WO2020189463A1

WO2020189463A1 - Room-temperature-curable resin composition, coating material, adhesive, sealing material, and article

Info

Publication number: WO2020189463A1
Application number: PCT/JP2020/010676
Authority: WO
Inventors: 大樹片山; 晃嗣藤原; 晃打它; 成紀安田; 山田　哲郎; 宗直廣神
Original assignee: 信越化学工業株式会社
Priority date: 2019-03-18
Filing date: 2020-03-12
Publication date: 2020-09-24
Also published as: JPWO2020189463A1; JP7513016B2

Abstract

A room-temperature-curable resin composition which comprises (A) 100 parts by mass of a polymer in which both ends of the molecular chain have been blocked with silanol groups or hydrolyzable silyl groups, (B) 0.1-30 parts by mass of a hydrolyzable organosilane compound represented by general formula (1) and/or a product of the partial hydrolytic condensation of the compound (in formula (1), the R¹ moieties are each independently an (un)substituted monovalent hydrocarbon group having 1-12 carbon atoms, R² is an (un)substituted monovalent hydrocarbon group having 1-12 carbon atoms, Y is a hydrolyzable group, and n is 0, 1, or 2), and (C) 0.001-20 parts by mass of a curing catalyst. The room-temperature-curable resin composition has excellent curability.

Description

Room temperature curable resin compositions, coatings, adhesives and sealants, and articles

In the present invention, as a silicon group that can be crosslinked by forming a siloxane bond (hereinafter, also referred to as "reactive silicon group"), it is bonded to a silicon atom (that is, a silanol group) bonded to a hydroxyl group or a hydrolyzable group. A room temperature curable resin composition containing a polymer having a silicon atom (that is, a hydrolyzable silyl group) at both ends of the molecular chain as a main agent (base polymer), particularly a silicone polymer (that is, both molecular chains) as the polymer. A room-temperature curable organopolysiloxane resin composition (room-curable organopolysiloxane resin composition) containing, as a main component, an organopolysiloxane structure having an organopolysiloxane structure in which the ends are sealed with a silanol group or a hydrolyzable silyl group and consisting of repeating diorganosiloxane units. (Reactive Silicone Resin Composition), and further coated, adhered and sealed with a coating agent, an adhesive and a sealing agent containing the room temperature curable resin composition, and a cured product of the room temperature curable resin composition. With respect to articles with at least one of them.

The polymer having a reactive silicon group is hydrolyzed and condensed in the presence of water. This polymer having a reactive silicon group can be crosslinked and cured in the presence of moisture and used as a room temperature curable resin composition.
Among these polymers, those whose main chain is a silicon-containing compound (particularly, organopolysiloxane) are generally known as silicone polymers. Room temperature curable resin compositions using these have the characteristic that they are liquid at room temperature and become rubber elastic bodies when cured, and by utilizing these characteristics, they are widely used in coating agents, adhesives, building sealants, etc. It is used. In these room temperature curable resin compositions, alkoxysilane, a partially hydrolyzed condensate thereof, and the like are used as a cross-linking agent and a storage stabilizer. These alkoxysilanes and their partially hydrolyzed condensates are widely and generally used in order to rapidly cure the room temperature curable resin composition (Patent Documents 1 to 5: JP-A-7-070551, JP-A-P. 11-15883A, 2003-147203, 2012-036397, 2016-079303).

However, even if these compounds are used, a sufficient curing rate has not been obtained. If a large amount of these compounds are blended in order to increase the curing rate, there may be a problem that curing is delayed, the cured product becomes too hard, or it is economically disadvantageous.

Japanese Unexamined Patent Publication No. 7-070551 Japanese Unexamined Patent Publication No. 11-15883 Japanese Unexamined Patent Publication No. 2003-147203 Japanese Unexamined Patent Publication No. 2012-036397 Japanese Unexamined Patent Publication No. 2016-079303

The present invention has been made in view of the above circumstances, and is a room temperature curable resin composition having excellent curability, a coating agent, an adhesive and a sealing agent composed of the room temperature curable resin composition, and the room temperature curable resin composition. It is an object of the present invention to provide an article which has been coated, adhered or sealed with a cured product of the substance.

As a result of diligent studies to achieve the above object, the present inventors have conducted a hydrolyzable organosilicon compound (organosilane compound and / or) containing a specific organooxymethyl group represented by the following general formula (1). It has been found that the partially hydrolyzed condensate) is useful for solving the above-mentioned problems, and has led to the present invention.

That is, the present invention provides the following room temperature curable resin compositions, coating agents, adhesives and sealing agents, articles and the like.
1. 1.
(A) Polymer in which both ends of the molecular chain are sealed with a silanol group or a hydrolyzable silyl group: 100 parts by mass,
(B) Hydrolyzable organosilane compound represented by the following general formula (1) and / or a partially hydrolyzed condensate thereof: 0.1 to 30 parts by mass,

(In the formula (1), R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ² is an unsubstituted or substituted monovalent group having 1 to 12 carbon atoms. It is a hydrocarbon group, Y is a hydrolyzable group, and n is 0, 1 or 2.)
(C) Curing catalyst: A room temperature curable resin composition containing 0.001 to 20 parts by mass.
2. 2.
Further, with respect to 100 parts by mass of the component (A),
(D) Filler: 1 to 1,000 parts by mass,
(E) Adhesion promoter (excluding component (B)): 0.1 to 30 parts by mass, and (F) Plasticizer: 1 or more selected from 1 to 1,000 parts by mass The room temperature curable resin composition according to 1.
3. 3.
Further, with respect to 100 parts by mass of the component (A),
(G) The room temperature curable resin according to 1 or 2, which contains 0.01 to 30 parts by mass of a storage stabilizer and / or a cross-linking agent (excluding components (B) and (E)). Composition.
4.
The component (A) is a diorganopolysiloxane in which both ends of the molecular chain represented by the following general formula (2a) are sealed with silanol groups, or both ends of the molecular chain represented by the following general formula (2b) are hydrolyzed. The room temperature curable resin composition according to any one of 1 to 3, which is a diorganopolysiloxane sealed with a sexyl group.

