represented by the following formulas: In addition, Me represents a methyl group.

[0144] [Chemistry 14]

[0145]

[0146] (B) The component may be used alone or in combination of two or more.

[0147] The component (B) is added to the first agent in an amount of 1 to 30 parts by mass, preferably 2 to 25 parts by mass, relative to 100 parts by mass of the total of the components (A) and (A'). If the amount of the component (B) is too small, sufficient crosslinking cannot be obtained when the composition is cured, and if it is too large, the mechanical properties (rubber properties) of the obtained cured product (silicone rubber) may be reduced, which may be economically disadvantageous.

[0148] [Component (C): Curing Catalyst]

[0149] The curing catalyst of the component (C) is used to promote the hydrolysis condensation reaction and is generally called a curing catalyst. As the curing catalyst, a known curing catalyst generally used in a room temperature curable silicone resin composition that cures in the presence of moisture can be used.

[0150] The curing catalyst of the component (C) is not particularly limited to a non-metallic organic catalyst, and any known curing accelerator for a condensation-curable organopolysiloxane composition can be used. For example, there can be mentioned compounds containing phosphazene such as N,N,N',N',N", and N"-hexamethyl-N"'-(trimethylsilylmethyl)-phosphorimidictriamide; quaternary ammonium salts such as benzyltriethylammonium acetate; dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine; silanes and siloxanes containing guanidine groups such as γ-(N,N,N',N'-tetramethylguanidino)propyltrimethoxysilane, γ-(N,N,N',N'-tetramethylguanidino)propylmethyldimethoxysilane, and γ-(N,N,N',N'-tetramethylguanidino)propyltris(trimethylsiloxy)silane. In addition, the non-metallic organic catalyst may be used alone or in combination of two or more.

[0151] The curing catalyst of the component (C) is not particularly limited to a metal-based catalyst, and a curing catalyst known as a curing catalyst for a condensation-curable organopolysiloxane can be used. Examples include alkyl tin ester compounds (tin catalysts) such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, dimethyltin dineodecanoate, dioctyltin dineodecanoate, and di-n-butyldimethoxytin; titanates or titanium chelates such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetra(2-ethylhexyloxy)titanium, dipropoxybis(acetylacetonate)titanium, and isopropoxyoctanediol titanium; zinc naphthenate, zinc stearate, and zinc 2-ethyloctoate; aluminum alkoxide compounds such as aluminum isopropoxide and aluminum sec-butoxide; aluminum chelates such as alkyl acetate-aluminum diisopropoxide and ethyl bisacetoacetate-monoacetylacetonate aluminum; organic metal compounds such as bismuth (III) neodecanoate, bismuth (III) 2-ethylhexanoate, bismuth (III) citrate, bismuth octoate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, and cobalt naphthenate; and lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, and lithium oxalate. The metal-based catalyst is not limited to these. The metal-based catalyst may be used alone or in combination of two or more.

[0152] In the present invention, any catalyst other than the tin catalyst added to the above catalysts exhibits the same curability and cured product performance as when the tin catalyst is added. Therefore, from the viewpoint of environmental protection, it is preferred to add other catalysts instead of the tin catalyst.

[0153] The (C) component is mixed in the first agent, and its mixing amount is 0.01 to 5 parts by mass, preferably 0.05 to 4 parts by mass, and more preferably 0.1 to 3 parts by mass relative to 100 parts by mass of the total of the (A) component and the (A') component. If the mixing amount of the (C) component is less than 0.01 parts by mass, good curability cannot be obtained, and thus the disadvantage of slow curing speed occurs. On the contrary, if it becomes an amount exceeding 5 parts by mass, the curability of the composition is too fast, and thus the permissible range of the working time after the composition is applied is shortened, or the mechanical properties of the obtained rubber are reduced.

[0154] [Component (D): curing accelerator]

[0155] Component (D) is an organic compound having a primary amino group (i.e., an amino group having a -NH2 structure, excluding a guanidine group), and is an optional component that can be incorporated as needed. It reacts with the cyclic ketone compound generated by hydrolysis of component (B) to generate water, thereby significantly improving the deep curing property of the composition. As the component (D), there is no particular limitation as long as it has a primary amino group, and specifically, examples thereof include aliphatic amines such as methylamine, ethylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, and dodecylamine; aliphatic polyamines such as ethylenediamine and triethylenetetramine; aromatic amines such as aniline; cyclic amines such as cyclopentylamine, cyclohexylamine, and 2-ethylcyclohexylamine; silane coupling agents containing primary amino groups such as aminosilanes such as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and 3-2-(aminoethylamino)propyltrimethoxysilane [another name: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane]; and organosilicon compounds containing primary amino groups such as polysiloxanes containing primary amino groups. These may be used alone or in combination of two or more.

