WO2022259815A1

WO2022259815A1 - Curable composition and cured product

Info

Publication number: WO2022259815A1
Application number: PCT/JP2022/020196
Authority: WO
Inventors: 修一後藤; 智広安江; 慧斌文
Original assignee: 綜研化学株式会社
Priority date: 2021-06-08
Filing date: 2022-05-13
Publication date: 2022-12-15
Also published as: CN117529524A; JPWO2022259815A1

Abstract

The present invention addresses the problem of providing a curable composition that cures rapidly without the use of a tin-based curing catalyst and is capable of forming a cured product that exhibits superior storage stability and mechanical properties, and a curable composition that exhibits superior adhesion properties.　A curable composition according to the present invention is characterized by containing: a (meth)acrylic polymer (A) that has a group represented by formula (1), has a number average molecular weight (Mn) of at least 1000, and contains at least 500 ppm elemental silicon; and a silane coupling agent (B) that is represented by formula (2) and has a molecular weight of less than 1000. Formula (1): -X-CH₂-SiR¹ ₃ Formula (2): Y-CH₂-SiR¹ ₃

Description

Curable composition and cured product

The present invention relates to curable compositions and cured products.

Polymers having reactive silicon groups in their molecules are known as compositions that crosslink and cure through the formation of siloxane bonds accompanied by hydrolysis of silyl groups by moisture present in the atmosphere or adherend. there is Among them, polymers having a reactive silicon group such as an alkoxysilyl group are widely used as adhesives, sealants, paints, etc. in construction/building material-related applications, automobile-related applications, and the like.

Among them, by using a polyoxyalkylene polymer or (meth)acrylic polymer having a specific structure of reactive silicon group, it has a fast curing property, excellent adhesiveness and storage stability curable composition is known to be obtained (see, for example, Patent Documents 1 to 3).

JP 2012-136685 A JP 2014-101499 A JP 2010-202863 A

A curable composition containing a polymer having a reactive silicon group in its molecule is usually cured using a catalyst such as a tin-based compound because the curing reaction is accelerated. However, the use of tin-based compounds and the like is not preferable from the viewpoint of environmental load and toxicity to the human body.

The composition described in Patent Document 1 above contains a tin compound as a condensation catalyst. On the other hand, the curable compositions described in Patent Documents 2 and 3 are characterized by good curing without using a tin-based compound. However, in the curable composition disclosed in Patent Document 2, the polymer having a silyl group represented by a predetermined formula has high reactivity, and the reaction progresses even with moisture in the air. In addition, the curable composition must be used up or discarded after being taken out of the storage container, resulting in poor storage stability.

An object of the present invention is to provide a curable composition that cures quickly without using a tin-based curing catalyst and can form a cured product with excellent storage stability and mechanical properties, or a curable composition that has excellent adhesiveness. to do.

The present invention relates to, for example, [1] to [7] below.

[1] A (meth)acrylic polymer (A) having a group represented by formula (1), having a number average molecular weight (Mn) of 1,000 or more and containing 500 ppm or more of silicon element;
A curable composition containing a silane coupling agent (B) represented by formula (2) and having a molecular weight of less than 1,000.

Formula ( ¹ ): -X- _CH2 - _SiR13
[In formula (1), R ¹ is each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and at least one of R ¹ is the alkoxy group or hydroxyl group X is -O-, -COO-, -S-, -N(R ² )-, -CH(OH)-CH ₂ -O-, -O-CO-NH- or -N(R ² ) A divalent group represented by —CO—N(R ³ )—, where R ² and R ³ are a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and R ² and R ³ may be the same or different. ]
Formula (2): Y _— CH ₂ —SiR ¹³
[In formula (2), R ¹ has the same definition as in formula (1); Y is a (meth)acryloyl group, an alkoxy group having 1 to 20 carbon atoms, a mercapto group, or an isocyanate group. ]
[2] The curable composition according to [1], which contains 0.1 to 20 parts by mass of (B) with respect to 100 parts by mass of the (meth)acrylic polymer (A).

[3] The curable composition according to [1] or [2], wherein the (meth)acrylic polymer (A) has at least a terminal group represented by the formula (1).

[4] The curable composition according to any one of [1] to [3], wherein the (meth)acrylic polymer (A) has a glass transition temperature (Tg) of -20°C or lower.

[5] The curable composition according to any one of [1] to [4], wherein the (meth)acrylic polymer (A) has a number average molecular weight of 1,000 to 100,000.

[6] Containing 0.05 to 10 parts by mass of an aminosilane compound (C) represented by the following formula (3) with respect to 100 parts by mass of the (meth)acrylic polymer (A) [1] to [5] The curable composition according to any one of.

Formula ( ₃ ): R ₄₂ _{--N--(CH 2} ⁾ _n --SiR ¹³
[In formula (3), n is an integer of 1 to 6; R ¹ has the same meaning as in formula (1); R ⁴ is each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or At least one hydrogen atom of the hydrocarbon group is a group substituted with a group selected from the group consisting of an unsubstituted amino group, a substituted amino group and an alkoxysilyl group. ]
[7] A cured product obtained from the curable composition according to any one of [1] to [6].

According to the present invention, a curable composition that can be cured without using a tin-based curing catalyst and can form a cured product having excellent storage stability and mechanical properties, or a curable composition that has excellent adhesion after long-term storage. can provide things.

The present invention will be specifically described below.

The curable composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains a (meth)acrylic polymer (A) and a silane coupling agent (B), which will be described below.

In this specification, (meth)acrylic is used as a generic term for acrylic and methacrylic, and may be either acrylic or methacrylic, and (meth)acrylate is used as a generic term for acrylate and methacrylate, and may be either acrylate or methacrylate. (Meth)acryloyl is used as a generic term for acryloyl and methacryloyl, and may be acryloyl or methacryloyl.

[(Meth) acrylic polymer (A)]
The (meth)acrylic polymer (A) (hereinafter also referred to as “polymer (A)”) has a group represented by formula (1) and has a number average molecular weight (Mn) of 1,000 or more. and a polymer containing 500 ppm or more of silicon element.

Formula ( ¹ ): -X- _CH2 - _SiR13
In formula (1), R ¹ is each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and at least one of R ¹ is the above alkoxy group or hydroxyl group. Yes; X is -O-, -COO-, -S-, -N(R ² )-, -CH(OH)-CH ₂ -O-, -O-CO-NH- or -N(R ² )—CO—N(R ³ )—, wherein R ² and R ³ are a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and R ² and R ³ are , may be the same or different.

Examples of alkyl groups having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, isopentyl group, neopentyl group and n-hexyl group. , 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, isooctyl group, 1- methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n -decyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, Examples include linear and branched alkyl groups such as n-octadecyl group and n-eicosyl group, preferably alkyl groups having 1 to 10 carbon atoms, more preferably alkyl groups having 1 to 3 carbon atoms. The alkyl groups may be straight or branched.

Examples of alkoxy groups having 1 to 20 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, n-pentyloxy, isopentyloxy, neo pentyloxy group, n-hexyloxy group, 1-methylpentyloxy group, 4-methyl-2-pentyloxy group, 3,3-dimethylbutyloxy group, 2-ethylbutyloxy group, n-heptyloxy group, 1 -methylhexyloxy group, n-octyloxy group, isooctyloxy group, 1-methylheptyloxy group, 2-ethylhexyloxy group, 2-propylpentyloxy group, n-nonyloxy group, 2,2-dimethylheptyloxy group , 2,6-dimethyl-4-heptyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy group, n-undecyloxy group, 1-methyldecyloxy group, n-dodecyloxy group, n -tridecyloxy group, 1-hexylheptyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n-hexadecyloxy group, n-heptadecyloxy group, n-octadecyloxy group, n-eico Linear and branched alkoxy groups such as siloxy groups can be mentioned, and alkoxy groups having 1 to 10 carbon atoms are preferred, and alkoxy groups having 1 to 3 carbon atoms are more preferred. The alkoxy groups may be straight or branched.