(In formulas (2a) and (2b), R ³ is a monovalent hydrocarbon group having 1 to 12 carbon atoms independently substituted or substituted, and A is an oxygen atom or 2 to 8 carbon atoms. It is a valent hydrocarbon group, X is a hydrolyzable group, b is 0 or 1, and m is an integer having a viscosity of this diorganopolysiloxane at 23 ° C. of 100 to 1,000,000 mPa · s. is there.)
5.
A coating agent comprising the room temperature curable resin composition according to any one of 1 to 4.
6.
An adhesive comprising the room temperature curable resin composition according to any one of 1 to 4.
7.
A sealant comprising the room temperature curable resin composition according to any one of 1 to 4.
8.
An article having a coating layer made of a cured product of the room temperature curable resin composition according to any one of 1 to 4.
9.
An article adhered and / or sealed with a cured product of the room temperature curable resin composition according to any one of 1 to 4.

The room temperature curable resin composition of the present invention cross-links a specific hydrolyzable organosilane compound containing an organooxymethyl group such as an alkoxymethyl group in the molecule and / or a partially hydrolyzed condensate thereof (curing agent). By containing the compound, it has the effect of curing extremely quickly at room temperature (23 ° C ± 15 ° C) due to the humidity in the air.

Hereinafter, the room temperature curable resin composition according to the present invention will be described in more detail.

(A) Ingredient:
The component (A) used in the room temperature curable resin composition of the present invention is a polymer in which both ends of the molecular chain are sealed with a silanol group (a hydroxyl group bonded to a silicon atom) or a hydrolyzable silyl group, and is a polymer of the present invention. It acts as the main agent (base polymer) of the room temperature curable resin composition. Such a base polymer has, in particular, a silicone polymer (that is, an organopolysiloxane structure in which both ends of the molecular chain are sealed with a silanol group or a hydrolyzable silyl group and consists of repeating diorganosiloxane units as a main chain. Basically, a linear polymer) is preferable, and the composition is preferably a room temperature curable organopolysiloxane resin composition (room temperature curable silicone resin composition) containing the silicone polymer.

Specifically, the silicone polymer is represented by a basically linear diorganopolysiloxane in which both ends of the molecular chain represented by the following general formula (2a) are sealed with silanol groups, or the following general formula (2b). A diorganopolysiloxane having both ends of the molecular chain sealed with a hydrolyzable silyl group is used.

(In formulas (2a) and (2b), R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and A is an oxygen atom. Alternatively, it is a divalent hydrocarbon group having 1 to 8 carbon atoms, X is a hydrolyzable group, b is 0 or 1, and m is the viscosity of this diorganopolysiloxane at 23 ° C. of 100 to 1, It is an integer of ,000,000 mPa · s.)

Here, in the general formulas (2a) and (2b), the unsubstituted or substituted monovalent hydrocarbon group represented by R ³ has 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms. Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group. , Dodecyl group and other alkyl groups; cyclopentyl group, cyclohexyl group and other cycloalkyl groups; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group, hexenyl group and other alkenyl groups; phenyl group, trill group , Aryl groups such as xsilyl group, α-, β-naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group, 3-phenylpropyl group; and some or all of the hydrogen atoms of these groups. Examples of groups substituted with halogen atoms such as F, Cl, Br, and cyano groups, such as 3-chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group, and the like can be exemplified. Among these, it is preferable to remove an aliphatic unsaturated hydrocarbon group such as an alkenyl group, an alkyl group such as a methyl group and an ethyl group and an aryl group such as a phenyl group are more preferable, and a methyl group is particularly preferable.

A is a divalent hydrocarbon group having an oxygen atom or a carbon atom number of 1 to 8, preferably a carbon atom number of 2 to 4, and the divalent hydrocarbon group is − (CH ₂ ) _p − or − (CH =). CH) alkylene groups such as _q − (p represents an integer of 1 to 8, preferably an integer of 2 to 4, and q represents an integer of 1 to 4) and an alkenylene group are preferable. Among these oxygen _{_{atoms, -CH 2 CH 2 -, -}} CH 2 CH 2 CH 2 -, - CH = CH- are preferred.