[0156] When the component (D) is added, it may be added in the first agent, in the second agent, or in both agents. The amount of the component (D) added is preferably 0 to 5 parts by mass in each of the first agent and the second agent (and at least 0.1 parts by mass is contained in either the first agent or the second agent), and more preferably 0 to 4 parts by mass (and at least 0.1 parts by mass is contained in either the first agent or the second agent) relative to 100 parts by mass of the total of the components (A) and (A'). That is, the total amount of the component (D) added in the composition is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.4 to 4 parts by mass relative to 100 parts by mass of the total of the components (A) and (A'). When the total amount of the component (D) added is less than 0.1 parts by mass, the amount of water generated by the reaction with the cyclic ketone compound generated by the hydrolysis of the component (B) is small, and sufficient deep curing property is not exhibited. When the amount of the component (D) added exceeds 10 parts by mass, it becomes disadvantageous in terms of the properties and storage stability of the obtained cured product.

[0157] [Component (E): Inorganic filler]

[0158] In the two-component type room temperature fast curing resin composition of the present invention, as required, the inorganic filler of (E) component can be matched as an optional component. (E) The inorganic filler of component is for giving the two-component type room temperature fast curing resin composition of the present invention The reinforcing property, non-reinforcing filler of rubber properties. As the inorganic filler of (E) component, the silicon dioxide-based fillers such as dry silica such as calcined silica, pyrogenic silica, precipitated silica, wet silica such as sol-gel silica, carbon black, talc, bentonite, surface-treated or untreated calcium carbonate, zinc carbonate, magnesium carbonate, surface-treated or untreated calcium oxide, zinc oxide, magnesium oxide, aluminum oxide, aluminum hydroxide, etc. can be exemplified, wherein preferably calcium carbonate, pyrogenic silica, precipitated silica, carbon black, aluminum oxide, more preferably the surface of the inorganic filler has been hydrophobized, calcium carbonate, pyrogenic silica, precipitated silica, carbon black, aluminum oxide. In this case, these inorganic fillers preferably have a small amount of water.

[0159] It should be noted that there is no particular limitation on the type, amount, treatment method, etc. of the surface treatment agent (hydrophobizing agent), and representatively, treatment agents such as chlorosilane, alkoxysilane, and organosilicon compounds such as organosilazane, fatty acids, paraffin, silane coupling agents, and titanium coupling agents can be used.

[0160] The inorganic filler of the component (E) may be used alone or in combination of two or more.

[0161] When the (E) component is added, it may be added in the first agent, in the second agent, or in both agents, and its amount is preferably 0 to 1000 parts by mass in each of the first agent and the second agent (and at least 0.1 parts by mass is contained in either the first agent or the second agent), and more preferably 0 to 500 parts by mass (and at least 0.1 parts by mass is contained in either the first agent or the second agent) relative to 100 parts by mass of the total of the (A) component and the (A') component. That is, the total amount of the composition when the (E) component is added is preferably 0.1 to 2000 parts by mass, more preferably 0.1 to 1000 parts by mass, and further preferably 1 to 500 parts by mass relative to 100 parts by mass of the total of the (A) component and the (A') component. If used in a larger amount than 2000 parts by mass, not only the viscosity of the composition increases, the workability deteriorates, but also the rubber strength after curing decreases, and it becomes difficult to obtain rubber elasticity.

[0162] [Component (F): Adhesion promoter]

[0163] The component (F) is an adhesion promoter, which is an optional component that can be added as needed and is used to provide sufficient adhesion to the cured product formed from the two-component room temperature rapid curing resin composition of the present invention. As the adhesion promoter, a known adhesion promoter is preferably used, and examples thereof include silane coupling agents such as hydrolyzable silanes containing functional groups (excluding the silane coupling agents containing primary amino groups described in the above-mentioned (B) component and the curing accelerator (D)). Specifically, examples thereof include vinyl silane coupling agents, (meth)acrylic silane coupling agents, epoxy silane coupling agents, mercapto silane coupling agents, and isocyanate silane coupling agents. Specifically, examples thereof include vinyl tris(β-methoxyethoxy)silane, γ-methacryloxypropyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl methyl diethoxysilane, γ-mercaptopropyl trimethoxysilane, and 3-isocyanate propyl triethoxysilane.