Hydrocarbon groups for R ² and R ³ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, n- Alkyl groups having 1 to 18 carbon atoms, preferably 1 to 3 carbon atoms, such as octyl group and isooctyl group; Cycloalkyl groups having 3 to 18 carbon atoms, preferably 5 to 8 carbon atoms, such as cyclopentyl group and cyclohexyl group an alkenyl group having 2 to 18 carbon atoms, preferably 2 to 5 carbon atoms, such as vinyl group, allyl group, 3-butenyl group, and 5-hexenyl group; 6 carbon atoms, such as phenyl group, naphthyl group and anthryl group; to 18, preferably 6 to 10 carbon atoms.

The halogenated hydrocarbon group for R ² and R ³ is a group in which at least part of the hydrogen atoms constituting the aforementioned hydrocarbon group has been substituted with halogen atoms. Halogen atoms include, for example, fluorine, chlorine, bromine and iodine atoms.

R ² and R ³ are preferably hydrogen atoms or hydrocarbon groups, more preferably hydrocarbon groups.

Examples of groups represented by -SiR ¹³ include dimethylmethoxysilyl _, dimethylethoxysilyl, methyldimethoxysilyl, methyldiethoxysilyl, trimethoxysilyl, triethoxysilyl and dimethylisopropoxysilyl groups. , methyldiisopropoxysilyl group and triisopropoxysilyl group.

From the viewpoint of curability and mechanical properties, the polymer (A) has a group represented by formula (1) and contains 500 ppm or more of silicon element, preferably 1,000 to 20,000 ppm, more preferably 1 , 500 to 10,000 ppm. In addition, "ppm" means wtppm. The silicon element content derived from the group represented by formula (1) in the polymer (A) can be calculated from the charge ratio, and can be measured by ICP emission spectrometry. Details are described in the Example column.

<(Meth)acrylic acid alkyl ester (a1)>
The polymer (A) is a polymerizable monomer component containing a (meth)acrylic acid alkyl ester (a1) (hereinafter also referred to as “monomer (a1)”) having 1 to 12 carbon atoms in the alkyl group. It is preferably coalesced. That is, the polymer (A) preferably has structural units derived from the monomer (a1).

The alkyl group may be linear or branched.

Examples of the monomer (a1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2 - ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate ) acrylates.

One or two or more monomers (a1) can be used.

The proportion of the monomer (a1) in the polymerizable monomer component constituting the polymer (A) is preferably 20% by mass or more, more preferably 20 to 85% by mass, still more preferably 20 to 75% by mass. % by weight, particularly preferably 22 to 55% by weight. The polymer (A) can have structural units derived from the monomer (a1) in the same range among all structural units. When the (meth)acrylic acid alkyl ester (a1) in which the alkyl group has 8 to 12 carbon atoms is used within the above range, a (meth)acrylic polymer having excellent mechanical properties can be obtained.

<Hydrolyzable silyl group-containing (meth)acryloyl monomer (a2)>
The polymer (A) is a hydrolyzable silyl group-containing (meth)acryloyl monomer (a2) (hereinafter “monomer (a2)”).

As the monomer (a2), for example, a compound represented by formula (a2-1) is preferable.

In formula (a2-1), R ^a is a hydrogen atom or a methyl group, and R ¹ has the same definition as R ¹ in formula (1).

Examples of the compound represented by formula (a2-1) include (meth)acryloxymethyldimethylmethoxysilane, (meth)acryloxymethyldimethylethoxysilane, ((meth)acryloxymethyl)methyldimethoxysilane, (( Examples include (meth)acryloxy group-containing silanes such as meth)acryloxymethyl)methyldiethoxysilane, (meth)acryloxymethyltrimethoxysilane, and (meth)acryloxymethyltriethoxysilane.

As the monomer (a2), a hydroxy group of a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, or an aminoalkyl (meth)acrylate such as 2-aminoethyl (meth)acrylate An isocyanate group of a compound represented by OCN _- CH ₂ -SiR ¹³ (R ¹ has the same meaning as the same symbol described in formula (1)) is added to the amino group of (meth)acrylate. Compounds may also be mentioned. Specific examples of the compound represented by OCN--CH ₂ _--SiR ¹³ will be described later.

One or two or more monomers (a2) can be used.

The proportion of the monomer (a2) in the polymerizable monomer component constituting the polymer (A) is preferably 0.01-10% by mass, more preferably 0.1-5% by mass. The polymer (A) can have structural units derived from the monomer (a2) in the same range among all structural units. When the monomer (a2) is used within the above range, the group represented by the formula (1) can be introduced into the polymer (A), so that the resulting polymer (A) has appropriate crosslinkability. , suitable for use in forming a crosslinked body.

<Other Monomers (a3)>
The polymer (A) may further have a structural unit derived from a monomer (a3) other than the monomers (a1) and (a2) as long as the objects of the present invention are not impaired.

Other monomers (a3) include, for example,
n-tridecyl (meth) acrylate, isodecyl (meth) acrylate, n-myristyl (meth) acrylate, isomyristyl (meth) acrylate, n-pentadecyl (meth) acrylate, isopentadecyl (meth) acrylate, n-cetyl (meth) ) acrylate, isocetyl (meth) acrylate, n-heptadecyl (meth) acrylate, isoheptadecyl (meth) acrylate, n-stearyl (meth) acrylate, isostearyl (meth) acrylate, n-nonadecyl (meth) acrylate, isononadecyl (meth) (meth)acrylic acid alkyl esters such as acrylates, n-eicosyl (meth)acrylates, isoeicosyl (meth)acrylates, etc., in which the number of carbon atoms in the alkyl group is 13 or more, preferably the upper limit of the number of carbon atoms in the alkyl group is 22;
Alicyclic hydrocarbon group- or aromatic hydrocarbon group-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, and phenyl (meth)acrylate;
Methoxymethyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, 3-ethoxypropyl (meth)acrylate, 4-methoxybutyl (meth)acrylate Alkoxyalkyl (meth)acrylates such as acrylates and 4-ethoxybutyl (meth)acrylate;
Methoxy polyethylene glycol mono (meth) acrylate, ethoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, polyethylene glycol Polyalkylene glycol (meth)acrylates such as mono(meth)acrylates and polypropylene glycol mono(meth)acrylates;
Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate;
(Meth)acrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid; β-carboxyethyl (meth)acrylate, 5-carboxypentyl (meth)acrylate, mono(meth)acryloyloxyethyl succinate, ω - carboxy group-containing monomers such as carboxy group-containing (meth)acrylates such as carboxypolycaprolactone mono(meth)acrylate;
Acid anhydride group-containing monomers such as phthalic anhydride and maleic anhydride;
Dialkylaminoalkyl (meth)acrylates such as 2-dimethylaminoethyl (meth)acrylate and 2-diethylaminoethyl (meth)acrylate;
(meth)acrylamide; N-alkyl (meth)acrylamide such as N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-hexyl (meth)acrylamide; N,N- Amide group-containing monomers such as N,N-dialkyl (meth)acrylamides such as dimethyl (meth)acrylamide and N,N-diethyl (meth)acrylamide;
(meth) cyano group-containing monomers such as acrylonitrile;
Nitrogen-based heterocyclic ring-containing monomers such as N-vinylpyrrolidone, N-vinylmorpholine, N-vinylcaprolactam, (meth)acryloylmorpholine, N-cyclohexylmaleimide, N-phenylmaleimide, N-laurylmaleimide, N-benzylmaleimide;
Styrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-chloromethylstyrene, p-methoxystyrene, p-tert-butoxystyrene, divinylbenzene, and indene;
vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl caproate, vinyl benzoate and vinyl cinnamate;

Among other monomers (a3), (meth)acrylic acid alkyl esters other than monomer (a1) and polyalkylene glycol (meth)acrylates are preferred, and (meth)acrylic acid alkyl esters other than monomer (a1) are more preferred.

One or two or more other monomers (a3) can be used.