X is a hydrolyzable group, for example, an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. An alkoxyalkoxy group having 2 to 4 carbon atoms such as a methoxyethoxy group, an ethoxyethoxy group and a methoxypropoxy group; an asyloxy group having 2 to 8 carbon atoms such as an acetoxy group, a propionoxy group, an octanoyloxy group and a benzoyloxy group. Alkoxyoxy group having 2 to 6 carbon atoms such as vinyloxy group, propenyloxy group, isopropenyloxy group, 1-ethyl-2-methylvinyloxy group; dimethylketooxime group, methylethylketooxime group, diethylketooxime group, etc. Ketooxime group having 3 to 7 carbon atoms; amino group having 2 to 6 carbon atoms such as dimethylamino group, diethylamino group, butylamino group and cyclohexylamino group; carbon atom number such as dimethylaminoxy group and diethylaminoxy group Examples thereof include 2 to 6 aminoxime groups; amide groups having 3 to 8 carbon atoms such as N-methylacetamide group, N-ethylacetamide group and N-methylbenzamide group. Of these, an alkoxy group is particularly preferable.
b is 0 or 1, and a preferable number can be used depending on the curability of the room temperature curable resin composition and the physical properties of the cured product.

m is a number having a viscosity of this diorganopolysiloxane at 23 ° C. of 100 to 1,000,000 mPa · s, and m is usually an integer of 20 to 2,000, preferably an integer of 20 to 1,600. It is more preferably an integer of 20 to 1,000, and even more preferably an integer of about 20 to 500.
Here, the viscosity of the diorganopolysiloxane at 23 ° C. is preferably 100 to 1,000,000 mPa · s, more preferably 300 to 500,000 mPa · s, and particularly preferably 500 to 100,000 mPa · s. It is 1,000 to 80,000 mPa · s. The viscosity is a numerical value measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, rheometer, etc.) (hereinafter, the same applies). The m value indicating the number of repetitions (or degree of polymerization) of the disiloxane unit ((R ³ ) ₂ SiO _2/2 ) constituting the main chain in the silicone polymer is usually gel permeation using toluene or the like as a developing solvent. It can be determined as a polystyrene-equivalent number average degree of polymerization (or number average molecular weight) or the like in an ion chromatography (GPC) analysis (hereinafter, the same applies).

Specific examples of the component (A) include the following.

(In each formula, R ³ , X, b, m are the same as above.)

The base polymer in which both ends of the molecular chain of the component (A) are sealed with a silanol group or a hydrolyzable silyl group can be used alone or in combination of two or more having different structures and degrees of polymerization.

(B) Ingredient:
The room temperature curable resin composition of the present invention contains a hydrolyzable organosilane compound represented by the following general formula (1) and containing an organooxymethyl group such as an alkoxymethyl group bonded to a silicon atom in the molecule and /. Alternatively, it is characterized by containing a partially hydrolyzed condensate thereof as a cross-linking agent (hardener). In the present invention, the "partially hydrolyzable condensate" is preferably two or more residual hydrolyzable groups in the molecule, which is produced by partially hydrolyzing and condensing the hydrolyzable organosilane compound. It means an organosiloxane oligomer having three or more.

(In the formula, R ¹ is an independently unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Reference numeral ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms, and Y is a hydrolyzable group. n is 0, 1 or 2)

Here, in the general formula (1), the unsubstituted or substituted carbon atom number 1 to 12, preferably the carbon atom number 1 to 8, more preferably the carbon atom number 1 to 4, represented by R ¹ , is monovalent. The hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and 2-ethylhexyl group. , Alkyl groups such as nonyl group, decyl group, dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group and hexenyl group. Aryl groups such as phenyl group, trill group, xsilyl group, α-, β-naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group and 3-phenylpropyl group; and hydrogen atoms of these groups A group partially or wholly substituted with a halogen atom such as F, Cl, Br, or a cyano group, for example, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethyl group, etc. It can be exemplified. Among these, it is preferable to remove an aliphatic unsaturated hydrocarbon group such as an alkenyl group, an alkyl group such as a methyl group and an ethyl group is more preferable, and a methyl group is particularly preferable.

Next, in the general formula (1), the unsubstituted or substituted carbon atom number 1 to 12, preferably the carbon atom number 1 to 8, and more preferably the carbon atom number 1 to 4 monovalent represented by R ^2. The hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group and 2-ethylhexyl group. , Alkyl groups such as nonyl group, decyl group, dodecyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; alkenyl groups such as vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group, pentenyl group and hexenyl group. Aryl groups such as phenyl group, trill group, xsilyl group, α-, β-naphthyl group; aralkyl groups such as benzyl group, 2-phenylethyl group and 3-phenylpropyl group; and hydrogen atoms of these groups A group partially or wholly substituted with a halogen atom such as F, Cl, Br, or a cyano group, for example, a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethyl group, etc. , Examples of alkyl groups in which some of the hydrogen atoms of these groups are substituted with lower alkoxy groups such as methoxy group and ethoxy group, for example, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group and the like. be able to. Among these, lower alkyl groups having 1 to 4 carbon atoms such as a methyl group and an ethyl group are preferable.

Further, in the general formula (1), Y is a hydrolyzable group, and for example, the number of carbon atoms of a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a tert-butoxy group and the like is 1. Alkoxy group of ~ 4; alkoxyalkoxy group having 2 to 4 carbon atoms such as methoxyethoxy group, ethoxyethoxy group, methoxypropoxy group; having 2 to 8 carbon atoms such as acetoxy group, octanoyloxy group, benzoyloxy group Asiloxy group; Alkoxyoxy group having 2 to 6 carbon atoms such as vinyloxy group, propenyloxy group, isopropenyloxy group, 1-ethyl-2-methylvinyloxy group; dimethylketooxym group, methylethylketooxime group, diethylketooxym Ketooxime group having 3 to 7 carbon atoms such as a group; amino group having 2 to 6 carbon atoms such as dimethylamino group, diethylamino group, butylamino group and cyclohexylamino group; carbon such as dimethylaminoxy group and diethylaminoxy group Aminoxy groups having 2 to 6 atoms; amide groups having 3 to 8 carbon atoms such as N-methylacetamide group, N-ethylacetamide group, N-methylbenzamide group and the like can be mentioned. Of these, an alkoxy group is particularly preferable. n is 0, 1 or 2, preferably 0 or 1, and more preferably 0.