[0164] Among these, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane and γ-acryloxypropyltrimethoxysilane, epoxy silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and isocyanate silanes such as 3-isocyanatepropyltriethoxysilane are particularly preferred.

[0165] When the (F) component is added, it can be added in the first agent, in the second agent, or in both agents, and its amount is preferably 0 to 5 parts by mass in each of the first agent and the second agent (and at least 0.1 parts by mass is contained in either the first agent or the second agent), and more preferably 0 to 3 parts by mass (wherein at least 0.2 parts by mass is contained in either the first agent or the second agent) relative to 100 parts by mass of the total of the (A) component and the (A') component. That is, the total amount of the composition when the (F) component is added is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and further preferably 0.3 to 3 parts by mass relative to 100 parts by mass of the total of the (A) component and the (A') component. Even when the adhesion promoter is not used and the adherend is bonded using an inorganic filler, it is not necessary to use it.

[0166] [Other ingredients]

[0167] In addition, the two-component room temperature fast curing resin composition of the present invention preferably has components (A), (A'), (B), and (C) as essential components, and further contains components (D), (E), and (F). In addition, known additives such as plasticizers, pigments, dyes, anti-aging agents, antioxidants, antistatic agents, flame retardants such as antifungal agents, antimicrobial agents, etc. can be contained as additives.

[0168] Examples of plasticizers that can be added to the two-component room temperature fast curing resin composition of the present invention 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), tetrahydrophthalate, dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutyl diethylene glycol adipate (BXA), bis(2-ethylhexyl) azelaic acid (DOZ), dibutyl sebacate (DBS), dioctyl sebacate (DOS), dibutyl maleate Examples of the above-mentioned plasticizers include but are not limited to: (DBM), di-2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP), tributyl phosphate (TBP), tri(2-ethylhexyl) phosphate (TOP), tri(chloroethyl) phosphate (TCEP), tri(dichloropropyl) phosphate (CPP), tri(butoxyethyl) phosphate (TBXP), tri(β-chloropropyl) phosphate (TMCPP), triphenyl phosphate (TPP), octyl diphenyl phosphate (ODP), acetyl triethyl citrate, acetyl tributyl citrate, etc., and examples thereof include trimellitic acid-based plasticizers, polyester-based plasticizers, chlorinated paraffins, stearic acid-based plasticizers, silicone oils (non-functional organopolysiloxanes) such as linear dimethyl polysiloxane, polyoxypropylene glycol, acrylic resins, acrylic polymers, paraffin-based, cycloparaffin-based, isoparaffin-based petroleum-based high-boiling point solvents, etc. These are used alone or in combination of two or more.

[0169] In addition, in the two-component room temperature fast curing resin composition of the present invention, an organic solvent can be used as needed. As the organic solvent, aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane, and isododecane can be listed; aromatic hydrocarbon compounds such as toluene and xylene; linear or branched siloxane oligomers such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and 2-(trimethylsiloxy)-1,1,1,2,3,3,3-heptamethyltrisiloxane; cyclic siloxane oligomers such as octamethylcyclopentasiloxane and decamethylcyclopentasiloxane, etc. The amount of the organic solvent can be appropriately adjusted within the range that does not hinder the effect of the present invention.

[0170] [Preparation of two-component room temperature fast curing resin composition]

[0171] The two-component room temperature fast curing resin composition of the present invention is composed of a first agent containing (A) component, (B) component and (C) component; and a second agent containing (A') component and excluding (B) component and (C) component. By preparing a two-component composition composed of the above-mentioned first agent and the second agent, the fast curing property and deep curing property are excellent. It is believed that this is because, when the above-mentioned first agent and the second agent are separated and stored, by making the crosslinking agent of the (B) component coexist only with the (A) component in the first agent of the whole base polymer, the amount of the crosslinking agent required to ensure storage stability can be reduced to the vicinity of the sufficient minimum amount required for crosslinking of the whole base polymer (that is, the total amount of the base polymer after mixing the two components) compared with the one-component room temperature curing resin composition, so compared with the one-component room temperature curing resin composition, the curing reaction proceeds relatively quickly, that is, the curing property (fast curing property, deep curing property) is improved. More preferably, an organic compound having a primary amino group is added as a curing accelerator, so that after the two components are mixed, the cyclic ketone compound produced by the hydrolysis of the (B) component in the early stage of curing reacts with the organic compound having a primary amino group of the (D) component to generate water in the system, thereby further promoting the hydrolysis and condensation reactions. Therefore, it is estimated that the curability (fast curability, deep curability) is improved as with the one-component room temperature curing resin composition.