The proportion of the other monomer (a3) in the polymerizable monomer components constituting the polymer (A) is preferably 1-65% by mass, more preferably 5-60% by mass. The polymer (A) can have structural units derived from other monomers (a3) in the same range among all the structural units.

<Mercapto group-containing compound (d)>
A mercapto group-containing compound (d) may be used as a chain transfer agent during the production of the polymer (A).

The mercapto group-containing compound (d) acts as a chain transfer agent because it has a functional group (-SH) with high chain transferability in radical polymerization. When the polymerizable monomer component is polymerized in the presence of the mercapto group-containing compound (d), a structural unit derived from the mercapto group-containing compound (d), particularly a mercapto group having a group represented by formula (1) When a group-containing compound is used, the group represented by formula (1) can be introduced at the molecular chain end of the polymer. Further, by introducing a mercapto group-containing compound (d) represented by formula (1) into a polymer having a polymerizable unsaturated group by an en-thiol reaction, the group represented by formula (1) is polymerized. It can also be introduced into coalescence. The curable composition using the polymer (A) having the group represented by formula (1) at the molecular chain end has excellent mechanical properties.

When the monomer (a2) is used, the group represented by formula (1) in the monomer (a2) and the group represented by formula (1) in the mercapto group-containing compound (d) are the same. may be different.

A compound represented by formula (d-1) is preferable as the mercapto group-containing compound (d).

Formula (d-1): HS--CH ₂ _--SiR ¹³
In formula (d-1), R ¹ has the same definition as R ¹ in formula (1).

Among the mercapto group-containing compounds (d), compounds represented by formula (d-1) include, for example, mercaptomethyldimethylmethoxysilane, mercaptomethyldimethylethoxysilane, mercaptomethyldimethylisopropoxysilane, mercaptomethylmethyldimethoxysilane. silane, mercaptomethylmethyldiethoxysilane, mercaptomethylmethyldiisopropoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltriisopropoxysilane. Among these, mercaptomethyldimethylmethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane are preferred. By using the compound represented by the formula (d-1), the group represented by the formula (1) can be introduced to the terminal of the molecular chain of the polymer (A).

Other mercapto group-containing compounds (d) include, for example, n-octylmercaptan, n-dodecylmercaptan, tert-dodecylmercaptan, laurylmercaptan, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 2, 2. Mercapto group-containing compounds such as mercaptopropyldimethylmethoxysilane, mercaptopropyldimethylethoxysilane, mercaptopropylmethyldimethoxysilane, mercaptopropylmethyldiethoxysilane, mercaptopropyltrimethoxysilane and mercaptopropyltriethoxysilane.

One or two or more compounds (d) can be used.

The mercapto group-containing compound (d) is preferably used in the range of 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, with respect to the total 100 parts by mass of the polymerizable monomer components. Used in range. With such an aspect, the number average molecular weight of the polymer (A) can be adjusted to an appropriate range.

<Production of polymer (A)>
Polymer (A) can be obtained by various polymerization methods, and the method is not particularly limited, but it is preferably obtained by, for example, the following method. The methods (i) to (iv) may be used in any combination.

(i) A method of copolymerizing a monomer (a2) having a polymerizable unsaturated group and a group represented by formula (1) with the above-described monomer (a1) having a (meth)acrylic structure.

(ii) A method of polymerizing a monomer (a1) having a (meth)acrylic structure in the presence of a mercapto group-containing compound (d) having a group represented by formula (1) as a chain transfer agent.

(iii) a compound having a polymerizable unsaturated group and a reactive functional group (e.g., a hydroxy group, an isocyanate group, or an amino group) and a reactive functional group obtained by copolymerizing a monomer component containing the monomer (a1) A polymer having a group is reacted with a compound (e) having a group capable of undergoing an addition reaction with the reactive functional group and capable of introducing the group represented by the formula (1) into the polymer by an addition reaction. Method.

Examples of the compound (e) include compounds represented by formulas (e-1) and (e-2) (hereinafter also referred to as "compound (e-1)" and "compound (e-2)", respectively). ) are mentioned.

Formula (e- ¹ ): OCN- _CH2 - _SiR13
R ¹ has the same meaning as the same symbol in formula (1).

Examples of the compound (e-1) include 1-isocyanatomethyldimethylmethoxysilane, 1-isocyanatomethyldimethylethoxysilane, 1-isocyanatomethyldimethylisopropoxysilane, (1-isocyanatomethyl)methyldimethoxysilane, (1-isocyanate methyl)methyldiethoxysilane, (1-isocyanatomethyl)methyldiisopropoxysilane, 1-isocyanatomethyltrimethoxysilane, 1-isocyanatomethyltriethoxysilane, 1-isocyanatomethyltriisopropoxysilane. Among these, 1-isocyanatomethyldimethylmethoxysilane, (1-isocyanatomethyl)methyldimethoxysilane, 1-isocyanatomethyltrimethoxysilane, and 1-isocyanatomethyltriethoxysilane are preferred.

Formula (e- ₂ ): R ⁴ —CH ₂ —SiR ¹³
R ¹ has the same meaning as the same symbol in formula (1), R ⁴ is a glycidyloxy group, amino group, alkylamino group, (aminoalkyl)amino group, (N,N-dialkylaminoalkyl)amino group or It is a halogenated hydrocarbon group.

Examples of the compound (e-2) include aminomethyltrimethoxysilane, aminomethyltriethoxysilane, (aminoethylamino)methyltrimethoxysilane, (N,N-dimethylamino)ethylaminomethyltrimethoxysilane, glycidyloxy Methyltrimethoxysilane can be mentioned.

One or two or more compounds (e) can be used.

The compound (e) is preferably used in an amount of 0.1 to 5 parts by mass, more preferably 0.2 to 3 parts by mass, based on 100 parts by mass of the total polymerizable monomer components.

(iv) the monomer (a1) is polymerized by a living polymerization method to introduce a functional group such as an alkenyl group or a hydroxy group at the molecular chain end, and then the resulting polymer and the compound (d) or the compound (e); Etc. How to react.

The polymer (A) can be produced by using a known polymerization method such as cationic polymerization, anionic polymerization, radical polymerization, etc., as in the methods (i) to (iv) described above, and the method is not particularly limited. , the versatility of the monomer and the industrial productivity, the radical polymerization method is preferred. As the radical polymerization method, a living radical polymerization method capable of introducing a specific functional group (for example, a group represented by formula (1)) at a controlled position such as a terminal, or a polymerization initiator is used. Free-radical polymerization methods are included in which predetermined monomeric units are copolymerized.

As the living polymerization method, a living cationic polymerization method, a living anionic polymerization method, and a living radical polymerization method can be applied, but from the viewpoint of industrial productivity, the living radical polymerization method is preferable. Living radical polymerization methods include atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, nitroxide-mediated polymerization (NMP), and organotellurium compound-mediated polymerization (TERP). , an iodine compound-mediated polymerization method (IRP), or the like can be used, and a polymer having terminal functional groups can be obtained by selecting the reaction conditions.

As a free radical polymerization method, for example, a polymerizable monomer component and, if necessary, a mercapto group-containing compound (d) are charged in a reaction vessel, a polymerization initiator is added, and the reaction temperature is about 40 to 90° C. for 2 hours. Allow to react for ~20 hours. In the reaction, if necessary, a polymerization solvent may be charged. For example, polymerization is performed in an inert gas atmosphere such as nitrogen gas. Moreover, a polymerizable monomer component, a polymerization initiator, a chain transfer agent, and a polymerization solvent may be added as appropriate during the polymerization reaction.

Examples of polymerization initiators include azo compound polymerization initiators, peroxide polymerization initiators, and radical photopolymerization initiators. In addition, it is more preferable not to use a metal catalyst. Since the polymer (A) produced using such a polymerization initiator does not contain a metal component derived from the catalyst in the polymer (A), inhibition of the cross-linking reaction and coloration can be improved. can. Moreover, since the depolymerization reaction caused by the metal component can be suppressed, it is possible to provide a cured product having excellent durability in use in various applications.