A hydrolyzable organosilane compound containing an organooxymethyl group such as an alkoxymethyl group bonded to a silicon atom in the molecule represented by the above general formula (1) according to the present invention, and a partially hydrolyzed condensate thereof. Specific examples include methoxymethyltrimethoxysilane, ethoxymethyltriethoxysilane, methoxymethylmethyldimethoxysilane, ethoxymethylmethyldiethoxysilane, methoxymethylethyldimethoxysilane, ethoxymethylethyldiethoxysilane, methoxymethylhexyldimethoxysilane, and ethoxy. Examples thereof include methylhexyldiethoxysilane, methoxymethyloctyldimethoxysilane, ethoxymethyloctyldiethoxysilane, methoxymethylphenyldimethoxysilane, ethoxymethylphenyldiethoxysilane, and a partially hydrolyzed condensate thereof.
For example, the structural formulas of methoxymethyltrimethoxysilane and ethoxymethyltriethoxysilane in the above specific example are as follows.

In the room temperature curable resin composition of the present invention, the hydrolyzable organosilane compound containing the organooxymethyl group of the component (B) and / or its partially hydrolyzed condensate is silanol in the base polymer of the component (A). It acts as a cross-linking agent (hardener) that forms a cross-linked structure by a reaction that hydrolyzes with a group or a hydrolyzable silyl group in the presence of moisture such as moisture and condenses, and the component (B) The amount of the hydrolyzable organosilane compound and / or its partially hydrolyzed condensate is 100 parts by mass of the base polymer in which both ends of the molecular chain of the component (A) are sealed with a silanol group or a hydrolyzable silyl group. It is 0.1 to 30 parts by mass, preferably 0.5 to 10 parts by mass. If the amount of the component (B) is too small, sufficient rubber physical properties may not be obtained even if the composition is cured, and if the amount is too large, the quick curing property is impaired or it is economically disadvantageous.

(C) component:
The component (C) of the present invention is a curing catalyst (non-metallic organic catalyst and / or metal-based catalyst), and acts to accelerate the curing of the room temperature curable resin composition of the present invention.

As the non-metallic organic catalyst of the curing catalyst, known ones as a curing accelerator of the condensation curing type organopolysiloxane composition can be used, and are not particularly limited. For example, phosphazene-containing compounds such as N, N, N', N', N'', N''-hexamethyl-N'''-(trimethylsilylmethyl) -phosphorimidic triamide, 3-aminopropyltrimethoxysilane. , 3-Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyl Hydrolytable aminosilane compounds such as aminoalkyl group-substituted alkoxysilanes such as (methyl) dimethoxysilane, N-β (aminoethyl) γ-aminopropyl (methyl) diethoxysilane and / or partially hydrolyzed condensates thereof, hexylamine. , Amine compounds such as dodecylamine phosphate or salts thereof, quaternary ammonium salts such as benzyltriethylammonium acetate, dialkylhydroxylamines such as dimethylhydroxylamine and diethylhydroxylamine, tetramethylguanidylpropyltrimethoxysilane, tetramethyl Examples thereof include hydrolyzable silanes and siloxanes containing guanidyl groups such as guanidylpropylmethyldimethoxysilane and tetramethylguanidylpropyltris (trimethylsiloxy) silane, but non-metallic organic catalysts are not limited thereto. .. Further, the non-metallic organic catalyst may be used alone or in combination of two or more.

As the metal-based catalyst of the curing catalyst, known ones as a curing accelerator of the condensation curing type organopolysiloxane composition can be used, and are not particularly limited. For example, alkyltin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctate, dioctyltin dineodecanoate, di-n-butyl-dimethoxytin, tetraisopropoxytitanium, tetra-n-butoxytitanium, Titanic acid esters or titanium chelate compounds such as tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetonato) titanium, titanium isopropoxyoctylene glycol, zinc naphthenate, zinc stearate, zinc-2-ethyloctate, Alcolate aluminum compounds such as iron-2-ethylhexoate, cobalt-2-ethylhexoate, manganese-2-ethylhexoate, cobalt naphthenate, aluminum isopropyrate, aluminum secondary butyrate, aluminum alkyl acetate. Aluminum chelate compounds such as diisopropylate, aluminum bisethylacetate acetate / monoacetylacetonate, bismuth neodecanoate (III), bismuth 2-ethylhexanoate (III), bismuth citrate (III), bismuth octylate and the like. Examples thereof include lower fatty acid salts of alkali metals such as metal compounds, potassium acetate, sodium acetate, and lithium oxalate, but metal-based catalysts are not limited thereto. Further, the metal-based catalyst may be used alone or in combination of two or more.