[0172] The first agent can be prepared by mixing all of the components (A), (B) and (C) with a part or all of the components (D), (E), (F) and other components used as needed according to a conventional method. The second agent can be prepared by uniformly mixing all of the component (A') with the remaining part or all of the components (D), (E), (F) and other components used as needed in a dry atmosphere according to a conventional method.

[0173] Regarding the mixing ratio of the component (A) in the first agent and the component (A') in the second agent, the component (A') is 90 to 10 parts by mass relative to 10 to 90 parts by mass of the component (A) (a total of 100 parts by mass), and preferably, the component (A') is 70 to 30 parts by mass relative to 30 to 70 parts by mass of the component (A) (a total of 100 parts by mass).

[0174] In addition, optional components (D), (E), (F) and other components may be incorporated into either the first agent or the second agent, or into either or both of them. It is particularly preferred that components (D), (E), and (F) are incorporated into the first agent, and components (D) and (E) are incorporated into the second agent.

[0175] When the component (D) is added to the first agent and the second agent, the ratio thereof is preferably 1:99 to 99:1, particularly 15:85 to 70:30, in terms of the storage stability of the composition.

[0176] When the component (E) is added to the first agent and the second agent, the ratio thereof is preferably 80:20 to 20:80, particularly 60:40 to 40:60, in terms of the uniformity of the composition during mixing (ease of mixing).

[0177] As for the ratio of the first agent to the second agent, from the aspects of workability and uniformity of the composition when the first agent and the second agent are mixed (ease of mixing), it is preferred that the first agent (whole) and the second agent (whole) are blended in a mass ratio of 1:1 to 10:1, particularly 1:1 to 4:1.

[0178] The two-component room temperature rapid curing resin composition of the present invention can be stored in an atmosphere free from moisture, with the first component and the second component produced as described above.

[0179] [Curing method of two-component room temperature fast curing resin composition]

[0180] The two-component room temperature fast curing resin composition of the present invention is mixed in a suitable ratio, specifically the ratio of the first agent to the second agent is 1:1 to 10:1, especially 1:1 to 4:1 by mass, and is usually placed in a room temperature environment (temperature 23°C ± 15°C, humidity 50% RH ± 5% RH) to cure for 10 minutes to 5 days. The molding method, curing conditions, etc. can adopt known methods and conditions that are consistent with the type of composition.

[0181] The two-component room temperature fast curing resin composition of the present invention has fast curing properties. When formed into a 2 mm thick sheet at 23°C and 50% RH, it usually cures in 7 to 10 days, but can be cured in a short time of 60 minutes to 3 days.

[0182] In addition, the two-component room temperature fast curing resin composition of the present invention has deep curing properties. When cured at 23°C and 50% RH in a glass dish with an inner diameter of 10 mm and a depth of 3 mm, it usually takes 5 hours to cure, but it can cure deeply in a short time of about 60 minutes.

[0183] The two-component room temperature fast curing resin composition of the present invention produces compounds from the cross-linking agent through a hydrolysis reaction during curing, which are cyclic ketone compounds such as cyclobutanone and cyclopentanone with high safety, taking human body and environment into consideration. Furthermore, as for cyclopentanone, the flash point is 35°C, which is higher than the dealcoholization type cross-linking agent that releases alcohol compounds such as methanol during curing of the composition, and has high flash point and high safety. Such a two-component room temperature fast curing resin composition of the present invention shows good curability by using various existing catalysts, and its cured product also has excellent adhesion.

[0184] Therefore, the two-component room temperature fast curing resin composition of the present invention can be used as an adhesive, a sealant, a potting agent, or a coating agent, etc. The method of using the two-component room temperature fast curing resin composition of the present invention as an adhesive, a sealant, a potting agent, or a coating agent can be according to a conventionally known method.

[0185] Examples of the target articles include automobile parts, electrical and electronic parts, building structures, and civil engineering structures.

[0186] Example

[0187] Synthesis examples, embodiments and comparative examples for specifically explaining the present invention are shown below, but the present invention is not limited to the following embodiments. The viscosity is a measured value obtained by using a rotational viscometer at 23° C. according to the method specified in JIS Z-8803. The molecular weight is a measured value obtained as a polystyrene-equivalent number average molecular weight in GPC analysis using tetrahydrofuran as an elution solvent.