Examples of azo compound polymerization initiators include 2,2′-azobisisobutyronitrile, 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-cyclopropylpropionitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(2-methylbutyronitrile), 1,1′-azobis(cyclohexane-1 -carbonitrile), 2-(carbamoylazo)isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis(2-amidinopropane) dihydrochloride, 2,2 '-azobis(N,N'-dimethyleneisobutyramidine), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propionamide], 2,2'-azobis(isobutyramide) dihydrate , 4,4′-azobis(4-cyanopentanoic acid), 2,2′-azobis(2-cyanopropanol), dimethyl-2,2′-azobis(2-methylpropionate), 2,2′- azobis[2-methyl-N-(2-hydroxyethyl)propionamide].

Peroxide-based polymerization initiators include, for example, t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-isopropyl peroxydicarbonate, di -2-ethylhexyl peroxydicarbonate, t-butyl peroxybivalate, 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 2,2-bis(4,4-di- t-amylperoxycyclohexyl)propane, 2,2-bis(4,4-di-t-octylperoxycyclohexyl)propane, 2,2-bis(4,4-di-α-cumylperoxycyclohexyl)propane , 2,2-bis(4,4-di-t-butylperoxycyclohexyl)butane and 2,2-bis(4,4-di-t-octylperoxycyclohexyl)butane.

As the photoradical polymerization initiator, compounds conventionally used as photoradical polymerization initiators are preferable. -dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-hydroxycyclohexylphenyl ketone , 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one, N,N-dimethylaminoacetophenone and other acetophenone initiators; 2-methylanthraquinone, 1-chloroanthraquinone, anthraquinone-based initiators such as 2-amyl anthraquinone; thioxanthone-based initiators; ketal-based initiators such as acetophenone dimethyl ketal and benzyl methyl ketal; benzophenone, methylbenzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dichlorobenzophenone, 4,4' - benzophenone initiators such as bisdiethylaminobenzophenone, Michler's ketone, 4-benzoyl-4'-methyldiphenylsulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4, Acylphosphine oxide initiators such as 4′-trimethylpentylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; 1-[4-(phenylthio)phenyl]octane-1,2-dione= Oxime ester initiators such as 2-(O-benzoyloxime); camphorquinone and α-hydroxyketone.

The radical photopolymerization initiator may be used singly or in combination of two or more.

The photoradical polymerization initiator may be combined with a sensitizer. Preferred sensitizers are anthracene compounds such as 9,10-dibutoxyanthracene and 9,10-bis(acyloxy)anthracene.

One or two or more polymerization initiators can be used.

The polymerization initiator may be used by successive addition over multiple times.

The amount of polymerization initiator used is usually 0.001 to 2 parts by mass, preferably 0.002 to 1 part by mass, per 100 parts by mass of the polymerizable monomer component. By using the polymerization initiator within the above range, the number average molecular weight of the polymer (A) can be adjusted within an appropriate range.

An organic solvent is preferable as the polymerization solvent. Examples of organic solvents include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane, cycloheptane, cyclo Alicyclic hydrocarbons such as octane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, 1,2- Halogenated hydrocarbons such as dichloroethane and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; ketones such as acetone, acetylacetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and cyclohexanone; N,N-dimethylformamide , N,N-dimethylacetamide and N-methylpyrrolidone; nitriles such as acetonitrile and benzonitrile; sulfoxides such as dimethylsulfoxide and sulfolane.

One or two or more polymerization solvents can be used.

<Physical properties of polymer (A)>
The number average molecular weight (Mn) of the polymer (A) is preferably 1,000 or more, more preferably 3,000 or more, and still more preferably 5,000 or more, from the viewpoint of the viscosity of the polymer and the mechanical properties of the resulting cured product. 000 or more, preferably 100,000 or less, more preferably 50,000 or less, still more preferably 40,000 or less from the viewpoint of the viscosity of the polymer.

The number average molecular weight (Mn) is measured by a gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the polymer (A) is preferably -20°C or lower, more preferably -90 to -25°C, still more preferably -80 to -30°C. Such an aspect is preferable from the viewpoint of low viscosity and excellent handleability. Tg is determined by differential scanning calorimetry (DSC).

Details of the measurement conditions for GPC and DSC are described in the Examples section below.

<Content of polymer (A)>
The composition of the invention can contain one or more polymers (A).

The total content of the polymer (A) in the composition of the present invention is preferably 5% by mass or more, more preferably 8 to 95% by mass, and even more preferably 10 to 90% by mass.

[Silane coupling agent (B)]
The composition of the present invention contains a silane coupling agent (B) together with the polymer (A).

The silane coupling agent (B) acts as a dehydrating agent in the composition of the present invention.

By having the group represented by formula (1) in the polymer (A), the composition of the present invention is cured without using a tin-based curing catalyst. However, the polymer (A) having a group represented by formula (1) alone has high reactivity, and the reaction proceeds even with moisture in the air. By containing the silane coupling agent (B), the reaction of the polymer (A) is suppressed, and a curable composition having excellent storage stability and excellent adhesiveness even after long-term storage can be obtained.

The dehydration effect of the silane coupling agent (B) is exhibited by the combination of the polymer (A) having the group represented by the formula (1) and the (B) having the group represented by the formula (2). do.

The silane coupling agent (B) is represented by formula (2).

Formula (2): Y _— CH ₂ —SiR ¹³
In formula (2), R ¹ has the same definition as in formula (1); Y is a (meth)acryloyl group, an alkoxy group having 1 to 20 carbon atoms, a mercapto group, or an isocyanate group.

Examples of the alkoxy group having ₁ to 20 carbon atoms and the group represented by -SiR ¹³ include the same groups as those described in the column of the polymer (A).

Examples of the silane coupling agent (B) in which Y is a (meth)acryloyl group include (meth)acryloxymethyldimethylmethoxysilane, (meth)acryloxymethyldimethylethoxysilane, (( meth)acryloxymethyl)methyldimethoxysilane, ((meth)acryloxymethyl)methyldiethoxysilane, (meth)acryloxymethyltrimethoxysilane, (meth)acryloxymethyltriethoxysilane and the like.

Examples of the silane coupling agent (B) in which Y is an alkoxy group having 1 to 20 carbon atoms include methoxymethyltrimethoxysilane, ethoxymethyltrimethoxysilane, and n-propyloxymethyltrimethoxysilane. silane, isopropyloxymethyltrimethoxysilane, n-butyloxymethyltrimethoxysilane, isobutyloxymethyltrimethoxysilane, n-pentyloxymethyltrimethoxysilane, isopentyloxymethyltrimethoxysilane, neopentyloxymethyltrimethoxysilane, n-hexyloxymethyltrimethoxysilane, 1-methylpentyloxymethyltrimethoxysilane, 4-methyl-2-pentyloxymethyltrimethoxysilane, 3,3-dimethylbutyloxymethyltrimethoxysilane, 2-ethylbutyloxymethyl trimethoxysilane, n-heptyloxymethyltrimethoxysilane, 1-methylhexyloxymethyltrimethoxysilane, n-octyloxymethyltrimethoxysilane, isooctyloxymethyltrimethoxysilane, 1-methylheptyloxymethyltrimethoxysilane, 2-ethylhexyloxymethyltrimethoxysilane, 2-propylpentyloxymethyltrimethoxysilane, n-nonyloxymethyltrimethoxysilane, 2,2-dimethylheptyloxymethyltrimethoxysilane, 2,6-dimethyl-4-heptyloxy methyltrimethoxysilane, 3,5,5-trimethylhexyloxymethyltrimethoxysilane, n-decyloxymethyltrimethoxysilane, n-undecyloxymethyltrimethoxysilane, 1-methyldecyloxymethyltrimethoxysilane, n- dodecyloxymethyltrimethoxysilane, n-tridecyloxymethyltrimethoxysilane, 1-hexylheptyloxymethyltrimethoxysilane, n-tetradecyloxymethyltrimethoxysilane, n-pentadecyloxymethyltrimethoxysilane, n-hexa Decyloxymethyltrimethoxysilane, n-heptadecyloxymethyltrimethoxysilane, n-octadecyloxymethyltrimethoxysilane, n-eicosyloxymethyltrimethoxysilane, these trimethoxysilyl groups are dimethylmethoxysilyl group and dimethyl ethoxysilyl group, methyldimethoxysilyl group, methyldiethoxysilyl group group, triethoxysilyl group, dimethylisopropoxysilyl group, methyldiisopropoxysilyl group, triisopropoxysilyl group, and the like. Among these, methoxymethyltrimethoxysilane, ethoxymethyltrimethoxysilane, n-propyloxymethyltrimethoxysilane, isopropyloxymethyltrimethoxysilane, n-butyloxymethyltrimethoxysilane and isobutyloxymethyltrimethoxysilane are preferred.