The blending amount of the curing catalyst of the component (C) is 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A). If the amount of the component (C) is too small, sufficient curability cannot be obtained, and if it is too large, the curability is too fast, resulting in insufficient working time, which is economically disadvantageous.

Ingredient (D):
The component (D) is a filler (inorganic filler and / or organic resin filler), and is an optional component to be blended in the room temperature curable resin composition of the present invention as needed, and is formed from this composition. It is used to give the cured product sufficient mechanical strength. Known fillers can be used, for example, dry silica such as pulverized silica, molten silica, spherical silica, fumes silica (fumed silica), and crystalline silica (fine powdered silica), and sedimentability. Silica-based fillers such as wet silica such as silica and sol-gel silica, hydrophobic silica-based fillers in which the surface of these silica-based fillers is surface-treated with an organic silicon compound, glass beads, glass balloons, transparent resin beads, etc. Metal oxides such as silica aerogel, diatomaceous earth, iron oxide, zinc oxide, titanium oxide, fuming metal oxide, reinforcing agents such as carbon black, talc, zeolite and bentonite, asbestos, glass fiber, carbon fiber, calcium carbonate, carbon dioxide. Metal carbonates such as magnesium and zinc carbonate, glass wool, fine powder mica, molten silica powder, polystyrene, polyvinyl chloride, synthetic resin powder such as polypropylene and the like are used. Among these fillers, inorganic fillers such as silica, calcium carbonate, and zeolite are preferable, and aerosol silica and calcium carbonate whose surface is hydrophobized are particularly preferable.

When the filler of the component (D) is blended, the blending amount is preferably 1 to 1,000 parts by mass, particularly 5 to 400 parts by mass with respect to 100 parts by mass of the component (A). The cured product obtained from this composition tends to exhibit sufficient mechanical strength when it is blended than when it is not blended, and when it is used in a larger amount than 1,000 parts by mass, the viscosity of the composition increases. Not only does the workability deteriorate, but the rubber strength after curing tends to decrease, making it difficult to obtain rubber elasticity.

(E) Ingredient:
The component (E) is an adhesion accelerator other than the above components (B) and (C), and is an optional component to be blended in the room temperature curable resin composition of the present invention, if necessary, from this composition. It is used to give sufficient adhesion to the cured product formed. Specifically, hydrolyzable epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- (meth) acryloxipropyltrimethoxysilane, Hydrolyzable (meth) acrylic silanes such as γ- (meth) acryloxypropyltriethoxysilane, hydrolyzable mercaptosilanes such as γ-mercaptopropyltrimethoxysilane, hydrolysis of γ-isocyanoxidetrimethoxysilane, etc. It contains functional groups (excluding amino groups and guanidyl groups) having heteroatoms such as nitrogen atom, oxygen atom and sulfur atom in addition to hydrolyzable groups such as sex isocyanate silanes (other than organooxymethyl group). It is preferable to blend a hydrolyzable organosilane compound (so-called carbon functional silane or silane coupling agent) having a monovalent hydrocarbon group in the molecule. The adhesion accelerator (carbon functional silane or silane coupling agent) of the component (E) does not contain an organooxy-substituted alkyl group such as an organooxymethyl group in the molecule other than the hydrolyzable group. In a certain point, it is clearly distinguished from the hydrolyzable organosilane compound of the component (B) and / or its partially hydrolyzed condensate, and is amino in the molecule other than the hydrolyzable group. It is clearly distinguished from the hydrolyzable aminosilane compound of the component (C) and / or its partially hydrolyzed condensate in that it does not contain a substituted alkyl group.

When the adhesion promoter of the component (E) is blended, the blending amount thereof is 0.1 to 30 parts by mass, particularly 0.2 to 20 parts by mass, particularly 0 with respect to 100 parts by mass of the component (A). .5 to 20 parts by mass is preferable. If it exceeds 30 parts by mass, the curability may be insufficient or it may be economically disadvantageous.

(F) component:
The component (F) is a plasticizer, which is an optional component to be blended in the room temperature curable resin composition of the present invention as needed, and exhibits the mechanical properties and flame retardancy of the cured product formed from this composition. The viscosity can be adjusted so that it is easy to handle in construction without damaging it.

Examples of the plasticizer used in the room temperature curable resin composition of the present invention include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), and diheptyl phthalate (DHP). ), Dioctyl phthalate (DOP), Diisononyl phthalate (DINP), Diisodecyl phthalate (DIDP), Ditridecyl phthalate (DTDP), Butylbenzyl phthalate (BBP), Dicyclohexyl phthalate (DCHP), Tetrahydrophthalate ester, Dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutyldiglycol adipate (BXA), bis (2-ethylhexyl) azelaate (DOZ), sebacin Dibutyl acid (DBS), dioctyl sebacate (DOS), dibutyl maleate (DBM), di-2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP) , Tributyl Phthalate (TBP), Tris (2-ethylhexyl) Phthalate (TOP), Tri (Chloroethyl) Phthalate (TCEP), Trisdichloropropyl Phthalate (CPP), Tributoxyethyl Phthalate (TBXP), Tris (β-Chloropropyl) Phthalate (TMCPP), Triphenyl Phthalate (TPP), Octyldiphenyl Phthalate (ODP), Acetyltriethyl Citrate, Tributyl Acetylcitrate, etc. Others include trimellitic acid-based plasticizers, polyester-based plasticizers, chlorinated paraffins. , Phthalate-based plasticizers, and silicone oils such as dimethylpolysiloxane and methylvinylpolysiloxane (that is, organopolysiloxanes that are non-functional to condensation curing reactions), recently polyoxypropylene glycol-based, paraffin-based, Examples thereof include petroleum-based high boiling point solvents such as naphthene-based and isoparaffin-based. These may be used alone or in combination of two or more. Among them, silicone oil is particularly preferable.