[0188] In addition, in all the examples and comparative examples, a planetary mixer (manufactured by Inoue, Ltd.) was used as a suitable mixer.

[0189] [Synthesis example 1]

[0190] <Synthesis of polyoxypropylene containing silanol groups at both ends of the molecular chain>

[0191] Into a 1L four-necked separable flask equipped with a stirrer, a reflux condenser, a thermometer and a dropping funnel were placed 600 g of polyoxypropylene with a number average molecular weight of 23,000 and end-capped with allyl groups at both ends of the molecular chain (0.058 mol of terminal allyl functional group conversion) and 2.4 g of a platinum catalyst (a toluene solution of Karstedt catalyst; platinum concentration 1 mass %), and the temperature was raised to 90°C while heating and stirring.

[0192] Next, 19.6 g of 1-hydroxy-octamethyltetrasiloxane (i.e., 1-hydroxy-7-hydrogen-1,1,3,3,5,5,7,7-octamethyltetrasiloxane) (the amount of terminal Si-H functional groups is 0.066 mol) was added dropwise under stirring, and the reaction temperature was kept at 90-95° C., and the reaction system was kept for 6 hours. After the reaction was completed, the reaction was cooled to room temperature (23° C.), and a polyoxypropylene compound containing silanol groups at both ends of the molecular chain (a polyoxyalkylene compound containing silanol groups at both ends of the molecular chain, wherein both ends of the molecular chain are blocked with -(CH2)3-[Si(Me)2O]4-H and the main chain is polyoxypropylene) was obtained. 2 =Methyl, R 3 = hydrogen atom, a=3, c=4, Y=polyoxypropylene group)) 570g (yield 92%, viscosity 24000mPa·s, number average molecular weight; 24000).

[0193] [Synthesis example 2]

[0194] <Synthesis of vinyltri(1-cyclopenten-1-yloxy)silane>

[0195] In a 5000 mL four-necked separable flask equipped with a mechanical stirrer, a thermometer, a reflux tube and a dropping funnel, 834 g (9.9 mol) of cyclopentanone, 825 g (8.2 mol) of triethylamine, 5 g (0.05 mol) of copper (I) chloride and 1500 ml of hexane were placed, and 400 g (2.47 mol) of vinyltrichlorosilane was added dropwise at 40 to 60° C. for about 2 hours. Then, after stirring at 80° C. for 12 hours, the generated triethylamine hydrochloride was filtered off, and after hexane was distilled off from the filtrate at 100° C. and normal pressure, vinyltri(1-cyclopenten-1-yloxy)silane (yield 532 g, yield 69%) was obtained by distillation at 180° C. and 300 Pa. The reaction formula is represented by the following formula [2].

[0196] [Chemistry 15]

[0197]

[0198] [Example 1]

[0199] Preparation of the first dose a

[0200] 100 parts by mass of polyoxypropylene (viscosity: 24000 mPa·s, number average molecular weight: 24000) containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 (component (A)) and 100 parts by mass of polyoxypropylene (viscosity: 24000 mPa·s, number average molecular weight: 24000) having a BET specific surface area of ​​130 m 2 / g of dry-process silica (pyrogenic silica), 10 parts by mass, (component (B)) vinyltri(1-cyclopenten-1-yloxy)silane 7 parts by mass, (component (C)) γ-(N,N,N',N'-tetramethylguanidino)propyltrimethoxysilane 0.8 parts by mass, and (component (D)) γ-aminopropyltrimethoxysilane 1 part by mass are uniformly mixed under reduced pressure to prepare a first agent a.

[0201] Preparation of the second dose a

[0202] 100 parts by mass of polyoxypropylene (viscosity 24000 mPa·s, number average molecular weight: 24000) containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 ((A') component) and ((E) component) having a BET specific surface area of ​​130 m 2 10 parts by mass of dry-process silica (fumed silica) of 1.547 W / g were uniformly mixed under reduced pressure to prepare a second agent a.

[0203] The first agent a and the second agent a were uniformly mixed at a mixing ratio (mass ratio) of 1:1 to prepare a composition 1, and the composition 1 was applied to a substrate in a manner to a thickness of 2.5 mm. Then, the composition was allowed to stand for 1 day and 3 days respectively at 23°C and 50% RH to cure, thereby obtaining cured products 1-1 and 1-2.