Examples of the silane coupling agent (B) in which Y is a mercapto group include mercaptomethyldimethylmethoxysilane, mercaptomethyldimethylethoxysilane, mercaptomethyldimethylisopropoxysilane, and mercaptomethylmethyldimethoxysilane. , mercaptomethylmethyldiethoxysilane, mercaptomethylmethyldiisopropoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyltriisopropoxysilane. Among these, mercaptomethyldimethylmethoxysilane, mercaptomethylmethyldimethoxysilane, mercaptomethyltrimethoxysilane, and mercaptomethyltriethoxysilane are preferred.

Examples of the silane coupling agent (B) in which Y is an isocyanate group include 1-isocyanatomethyldimethylmethoxysilane, 1-isocyanatomethyldimethylethoxysilane, 1-isocyanatomethyldimethylisopropoxysilane, (1-isocyanatomethyl)methyldimethoxysilane, (1-isocyanatomethyl)methyldiethoxysilane, (1-isocyanatomethyl)methyldiisopropoxysilane, 1-isocyanatomethyltrimethoxysilane, 1-isocyanatomethyltriethoxysilane, 1 -isocyanatomethyltriisopropoxysilane. Among these, 1-isocyanatomethyldimethylmethoxysilane, (1-isocyanatomethyl)methyldimethoxysilane, 1-isocyanatomethyltrimethoxysilane, and 1-isocyanatomethyltriethoxysilane are preferred.

When the monomer (a2) and/or the mercapto compound (d) are used to produce the polymer (A), the silane coupling agent (B) is the same as the monomer (a2) and/or the mercapto compound (d). may be different.

<Physical properties of silane coupling agent (B)>
As the molecular weight of the silane coupling agent (B), the lower limit is preferably 80 or more, more preferably 100 or more, still more preferably 120 or more, and the upper limit is less than 1,000, preferably 750 or less, or more. Preferably it is 500 or less.

<Content of silane coupling agent (B)>
The composition of the present invention can contain one or more silane coupling agents (B).

In the composition of the present invention, the total amount of the silane coupling agent (B) is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, based on 100 parts by mass of the polymer (A). , more preferably 1 to 10 parts by mass. When the content of the silane coupling agent (B) is within the above range, a curable composition having excellent storage stability and excellent adhesiveness even after long-term storage can be obtained.

[Aminosilane compound (C)]
The composition of the present invention preferably contains an aminosilane compound (C) together with the polymer (A) and the silane coupling agent (B).

The aminosilane compound (C) acts as a curing catalyst and dehydrating agent in the composition of the present invention.

The aminosilane compound (C) has a group represented by the following formula (3).

Formula ( ₃ ): R ₄₂ _{--N--(CH 2} ⁾ _n --SiR ¹³
[In formula (3), n is an integer of 1 to 6; R ¹ has the same meaning as in formula (1); R ⁴ is each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or A group in which at least one hydrogen atom of a hydrocarbon group is substituted with a group selected from the group consisting of an unsubstituted amino group, a substituted amino group and an alkoxysilyl group. ]
Examples of the aminosilane compound (C) represented by formula (3) include N-(2-aminoethyl)aminomethyltrimethoxysilane, N-(2-aminoethyl)-2-aminoethyltrimethoxysilane, N -(2-aminoethyl)-3-aminopropyltrimethoxysilane, aminomethyltrimethoxysilane, 2-aminoethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, aminomethyltriethoxysilane, 2-aminoethyltriethoxy Silane, 3-aminopropyltriethoxysilane, N-[2-(N,N-dimethylamino)ethyl]aminomethyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-cyclohexyl-3-amino Propylmethyldimethoxysilane, N-[2-(N-vinylbenzylamino)ethyl]-3-aminopropyltrimethoxysilane, bis[3-(trimethoxysilyl)propyl]amine, 3-[2-(2-amino) Ethylamino)ethylamino]propyltrimethoxysilane, N-[3-(trimethoxysilyl)propyl]-1-butanamine.

Among the aminosilane compounds (C), it is preferable to use an aminosilane compound represented by the following formula (3-1) from the viewpoint of improving the tack-free time of the composition of the present invention.

Formula (3-1): R4' ^- NH-( _CH2 ) _n' _- ^SiR1'3
In formula (3-1), n' is an integer of 1 to 3; R ^1' is an alkoxy group having 1 to 6 carbon atoms; R ⁴ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, Alternatively, at least one hydrogen atom of the hydrocarbon group is substituted with at least one group selected from the group consisting of unsubstituted amino groups, substituted amino groups and alkoxysilyl groups.

One or two or more aminosilane compounds (C) can be used.

The composition of the present invention is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 8 parts by mass, and further the aminosilane compound (C) in total with respect to 100 parts by mass of the polymer (A). It preferably contains 0.5 to 5 parts by mass. When the content of the aminosilane compound (C) is within the above range, a curable composition having excellent storage stability and excellent adhesiveness even after long-term storage can be obtained.

[Other ingredients]
The composition of the present invention contains, in addition to the polymer (A), if necessary, a polymer (D) having a polyether skeleton, a plasticizer, a filler, silica, a pigment, an antioxidant, a dehydrating agent, an amino Other components such as silane coupling agents having groups, curing catalysts, tackifying resins, dispersants, rheology control agents, antifoaming agents, and adhesion-imparting agents can be contained alone or in combination of two or more.

<Polymer (D)>
The composition of the present invention may optionally contain a polymer having a polyether skeleton in addition to the polymer (A). The polymer (D) preferably has a reactive silicon group, and more preferably has a group represented by the above formula (1).

The polymer (D) has a polyether skeleton as its main chain skeleton. The polyether skeleton is preferably a polyoxyalkylene skeleton, such as a polyoxyethylene skeleton, a polyoxypropylene skeleton, a polyoxybutylene skeleton, a polyoxytetramethylene skeleton, a polyoxyethylene-polyoxypropylene skeleton, and a polyoxypropylene skeleton. - A polyoxybutylene skeleton is mentioned, and a polyoxypropylene skeleton is preferred. The polyoxyalkylene skeleton may consist of only one kind of repeating unit, or may consist of two or more kinds of repeating units. The repeating units here are oxyalkylene units. Polymer (D) may have a urethane skeleton between polyether skeletons.

The number average molecular weight (Mn) of the polymer (D) is preferably 10,000 to 50,000. When the number average molecular weight (Mn) satisfies such conditions, it is preferable from the viewpoint of compatibility with the polymer (A), handling properties of the curable composition, and mechanical properties. Number average molecular weight (Mn) is measured by the GPC method.

The details of the GPC measurement conditions are described in the Examples section below.

By using the polymer (D) together with the polymer (A), a curable composition with excellent mechanical properties can be obtained.

When the polymer (D) is used, the group represented by the formula (1) in the polymer (A) and the group represented by the formula (1) in the polymer (D) are the same. may be different.

In one embodiment, the polymer (D) preferably has a group represented by formula (1) at the molecular chain end of the polymer, and represented by formula (1) at the molecular chain end of the polyether polymer. It is more preferable to have a group with

The polymer (D) is, for example, a terminal hydroxyl group of a polyether polymer and the compound (e- ₁ ) represented by OCN--CH ₂ --SiR ¹³ (R ¹ is the same symbol in formula (1) is synonymous with) can be obtained by reacting with an isocyanate group.