As the above-mentioned silicone oil (non-functional organopolysiloxane), preferably, an organopolysiloxane represented by the following general formula (3) can be used.

In the formula (3), R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms independently substituted or substituted, and d has a viscosity of the organopolysiloxane at 23 ° C. of 1.5 to 1. , Million mPa · s.)

In the above formula (3), R ⁴ is a monovalent hydrocarbon group having 1 to 20 carbon atoms independently substituted or substituted, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, and the like. Alkyl groups such as butyl group, isobutyl group, tert-butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group; vinyl group, allyl group, propenyl group, isopropenyl group, butenyl group Alkenyl groups such as groups, pentenyl groups and hexenyl groups; aryl groups such as phenyl group, trill group, xsilyl group and naphthyl group; aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group and hydrogen atoms of these groups. Part or all of the above is substituted with a halogen atom such as F, Cl, Br, etc., for example, a chloromethyl group, a chloropropyl group, a bromoethyl group, a trifluoropropyl group and the like can be mentioned. As R ⁴ , an alkyl group such as a methyl group, a phenyl group, or a vinyl group is preferable.

In the organopolysiloxane represented by the above formula (3), the value of d indicating the number of repetitions (degree of polymerization) of the diorganosiloxane unit is usually 3 to 3,000, preferably 5 to 2,000. , More preferably, it may be an integer of about 10 to 1,000.

When the component (F) is blended, the blending amount thereof is preferably 1 to 1,000 parts by mass, more preferably 2 to 500 parts by mass, still more preferably 2 parts by mass with respect to 100 parts by mass of the component (A). Is 5 to 200 parts by mass. When the amount of the component (F) is within the above range, the viscosity can be adjusted to be easy to handle in construction without impairing the mechanical properties and flame retardancy of the room temperature curable resin composition of the present invention, which is preferable.

(G) component:
The component (G) is a storage stabilizer and / or a cross-linking agent (curing agent) other than the above components (B) and (E), and can be optionally blended in the room temperature curable resin composition of the present invention. It is an ingredient and is used to provide the storage stability and sufficient mechanical strength of the cured product formed from this composition. As the component (G), a (organo) silane compound having 3 or more, preferably 3 or 4 hydrolyzable groups such as an alkoxy group in the molecule and a partially hydrolyzed condensate thereof (that is, the (organo)). ) (Organo) siloxane oligomer (organo) having 3 or more residual hydrolyzable groups in the molecule, which is obtained by partially hydrolyzing and condensing a silane compound), and specific examples thereof include tetramethylsilane and tetraethylsilane. , Methylsilicate, Ethylsilicate and other tetraalkoxysilanes and their partial hydrolysis condensates, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, methyltris (methoxyethoxy). Organotrialkoxysilanes such as silane and vinyltris (methoxyethoxy) silanes, organotrialkoxysilanes such as methyltripropenoxysilanes, vinyltriisopropenoxysilanes and phenyltriisopropenoxysilanes, methyltriacetoxysilanes and vinyltriacetoxy Examples thereof include, but are not limited to, trifunctional hydrolyzable organosilane compounds such as organotriacyloxysilane such as silane, and partial hydrolysis condensates thereof. These can be used alone or in combination of two or more.

The (organo) silane compound having three or more hydrolyzable groups as a storage stabilizer and / or a cross-linking agent (hardener) of the component (G) and their partially hydrolyzable condensates are hydrolyzable groups. Other than this, it is clearly distinguished from the hydrolyzable organosilane compound of the above component (B) in that it does not contain an organooxy-substituted alkyl group such as an organooxymethyl group in the molecule. In addition to the hydrolyzable group, the component (G) does not contain a substituted monovalent hydrocarbon group containing a functional group having a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom in the molecule. In that respect, it is also clearly distinguished from the adhesion accelerator (carbon functional silane or silane coupling agent) of the above component (E).

When a storage stabilizer and / or a cross-linking agent (curing agent) for the component (G) is blended, the blending amount thereof is 0.01 to 30 parts by mass with respect to 100 parts by mass of the component (A). 0.1 to 30 parts by mass, particularly 1 to 10 parts by mass is preferable. If it exceeds 30 parts by mass, the mechanical properties of the obtained rubber property are also deteriorated, which causes a problem that it is economically disadvantageous.

[Other ingredients]
In addition, the room temperature curable resin composition of the present invention contains known additives such as pigments, dyes, antioxidants, antioxidants, antistatic agents, antimony oxides, and flame retardants such as chlorinated paraffin as additives. can do. Further, a polyether as a thixophilic improver, a fungicide, and an antibacterial agent can be blended.