[0204] [Example 2]

[0205] Preparation of the second dose b

[0206] 100 parts by mass of polyoxypropylene (viscosity 24000 mPa·s, number average molecular weight: 24000) containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 ((A') component) and 100 parts by mass of polyoxypropylene (viscosity 24000 mPa·s, number average molecular weight: 24000) having a BET specific surface area of ​​130 m 2 10 parts by mass of dry-process silica (fumed silica) having a value of 1.3477 g / g and 4 parts by mass of octylamine (component (D)) were uniformly mixed under reduced pressure to prepare a second agent b.

[0207] The first agent a and the second agent b prepared in the same manner as in Example 1 were uniformly mixed at a mixing ratio (mass ratio) of 1:1 to produce a composition 2, which was then applied to a substrate in a manner to a thickness of 2.5 mm. The composition was then cured by standing at 23° C. and 50% RH for 1 day and 3 days, respectively, to obtain cured products 2-1 and 2-2.

[0208] [Example 3]

[0209] Preparation of the first dose b

[0210] 100 parts by mass of polyoxypropylene (viscosity: 24000 mPa·s, number average molecular weight: 24000) containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 (component (A)) and 100 parts by mass of polyoxypropylene (viscosity: 24000 mPa·s, number average molecular weight: 24000) having a BET specific surface area of ​​130 m 2 / g of dry-process silica (pyrogenic silica), 10 parts by mass, (component (B)) vinyltri(1-cyclopenten-1-yloxy)silane 7 parts by mass, (component (C)) γ-(N,N,N',N'-tetramethylguanidino)propyltrimethoxysilane 0.8 parts by mass, (component (D)) γ-aminopropyltrimethoxysilane 1 part by mass, and (component (F)) γ-glycidoxypropyltrimethoxysilane 1 part by mass are uniformly mixed under reduced pressure to prepare a first agent b.

[0211] The first agent b and the second agent b prepared in the same manner as in Example 2 were uniformly mixed at a mixing ratio (mass ratio) of 1:1 to produce a composition 3, which was then applied to a substrate in a manner to a thickness of 2.5 mm. The composition was then cured by standing at 23° C. and 50% RH for 1 day and 3 days, respectively, to obtain cured products 3-1 and 3-2.

[0212] [Example 4]

[0213] Preparation of the first dose c

[0214] (Component (A)) Kaneka MS polymer S303H (polyoxypropylene having dimethoxy(methyl)silylpropyl groups capped at both ends of the molecular chain (in the above general formula (2), R 2 =R 4 =Methyl, R 3 = hydrogen atom, a=3, b=2, Y=polyoxypropylene group), manufactured by Kaneka Co., Ltd., number average molecular weight: 17500), 100 parts by mass, (component (E)) BET specific surface area: 130 m 2 / g of dry-process silica (pyrogenic silica), 10 parts by mass, (component (B)) vinyltri(1-cyclopenten-1-yloxy)silane 7 parts by mass, (component (C)) γ-(N,N,N',N'-tetramethylguanidino)propyltrimethoxysilane 0.8 parts by mass, (component (D)) γ-aminopropyltrimethoxysilane 1 part by mass, (component (F)) γ-glycidoxypropyltrimethoxysilane 1 part by mass are uniformly mixed under reduced pressure to prepare a first dose c.

[0215] The first agent c and the second agent b prepared in the same manner as in Example 2 were uniformly mixed at a mixing ratio (mass ratio) of 1:1 to produce a composition 4, which was then applied to a substrate in a manner to a thickness of 2.5 mm. The composition was then cured by standing at 23° C. and 50% RH for 1 day and 3 days, respectively, to obtain cured products 4-1 and 4-2.

[0216] [Comparative Example 1]

[0217] Preparation of the first dose

[0218] 100 parts by mass of polyoxypropylene (viscosity: 24000 mPa·s, number average molecular weight: 24000) containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 (component (A)) and 100 parts by mass of polyoxypropylene (viscosity: 24000 mPa·s, number average molecular weight: 24000) having a BET specific surface area of ​​130 m 2 / g of dry-process silica (fumed silica), 10 parts by mass, (as a substitute for the above-mentioned component (B)) vinyltrimethoxysilane 5 parts by mass, (component (C)) dioctyltin dilaurate 0.1 parts by mass, (component (D)) γ-aminopropyltrimethoxysilane 1 part by mass, and (component (F)) γ-glycidoxypropyltrimethoxysilane 1 part by mass are uniformly mixed under reduced pressure to prepare a first dose d.