The polymer (D) is also obtained by obtaining ^a polyether polymer having terminal isocyanate groups from a polyether polymer, and combining the terminal isocyanate groups of the polymer with R ⁴ —CH ₂ —SiR ¹³ (R ₁ is synonymous with the same symbol as explained in formula (1)), wherein R ⁴ is an amino group, an alkylamino group, a (aminoalkyl)amino group, or (N, It can also be obtained by reacting an N-dialkylaminoalkyl)amino group with an amino group. A polyether polymer having a terminal isocyanate group can be obtained, for example, by a urethane reaction between a polyether polymer having a terminal hydroxyl group and a diisocyanate compound. Such polyether polymers have urethane skeletons between polyether skeletons.

The polymer (D) is obtained by obtaining a polyether polymer having an amino group at the terminal from the polyether polymer, and combining the terminal amino group of the polymer with the isocyanate group of the compound (e-1). It can also be obtained by reacting.

Examples of the diisocyanate compound include
Ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl-1,6-hexa Aliphatic diisocyanates having 4 to 30 carbon atoms such as methylene diisocyanate;
Alicyclic diisocyanates having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylylene diisocyanate;
aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenylether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate;

The composition of the present invention can contain one or more polymers (D).

The content of polymer (D) in the composition of the present invention is preferably 10 to 900 parts by mass, more preferably 20 to 800 parts by mass, based on 100 parts by mass of polymer (A). Such an aspect is preferable from the viewpoint of obtaining a cured product having excellent mechanical properties.

<Plasticizer>
The compositions of the invention can further contain a plasticizer. By using a plasticizer, the flexibility and elongation of the cured product formed from the curable composition can be improved.

Examples of plasticizers include phthalates such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, diisodecyl phthalate, benzyl butyl phthalate, and diisononyl phthalate; Non-phthalates such as diisononyl cyclohexanedicarboxylate and trioctyl trimellitate; aliphatic carboxylic acid esters such as dioctyl adipate, diisodecyl succinate, dibutyl sebacate and butyl oleate; diethylene glycol dibenzoate and triethylene glycol dibenzoate , alcohol esters such as pentaerythritol esters; phosphate esters such as trioctyl phosphate and tricresyl phosphate; epoxy plasticizers such as epoxidized soybean oil, dioctyl 4,5-epoxyhexahydrophthalate, and benzyl epoxystearate; Chlorinated paraffin; Hydrocarbons such as normal paraffin and isoparaffin; Alkane (C=10-21) alkylsulfonic acid phenyl ester such as phenyl sulfonate; polyethylene glycol and its derivatives, polypropylene glycol and its derivatives such as polyethylene glycol or polypropylene Polyethers such as glycol hydroxyl groups capped with alkyl ether, poly-α-methylstyrene, polystyrene oligomers such as polystyrene, polybutadiene, butadiene-acrylonitrile copolymer, polychloroprene, polyisoprene, polybutene, hydrogenation Oligomers such as polybutene and epoxidized polybutadiene, and polymer plasticizers such as (meth)acrylic polymers other than the polymer (A) can be used.

One or more plasticizers can be used.

In one embodiment, the content of the plasticizer in the composition of the present invention is preferably 10 parts per 100 parts by mass of the polymer component from the viewpoint of the coatability of the curable composition and the weather resistance of the cured product. It is up to 400 parts by mass, more preferably 50 to 300 parts by mass.

<Filler>
The compositions of the invention can further contain fillers.

Fillers include, for example, heavy calcium carbonate, light calcium carbonate, colloidal calcium carbonate, semi-colloidal calcium carbonate, slight calcium carbonate, and those obtained by surface-treating the surface of these calcium carbonates with fatty acids or resin acid-based organic substances. Calcined clay; Talc; Titanium oxide; Bentonite; Ferric oxide; Zinc oxide; Inorganic hollow bodies such as ash balloons, alumina balloons, zirconia balloons, carbon balloons; Organic resin hollow bodies (plastic balloons) such as methacrylate balloons, polyvinyl alcohol balloons, styrene-(meth)acrylic resin balloons, polyacrylonitrile balloons; resin beads, wood flour, pulp, cotton chips, mica, walnut flour, rice flour, powdery fillers such as graphite, fine aluminum powder and flint powder; and fibrous fillers such as glass fiber, glass filament, carbon fiber, Kevlar fiber and polyethylene fiber. Among these, calcium carbonate surface-treated with a fatty acid or the like is preferable from the viewpoint of dispersibility, and shirasu balloons, glass balloons, polystyrene balloons, and acrylic resin balloons are preferable from the viewpoint of reducing specific gravity and imparting heat insulating properties.

One or more fillers can be used.

The content of the filler in the composition of the present invention is preferably 0.1 to 1,000 parts by mass, more preferably 0.2 to 500 parts by mass, relative to 100 parts by mass of the polymer (A). . In the present invention, a curable composition having excellent filler dispersibility can be obtained.

<Silica>
The composition of the invention can further contain silica. By using silica, the coatability of the curable composition is improved, and a cured product having excellent weather resistance and elongation can be obtained.

Silica includes, for example, fumed silica. Silica includes hydrophobic silica and hydrophilic silica, with hydrophobic silica being preferred.

One or two or more types of silica can be used.

In one embodiment, the content of silica in the composition of the present invention is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, relative to 100 parts by mass of polymer (A).

<Pigment>
The composition of the invention can further contain pigments.

Examples of pigments include inorganic pigments such as iron oxide, chromium oxide, titanium oxide, and cobalt aluminate; and organic pigments such as phthalocyanine blue and phthalocyanine green. The use of pigments is preferred from the viewpoint of improving toning and weather resistance.

One or two or more pigments can be used.

In one embodiment, the content of the pigment in the composition of the present invention is preferably 1-200 parts by mass, more preferably 3-100 parts by mass, relative to 100 parts by mass of the polymer (A).

<Anti-aging agent>
The composition of the present invention may further contain anti-aging agents such as UV absorbers, light stabilizers and antioxidants.

Examples of ultraviolet absorbers include benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers, with benzotriazole-based ultraviolet absorbers being preferred. Examples of benzotriazole-based UV absorbers include 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis( 1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethyl Butyl)phenol, reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate with polyethylene glycol, 2-(2H-benzotriazole- 2-yl)-p-cresol.

Examples of light stabilizers include hindered amine light stabilizers. Examples of hindered amine light stabilizers include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate. , decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3, 5-triazine).

Examples of antioxidants include hindered phenol antioxidants, monophenol antioxidants, bisphenol antioxidants, polyphenol antioxidants, and phosphorus antioxidants.

One or more anti-aging agents can be used.

In one embodiment, the content of the anti-aging agent in the composition of the present invention is preferably 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the polymer (A). part by mass.

<Dehydrating agent>
In order to further improve storage stability, the composition of the present invention may contain a dehydrating agent as long as it does not adversely affect curability and flexibility.

Examples of dehydrating agents include hydrolyzable organosilicon compounds such as methyltrimethoxysilane, methyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and vinyltrimethoxysilane. alkyl orthoformate such as methyl orthoformate and ethyl orthoformate; alkyl orthoacetate such as methyl orthoacetate and ethyl orthoacetate; isocyanate compound such as p-toluenesulfonyl isocyanate.

In one embodiment, the content of the dehydrating agent in the composition of the present invention is preferably 0.1- 20 parts by mass, more preferably 1 to 10 parts by mass. The polymer component may contain the polymer (D) in addition to the polymer (A).

<Tackifying resin>
The composition of the present invention can further contain a tackifying resin.

A cured product containing a tackifying resin has moderate tackiness, and a pressure-sensitive adhesive layer with excellent shear adhesive strength can be obtained.

Examples of tackifying resins include rosin-based tackifying resins such as rosin ester-based resins, terpene-based tackifying resins such as terpene-phenol-based resins, styrene-based tackifying resins, and alicyclic saturated hydrocarbon resins.