Further, the room temperature curable resin composition of the present invention may use an organic solvent if necessary. Examples of the organic solvent include aliphatic hydrocarbon compounds such as n-hexane, n-heptane, isooctane, and isododecane, aromatic hydrocarbon compounds such as toluene and xylene, hexamethyldisiloxane, octamethyltrisiloxane, and decamethyltetra. Siloxane, dodecamethylpentasiloxane, chain siloxane such as 2- (trimethylsiloxy) -1,1,1,2,3,3,3-heptamethyltrisiloxane, octamethylcyclopentasiloxane, decamethylcyclopentasiloxane, etc. Cyclic siloxane and the like. The amount of the organic solvent may be appropriately adjusted within a range that does not interfere with the effects of the present invention.

The room temperature curable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components and predetermined amounts of the above-mentioned various additives in a dry atmosphere. Further, the room temperature curable resin composition of the present invention is cured by being left at room temperature, and known methods and conditions depending on the type of the composition can be adopted as the molding method, curing conditions and the like. ..

The room temperature curable resin composition of the present invention, particularly the one-component composition, is stored at room temperature (23) in the absence of moisture, that is, in a closed container in which moisture is shielded, and exposed to moisture in the air during use. It cures easily at ° C. ± 15 ° C.).

Further, the obtained cured product shows good flexibility and has rubber elasticity, so that it is useful as a coating agent, an adhesive, and a sealing agent (for example, a building sealant). The method of using the room temperature curable resin composition of the present invention as a coating agent, an adhesive, and a sealing agent may be in accordance with conventionally known usage methods, and is not particularly limited.

Examples of articles on which a coating layer made of a cured product of the room temperature curable resin composition of the present invention is formed include articles composed of glasses, various resins, various metals, and the like. The material and shape of the above are not particularly limited.

Examples of the article to be adhered and / or sealed with the cured product of the room temperature curable resin composition of the present invention include articles composed of glass, various metals and the like, and the material and shape of the base material. Is not particularly limited.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following specific example, "part" means "part by mass", and the viscosity indicates a value measured by a rotational viscometer at 23 ° C.

[Example 1]
A linear dimethylpolysiloxane in which both ends of a molecular chain having a viscosity of 5,000 mPa · s are sealed with a hydroxyl group (silanol group) bonded to a silicon atom (in the general formula (2a), R ³ = methyl group, A = oxygen atom). 100 parts (corresponding to m = about 400), 4.6 parts of methoxymethyltrimethoxysilane, and 1.0 part of tetramethylguanidylpropyltrimethoxysilane are mixed until they become uniform under moisture isolation. Composition 1 was prepared.

[Example 2]
In Example 1, 6.2 parts of ethoxymethyltriethoxysilane was used instead of 4.6 parts of methoxymethyltrimethoxysilane, and the composition 2 was prepared in the same manner as in Example 1 except for the above.

[Example 3]
In Example 1, 1.0 part of 3-aminopropyltriethoxysilane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 1.0 part of tetramethylguanidylpropyltrimethoxysilane. The composition 3 was prepared in the same manner as in Example 1 except for the above.

[Example 4]
In Example 2, 1.0 part of 3-aminopropyltriethoxysilane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 1.0 part of tetramethylguanidylpropyltrimethoxysilane. The composition 4 was prepared in the same manner as in Example 2 except for the above.

[Comparative Example 1]
In Example 1, 3.8 parts of methyltrimethoxysilane (KBM-13: manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 4.6 parts of methoxymethyltrimethoxysilane, and other than that, the same as in Example 1. The composition 5 was prepared.

[Comparative Example 2]
In Example 1, 4.1 parts of methyltriethoxysilane (KBE-13: manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 4.6 parts of methoxymethyltrimethoxysilane, and other than that, the same as in Example 1. The composition 6 was prepared.

[Comparative Example 3]
In Example 3, 3.8 parts of methyltrimethoxysilane (KBM-13: manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 4.6 parts of methoxymethyltrimethoxysilane, and other than that, the same as in Example 3. The composition 7 was prepared.

〔Evaluation test〕
The tack-free time of each composition prepared in Examples 1 to 4 and Comparative Examples 1 to 3 was measured according to JIS K-6249.
Further, each composition immediately after preparation prepared in Examples 1 to 4 and Comparative Examples 1 to 3 was extruded into a sheet having a thickness of 2 mm, and left in air at 23 ° C. and 50% RH for 7 days. The physical properties of the cured product (initial physical properties: hardness, maximum point strength, fracture point elongation) were measured in accordance with JIS K-6249. The hardness was measured using a JIS K-6249 Durometer A hardness tester.
The above results are shown in Table 1.
In the table, the tack free time of "240 minutes or more" means that the film has not yet cured after 240 minutes (there is a tack feeling), and the curing (no tack feeling) has been confirmed after being left for 7 days. "Uncured" means that it has not been cured even after being left for 7 days.

From the results in Table 1, it was clarified that Examples 1 to 4 have higher curability than Comparative Examples 1 to 3 without impairing the characteristics of the cured resin product.

[Example 5]
Linear dimethylpolysiloxane in which both ends of a molecular chain having a viscosity of 20,000 mPa · s are sealed with a trimethoxysilyl group (in general formula (2b), X = methoxy group, R ³ = methyl group, b = 0, A = 100 parts of silicone polymer A), which is an oxygen atom and corresponds to m = about 600, 4.6 parts of methoxymethyltrimethoxysilane, and 1.0 part of tetramethylguanidylpropyltrimethoxysilane under moisture isolation. Composition 8 was prepared by mixing until uniform.