[0219] The first agent d and the second agent b prepared in the same manner as in Example 2 were uniformly mixed at a mixing ratio (mass ratio) of 1:1 to produce a composition 5, which was then applied to a substrate in a manner to a thickness of 2.5 mm. The composition was then cured by standing at 23° C. and 50% RH for 1 day and 3 days, respectively, to obtain cured products 5-1 and 5-2.

[0220] [Comparative Example 2]

[0221] Preparation of the first dose

[0222] 100 parts by mass of polyoxypropylene (viscosity: 24000 mPa·s, number average molecular weight: 24000) containing silanol groups at both ends of the molecular chain synthesized in Synthesis Example 1 (component (A)) and 100 parts by mass of polyoxypropylene (viscosity: 24000 mPa·s, number average molecular weight: 24000) having a BET specific surface area of ​​130 m 2 / g of dry-process silica (fumed silica), 10 parts by mass, (as a substitute for the above-mentioned component (B)) vinyl tri(methyl ethyl ketoxime) silane 7 parts by mass, (component (C)) dioctyltin dilaurate 0.1 parts by mass, (component (D)) γ-aminopropyltrimethoxysilane 1 part by mass, and (component (F)) γ-glycidoxypropyltrimethoxysilane 1 part by mass are uniformly mixed under reduced pressure to prepare a first agent e.

[0223] The first agent e and the second agent b prepared in the same manner as in Example 2 were uniformly mixed at a mixing ratio (mass ratio) of 1:1 to produce a composition 6, which was then applied to a substrate in a manner to a thickness of 2.5 mm. The composition was then cured by standing at 23° C. and 50% RH for 1 day and 3 days, respectively, to obtain cured products 6-1 and 6-2.

[0224] [Test method]

[0225] Using each composition prepared in Examples 1 to 4 and Comparative Examples 1 and 2, curability, rubber properties, and adhesiveness were evaluated by the methods described below.

[0226] [Curing properties]

[0227] Using each of the compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2, the tack-free time (dry to touch time) was measured according to the method specified in JIS A-5758.

[0228] In addition, each composition prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was filled in a glass dish with an inner diameter of 10 mm, and the thickness from the surface part in contact with air to the cured part after 60 minutes at 23°C and 50% RH was measured to evaluate the deep curability. The case where the deep curability could be measured after 60 minutes was considered acceptable.

[0229] [Rubber properties]

[0230] Each composition immediately after preparation prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was extruded into a sheet having a thickness of 2 mm and exposed to air at 23° C. and 50% RH. The sheet was then left in the same atmosphere for 1 day or 3 days, and the rubber properties (hardness, elongation at break, tensile strength) of the obtained cured product were measured in accordance with JIS K-6249. The hardness was measured using a Durometer A durometer in JIS K-6249.

[0231] [Adhesion]

[0232] The compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were used to prepare the adherends of aluminum having a width of 25 mm and a length of 100 mm. The adherends were bonded to each other using the above compositions with a bonding area of ​​2.5 mm for each test piece. 2 , shear (shear) bonding test specimens with a bonding thickness of 1 mm were cured at 23°C and 50% RH for 1 day or 3 days, and then the shear bonding strength to aluminum was measured using the method specified in JIS K-6249.

[0233] The test results of Examples 1 to 4 are shown in Table 1, and the test results of Comparative Examples 1 and 2 are shown in Table 2. In addition, Tables 1 and 2 also show the compounds released from the curing agent during curing and the presence or absence of health hazards and environmental hazards of the compounds.

[0234] [Table 1]

[0235]

[0236] [Table 2]

[0237]

[0238] From the above results, it can be seen that the two-component room temperature fast curing resin composition of the present invention (the compositions of Examples 1 to 4) is excellent in deep curing, and the difference in rubber properties and bonding strength between curing for 1 day and curing for 3 days is small. Therefore, it has high curing properties compared with the conventional dealcoholization type (composition of Comparative Example 1) and deoxime type (composition of Comparative Example 2) curing forms.