A rosin ester-based resin is a resin obtained by esterifying a rosin-based resin with alcohol. Examples of rosin-based resins include rosin resins, disproportionated rosin resins, and hydrogenated rosin resins containing resin acids such as abietic acid as main components, and dimers of resin acids such as abietic acid (polymerized rosin resins). is mentioned. Examples of alcohols include polyhydric alcohols such as ethylene glycol, glycerin, and pentaerythritol.

Resin obtained by esterifying rosin resin is rosin ester resin, resin obtained by esterifying disproportionated rosin resin is disproportionated rosin ester resin, and resin obtained by esterifying hydrogenated rosin resin is hydrogenated rosin ester resin. A polymerized rosin ester resin is obtained by esterifying a polymerized rosin resin.

A terpene phenolic resin is a resin obtained by polymerizing terpene in the presence of phenol.

Examples of disproportionated rosin ester resins include Superester A75 (10 or less), Superester A100 (10 or less), Superester A115 (20 or less), and Superester A125 (20 or less). Polymerized rosin ester resins include, for example, Pencel D-125 (10 to 16), Pencel D-135 (10 to 16), and Pencel D-160 (10 to 16). The above products are manufactured by Arakawa Chemical Industries, Ltd., and the values in parentheses are acid values (mgKOH/g).

Examples of terpene-based tackifying resins include YS Polystar T30 (1 or less), YS Polystar T80 (1 or less), YS Polystar T130 (1 or less), Clearon 100 (1 or less), and Clearon 110 (1 or less). . The above products are manufactured by Yasuhara Chemical, and the values in parentheses are acid values (mgKOH/g).

Examples of styrene-based tackifying resins include FMR-0150 (0.1 or less), FTR-6100 (0.1 or less), FTR-6110 (0.1 or less), FTR-6125 (0.1 or less), FTR-7100 (0.1 or less), FTR-8120 (0.1 or less), FTR-0100 (0.1 or less), FTR-2120 (0.1 or less), FTR-2140 (0.1 or less) mentioned. The above products are manufactured by Mitsui Chemicals, and the values in parentheses are acid values (mgKOH/g). Also, SX-100 (1 or less) manufactured by Yasuhara Chemical Co., Ltd. may be mentioned.

Examples of alicyclic saturated hydrocarbon resins include Alcon P-90, Alcon P-100, Alcon P-115, Alcon P-125, Alcon M-90, Alcon M-100, Alcon M-115, Alcon M- 135 can be mentioned. The above products are manufactured by Arakawa Chemical Industries.

The tackifying resin can be used alone or in combination of two or more.

Among these, from the viewpoint of the storage stability of the curable composition, tackifying resins having an acid value of 1 mgKOH/g or less are preferable, and an acid value of 0.1 mgKOH/g or less is particularly preferable. By using a tackifying resin having an acid value of 0.1 mgKOH/g or less, a curable composition having particularly excellent storage stability can be obtained. The acid value refers to the number of mg of potassium hydroxide required to neutralize 1 g of the tackifying resin, and can be measured based on JIS K0070.

The composition of the present invention preferably contains 1 to 500 parts by mass, more preferably 5 to 300 parts by mass, of the tackifying resin with respect to 100 parts by mass of the polymer (A). In such a mode, the pressure-sensitive adhesive layer has appropriate tackiness and excellent adhesion to various adherends.

<Rheology control agent>
The compositions of the present invention can further contain rheology control agents. A rheology control agent can improve the smoothness of the film surface. As the rheology control agent, acrylic, urea, urethane, amide, polyester, and layered inorganic compound rheology control agents can be used. Among these, a polyester type represented by "BYK R606 (polyhydroxycarboxylic acid ester)" manufactured by BYK-Chemie Japan is preferable.

The composition of the present invention preferably contains 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass, of the rheology control agent with respect to 100 parts by mass of the polymer (A). With such an aspect, a curable composition having excellent thixotropy and pseudoplasticity can be obtained.

[Use of curable composition, cured product]
Since the composition of the present invention contains a polymer (A) and a salt compound (B) composed of an acid and a base that satisfies a predetermined pKa, it can be cured under a desired thermal environment, and has storage stability and mechanical properties. Excellent physical properties.

In addition, since the composition of the present invention has good crosslinkability, it can be used for applications such as curing by crosslinking or utilizing the elasticity of the cured body. In the composition, due to moisture present in the air or in the adherend to which the curable composition is applied, for example, the group represented by formula (1) possessed by the polymer (A) and the polymer (D) When using, the group represented by the formula (1) in the polymer (D) is hydrolyzed to form a silanol group, and then the silanol groups are cured by dehydration condensation to form a siloxane bond, It is believed that a cured product is formed.

The composition of the present invention or the mixed/stirred two-part curable composition is suitably used as a sealant, adhesive, hot-melt adhesive, paint, or the like, for example, in construction/building material applications, automobile applications, and the like. . In addition, inorganic materials (e.g. cement, mortar, metal, glass) surface coating agents, sheet-forming compositions (sheet examples: breathable sheets, protective sheets, waterproof sheets, damping sheets, transfer sheets, light control sheet, antistatic sheet, conductive sheet, curing sheet, sound insulation sheet, light shielding sheet, decorative sheet, marking sheet, flame retardant sheet), film forming composition (film examples: marking film, protective film, ink fixing film , laminate film), foam-forming composition (examples of foam: rigid foam, soft foam, semi-rigid foam, flame-retardant foam), damping material, sound insulation material, sound insulation material, sound absorption material, artificial Forming compositions for leather, artificial skin, synthetic leather, various industrial parts, daily necessities, toiletry moldings, etc., paint vehicles, primer resins, various binders (e.g. ink binders, magnetic recording media binders, casting binders, binders for fired bodies, and binders for glass fiber sizing materials).

The cured product of the present invention is obtained from the composition of the present invention or the two-component curable composition. Curing conditions are not particularly limited, but the composition of the present invention is coated on a support, for example, in an environment of -20 to 120°C and 10 to 95% RH, preferably 20 to 90°C and 30 to 85% RH. Curing can proceed satisfactorily by leaving it in the environment for a predetermined period of time.

The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples. In the following descriptions of Examples, Comparative Examples, etc., "parts" means "mass parts" unless otherwise specified.

[Evaluation method of polymer etc.]
Methods for evaluating each physical property of the polymer are described below.

<Number average molecular weight (Mn) and weight average molecular weight (Mw)>
The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the polymer and the like were analyzed by gel permeation chromatography (GPC) and calculated by polystyrene conversion under the following conditions.

・ Apparatus: GPC-8220 (manufactured by Tosoh)
・Column: G7000HXL/7.8mmID x 1 +
GMHXL/7.8mm ID x 2 +
G2500HXL/7.8 mm ID x 1 ・Medium: Tetrahydrofuran ・Flow rate: 1.0 mL/min
・Concentration: 1.5mg/ml
・Injection volume: 300 μL
・Column temperature: 40°C
<Glass transition temperature (Tg)>
The glass transition temperature (Tg) of each polymer was measured with a differential scanning calorimeter (DSC).

・Equipment: DSC7000X (manufactured by Hitachi High-Tech Science)
・Temperature condition: Temperature rise from -100°C to 30°C at 10°C/min ・Sample container: Aluminum open cell ・Sample amount: 5 mg
<Silicon element content>
The silicon element content of each polymer was determined by adding 7 mL of a mixed acid containing hydrogen fluoride to 0.2 g of the polymer, wet ashing with a microwave decomposition device (manufactured by Antor Japan), and adding ultrapure water to the ashed sample. After adding and adjusting the volume to 50 mL, measurement was performed with an inductively coupled plasma atomic emission spectrometer (ICP-AES).