[Example 6]
In Example 5, 1.0 part of 3-aminopropyltriethoxysilane (KBE-903: manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 1.0 part of tetramethylguanidylpropyltrimethoxysilane. The composition 9 was prepared in the same manner as in Example 5 except for the above.

[Example 7]
In Example 5, instead of 100 parts of linear dimethylpolysiloxane (silicone polymer A) in which both ends of the molecular chain having a viscosity of 20,000 mPa · s are sealed with a trimethoxysilyl group, a molecule having a viscosity of 30,000 mPa · s Linear dimethylpolysiloxane in which both ends of the chain are sealed with a trimethoxysilylethyl group (in the general formula (2b), X = methoxy group, R ³ = methyl group, b = 0, A = -CH ₂ CH _2- The composition 10 was prepared in the same manner as in Example 5 except that 100 parts of the silicone polymer B) corresponding to m = about 750 was used.

[Comparative Example 4]
In Example 6, 3.8 parts of methyltrimethoxysilane (KBM-13: manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of 4.6 parts of methoxymethyltrimethoxysilane, and other than that, the same as in Example 6. The composition 11 was prepared.

[Comparative Example 5]
In Example 6, instead of 100 parts of linear dimethylpolysiloxane (silicone polymer A) in which both ends of the molecular chain having a viscosity of 20,000 mPa · s are sealed with a trimethoxysilyl group, a molecule having a viscosity of 20,000 mPa · s Using 100 parts of linear dimethylpolysiloxane (silicone polymer C) with both ends of the chain sealed with silanol groups, instead of 4.6 parts of methoxymethyltrimethoxysilane, methyltrimethoxysilane (KBM-13: Shinetsu Kagaku) The composition 12 was prepared in the same manner as in Example 6 except that 3.8 parts (manufactured by Kogyo Co., Ltd.) was used.

〔Evaluation test〕
The tack free time of each composition prepared in Examples 5 to 7 and Comparative Examples 4 and 5 was measured according to JIS K-6249.
In addition, each composition immediately after preparation prepared in Examples 5 to 7 and Comparative Examples 4 and 5 was extruded into a sheet having a thickness of 2 mm and exposed in air at 23 ° C. and 50% RH for 7 days. , It was confirmed whether or not a cured product could be obtained.
As a result of the test, when the tack free time is within 60 minutes, the case where the cured product is obtained is good (symbol 〇), and when the tack free time is more than 60 minutes, the case where the cured product is not obtained is bad (symbol 〇). It was evaluated as a symbol ×).
Further, each composition prepared in Examples 5 to 7 and Comparative Examples 4 and 5 was filled in a polyethylene cartridge and stored in a dryer at 70 ° C. for 7 days. The curability of the composition returned to room temperature after storage was evaluated in the same manner as immediately after preparation.
The above results are shown in Table 2.

From the results in Table 2, it was clarified that Examples 5 to 7 had better curability than Comparative Examples 4 and 5. It was also found that Examples 5 to 7 had good storage stability.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any one having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same action and effect is of the present invention. Included in the technical scope.

Claims

(A) Polymer in which both ends of the molecular chain are sealed with a silanol group or a hydrolyzable silyl group: 100 parts by mass,
(B) Hydrolyzable organosilane compound represented by the following general formula (1) and / or a partially hydrolyzed condensate thereof: 0.1 to 30 parts by mass,

(In the formula (1), R 1 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and R 2 is an unsubstituted or substituted monovalent group having 1 to 12 carbon atoms. It is a hydrocarbon group, Y is a hydrolyzable group, and n is 0, 1 or 2.)
(C) Curing catalyst: A room temperature curable resin composition containing 0.001 to 20 parts by mass.
Further, with respect to 100 parts by mass of the component (A),
(D) Filler: 1 to 1,000 parts by mass,
(E) Adhesion promoter (excluding component (B)): 0.1 to 30 parts by mass, and (F) Plasticizer: 1 or more selected from 1 to 1,000 parts by mass The room temperature curable resin composition according to claim 1.
Further, with respect to 100 parts by mass of the component (A),
(G) Room temperature curing according to claim 1 or 2, which contains 0.01 to 30 parts by mass of a storage stabilizer and / or a cross-linking agent (excluding components (B) and (E)). Sex resin composition.
The component (A) is a diorganopolysiloxane in which both ends of the molecular chain represented by the following general formula (2a) are sealed with silanol groups, or both ends of the molecular chain represented by the following general formula (2b) are hydrolyzed. The room temperature curable resin composition according to any one of claims 1 to 3, which is a diorganopolysiloxane sealed with a sexyl group.

(In formulas (2a) and (2b), R 3 is a monovalent hydrocarbon group having 1 to 12 carbon atoms independently substituted or substituted, and A is an oxygen atom or 2 to 8 carbon atoms. It is a valent hydrocarbon group, X is a hydrolyzable group, b is 0 or 1, and m is an integer having a viscosity of this diorganopolysiloxane at 23 ° C. of 100 to 1,000,000 mPa · s. is there.)
A coating agent containing the room temperature curable resin composition according to any one of claims 1 to 4.
An adhesive comprising the room temperature curable resin composition according to any one of claims 1 to 4.
A sealing agent containing the room temperature curable resin composition according to any one of claims 1 to 4.
An article having a coating layer made of a cured product of the room temperature curable resin composition according to any one of claims 1 to 4.
An article adhered and / or sealed with a cured product of the room temperature curable resin composition according to any one of claims 1 to 4.