[0239] In addition, the compound that the composition of embodiment releases in solidification is cyclopentanone, which is a compound with high safety and no reported example of environmental harmfulness such as carcinogenicity, reproductive toxicity, aquatic toxicity, etc. for human body. On the other hand, the compound that the composition of comparative example releases in solidification all shows health harmfulness in SDS (safety data sheet) etc., which is 2-butanone oxime that may cause cancer, has toxicity for aquatic organisms, is designated as highly toxic, and has strong harmful methanol for human body. In addition, methanol is compared with cyclopentanone, and flash point and boiling point are low, so it can be known that two-component type room temperature fast curing resin composition of the present invention is more excellent from the viewpoint of health, safety, environmental protection of human body.

Claims

1. A two-component room temperature fast curing resin composition, which consists of a first component and a second component, wherein the first component contains: (A) an organic polymer having a molecular chain terminal blocked with a hydrolyzable silyl group and / or a hydroxysilyl group and having no organopolysiloxane structure in the polymer main chain: 10 to 90 parts by mass, wherein: The total amount of the component (A) and the component (A') described below is 100 parts by mass. (B) a hydrolyzable organosilane compound represented by the following general formula (1) and / or a partially hydrolyzed condensate thereof: 1 to 30 parts by mass based on 100 parts by mass of the total of the components (A) and (A'); and [Chemistry 1] In the formula, R 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms, n is an integer of 1 to 8, m is 3 or 4, (C) Curing catalyst: 0.01 to 5 parts by mass based on 100 parts by mass of the total of the components (A) and (A'); The second dose contains: (A') an organic polymer having a molecular chain terminal blocked with a hydrolyzable silyl group and / or a hydroxysilyl group and containing no organopolysiloxane structure in the polymer main chain: 10 to 90 parts by mass, wherein the total of the components (A) and (A') is 100 parts by mass.

2. The two-component room temperature fast curing resin composition according to claim 1, wherein: The first and second agents each contain 0 to 5 parts by mass of a (D) curing accelerator: an organic compound having a primary amino group, based on 100 parts by mass of the total of the components (A) and (A'), and the curing accelerator is contained in an amount of 0.1 parts by mass or more in at least one of the first and second agents.

3. The two-component room temperature fast curing resin composition according to claim 1, wherein: The hydrolyzable organosilane compound of the component (B) and / or its partially hydrolyzed condensate releases the cyclic ketone compound by hydrolysis.

4. The two-component room temperature fast curing resin composition according to claim 3, wherein: The cyclic ketone compound released is cyclobutanone or cyclopentanone.

5. The two-component room temperature fast curing resin composition according to claim 1, wherein: The number average molecular weight of the organic polymer of the component (A) and the component (A') is 2,000 to 50,000.

6. The two-component room temperature fast curing resin composition according to claim 1, wherein: (C) The curing catalyst does not contain a tin catalyst.

7. The two-component room temperature fast curing resin composition according to claim 1, wherein: The first and second agents each contain 0 to 1000 parts by mass of an (E) inorganic filler based on 100 parts by mass of the total of the components (A) and (A′), and the inorganic filler is contained in at least 0.1 parts by mass in either the first or second agent.

8. The two-component room temperature fast curing resin composition according to claim 7, wherein: The component (E) is one or more inorganic fillers selected from the group consisting of calcium carbonate, fumed silica, precipitated silica, carbon black and alumina.

9. The two-component room temperature fast curing resin composition according to claim 1, wherein: The first and second agents each contain 0 to 5 parts by mass of an adhesion promoter (F) based on 100 parts by mass of the total of the components (A) and (A′), and the adhesion promoter is contained in at least 0.1 parts by mass in either the first or second agent.

10. The two-component room temperature fast curing resin composition according to claim 1, wherein: The mixing ratio of the first agent to the second agent is 1:1 to 10:1 by mass. 11 . An automobile part comprising a cured product of the two-component room temperature rapid curing resin composition according to claim 1 . 12 . An electric or electronic component comprising a cured product of the two-component room temperature rapid curing resin composition according to claim 1 .

13. A building structure comprising a cured product of the two-component room temperature rapid curing resin composition according to any one of claims 1 to 10.

14. A civil engineering structure comprising a cured product of the two-component room temperature rapid curing resin composition according to any one of claims 1 to 10.

15. An adhesive comprising the two-component room temperature rapid curing resin composition according to any one of claims 1 to 10.

16. A sealant comprising the two-component room temperature rapid curing resin composition according to any one of claims 1 to 10.

17. A potting agent comprising the two-component room temperature rapid curing resin composition according to any one of claims 1 to 10.

18. A coating agent comprising the two-component room temperature rapid curing resin composition according to any one of claims 1 to 10.

Images