・Equipment: ICPE-9000 (manufactured by Shimadzu Corporation)
・High frequency power: 1.20 kW
・Plasma gas: 10.00 L/min
・Auxiliary gas: 0.60 L/min
・Carrier gas: 0.70 L/min
・Observation direction: axial direction [manufacturing example 1]
74 parts of n-butyl acrylate, 25 parts of 2-ethylhexyl acrylate, and 1 part of acryloxymethyltrimethoxysilane are charged into a stainless steel flask equipped with a stirrer, nitrogen gas inlet tube, thermometer and reflux condenser, and nitrogen is replaced. After that, the temperature was raised to 70°C. Then, while maintaining the contents in the flask at 75° C., 0.9 part of 3-mercaptopropyltrimethoxysilane is added, followed by 0.05 part of 2,2′-azobisisobutyronitrile (AIBN). was added to initiate the reaction. 0.05 part of AIBN was added 3 hours after the start of the reaction. After 6 hours from the start of the reaction, volatile components were distilled off under reduced pressure at 110° C. for 3 hours to obtain a (meth)acrylic polymer (A-1). The silicon element content of the polymer (A-1) was 1,820 ppm, Mn was 21,000, Mw was 54,000, and Tg was -64°C.

[Example 1]
(Meth) acrylic polymer (A-1) 100 parts, 1,2-cyclohexanedicarboxylic acid diisononyl ester "Hexamoll DINCH" (manufactured by BASF) 170 parts as a plasticizer, and polyhydroxycarboxylic acid ester "BYK R606" as a thixotropic agent ” (manufactured by BYK), 10 parts of fumed silica “HDK H18” (manufactured by Asahi Kasei Wacker), and 350 parts of heavy calcium carbonate “Whiten 305” (manufactured by Toyo Fine Chemicals) in a rotation / revolution mixer (ARE -310, manufactured by Thinky) at a rotation speed of 2,000 rpm for 3 minutes. Then, 4 parts of acryloxymethyltrimethoxysilane "X-12-1169MS" (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 206) as a silane coupling agent (B), N-2-(aminoethyl)-3-aminopropyltri A curable composition was obtained by mixing 1 part of methoxysilane “KBM-603” (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 222) with ARE-310 at a rotation speed of 2,000 rpm for 1 minute.

Various evaluations were performed on the obtained curable composition.

[Examples 2 to 10, Comparative Examples 1 to 6]
A curable composition was obtained in the same manner as in Example 1 except that the formulation composition was changed as described in Tables 1-1 and 1-2, and various evaluations were performed. The evaluation method will be described later.

The meaning of each component notation in Tables 1-1 and 1-2 is as follows.

· X-12-1169MS: acryloxymethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: 206)
· X-12-1303MS: methacryloxymethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: 220)
· X-12-1312MS: methoxymethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: 166)
· X-12-1307: mercaptomethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: 168)
· KBM-1003: vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: 148)
· KBM-5013: acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: 234)
· KBM-6103: N-2-(aminoethyl)-3-aminomethyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: 194)
・Isocyanatomethyltrimethoxysilane (molecular weight: 177)
· KBM-603: N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight: 222)
[Method for evaluating curable composition]
Methods for evaluating each physical property of the curable composition are described below.

<Tuck free time>
The curable compositions obtained in Examples and Comparative Examples were coated on a Teflon (registered trademark) sheet with a doctor blade so that the cured product layer had a thickness of 2 mm, and was heated at 23° C./50% RH. The time from the start of curing under the conditions until no adhesion was confirmed when a SUS spatula was brought into contact with the composition (cured product) was measured.

<Stress at break, elongation>
The curable compositions obtained in Examples and Comparative Examples were coated on a Teflon (registered trademark) sheet with a doctor blade so that the cured product layer had a thickness of 2 mm, and was heated at 23° C./50% RH. Cured for 7 days under conditions. After that, the obtained cured product was punched into a JIS No. 3 dumbbell shape to prepare a sample. According to JIS K6251: 2010 (vulcanized rubber and thermoplastic rubber-determination of tensile properties), the obtained sample was subjected to a tensile test at a tensile speed of 200 mm / min and at 23 ° C., and the stress at break and Elongation was measured.

<Shear adhesive strength>
The curable compositions obtained in Examples and Comparative Examples are made of aluminum (A1050, thickness 1 mm) in accordance with JIS-K6850: 1999 (adhesives-testing method for tensile shear bond strength of rigid adherends). was applied to two test pieces of No. 2, allowed to stand for 2 minutes, and laminated so that the thickness of the curable composition layer was 0.2 mm. The shear adhesive strength after curing for 7 days under the conditions of 23 ° C./50% RH was measured using a universal tensile tester AG-X (Shimadzu manufactured by Seisakusho).

<Gel fraction>
The curable compositions obtained in Examples and Comparative Examples were coated on a Teflon (registered trademark) sheet with a doctor blade so that the cured product layer had a thickness of 2 mm, and was heated at 23° C./50% RH. Cured for 7 days under conditions. After that, 0.2 g of the obtained cured product was weighed in a sample bottle in terms of dry mass, 40 g of ethyl acetate was added to the sample bottle, and the sample bottle was allowed to stand in an environment of 23° C. for one day. After filtration through a stainless steel wire mesh of 200 mesh made of SUS, the residue on the wire mesh was dried at 90° C. for 2 hours, the mass of the residue obtained was weighed, and the gel fraction was determined by the following formula.

Gel fraction (%) = (weighed value of residue after drying) / (weighed value of cured product after curing) x 100
<Shear adhesive strength after storage stability test>
The curable compositions obtained in Examples and Comparative Examples were filled into paper cartridges (capacity: 330 mL) and allowed to stand in an environment of 60° C. for one month as a storage stability test. After that, the shear adhesive strength was measured by the same method as above. The shear adhesive strength of the cured product after the storage stability test was left at 60°C for 1 month, and the shear adhesive strength of the cured product before the storage stability test after curing for 7 days at 23°C/50% RH. The change rate [%] of the shear adhesive strength was calculated by dividing by .

Claims

a (meth)acrylic polymer (A) having a group represented by formula (1), having a number average molecular weight (Mn) of 1,000 or more and containing 500 ppm or more of silicon element;
A curable composition containing a silane coupling agent (B) represented by formula (2) and having a molecular weight of less than 1,000.
Formula ( 1 ): -X- CH2 - SiR13
[In formula (1), R 1 is each independently an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydroxyl group, and at least one of R 1 is the alkoxy group or hydroxyl group X is -O-, -COO-, -S-, -N(R 2 )-, -CH(OH)-CH 2 -O-, -O-CO-NH- or -N(R 2 ) A divalent group represented by —CO—N(R 3 )—, where R 2 and R 3 are a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group, and R 2 and R 3 may be the same or different. ]
Formula (2): Y — CH 2 —SiR 13
[In formula (2), R 1 has the same definition as in formula (1); Y is a (meth)acryloyl group, an alkoxy group having 1 to 20 carbon atoms, a mercapto group, or an isocyanate group. ]
The curable composition according to claim 1, comprising 0.1 to 20 parts by mass of the (B) with respect to 100 parts by mass of the (meth)acrylic polymer (A).
The curable composition according to claim 1, wherein the (meth)acrylic polymer (A) has at least a terminal group represented by the formula (1).
The curable composition according to claim 1, wherein the (meth)acrylic polymer (A) has a glass transition temperature (Tg) of -20°C or lower.
The curable composition according to claim 1, wherein the (meth)acrylic polymer (A) has a number average molecular weight of 1,000 to 100,000.
The curable composition according to claim 1, which contains 0.05 to 10 parts by mass of an aminosilane compound (C) represented by the following formula (3) with respect to 100 parts by mass of the (meth)acrylic polymer (A). .
Formula ( 3 ): R 42 --N--(CH 2 ) n --SiR 13
[In formula (3), n is an integer of 1 to 6; R 1 has the same meaning as in formula (1); R 4 is each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or At least one hydrogen atom of the hydrocarbon group is a group substituted with a group selected from the group consisting of an unsubstituted amino group, a substituted amino group and an alkoxysilyl group. ]
A cured product obtained from the curable composition according to any one of claims 1 to 6.