(meth)acrylate-based copolymer and curable composition thereof

Abstract

A (meth)acrylate copolymer (B) having a reactive silicon group represented by general formula (1). The monomer components constituting the copolymer contain: a (meth)acrylate (b1); a (meth)acrylate polymer having more than one (meth)acryloyl group in the molecule (b2); and a chain transfer agent having a mercapto group (b3). The above monomer components further contain a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group, and / or the chain transfer agent (b3) having a mercapto group further has a reactive silicon group. -SiR 5 c X 3‑c (1) (in the formula, R 5 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. X represents a hydroxyl group or a hydrolyzable group. c represents 0 or 1.)

Description

TECHNICAL FIELD

[0001] The present application relates to a (meth)acrylate copolymer having a reactive silicon group, a production method thereof, and a curable composition containing the copolymer. BACKGROUND

[0002] An organic polymer having a hydroxyl group or a hydrolyzable group on a silicon atom and having a silicon group capable of forming a siloxane bond through a hydrolysis / condensation reaction (hereinafter also referred to as "reactive silicon group") reacts due to moisture or the like even at room temperature. It is known that the organic polymer is crosslinked through a siloxane condensation reaction of the reactive silicon group, thereby obtaining a rubber-like cured product.

[0003] Among these organic polymers, a polyoxyalkylene polymer having a reactive silicon group is excellent in handleability at the time of production or use of a compounded composition because the viscosity is relatively low. In addition, since the performance balance of mechanical properties, weather resistance, dynamic durability, and the like of the obtained cured product is good, it is widely used for applications such as sealing materials, adhesives, paints, and the like (see Patent Document 1).

[0004] It is known that a curable composition in which a polyoxyalkylene polymer having a reactive silicon group and a (meth)acrylate-based polymer having a reactive silicon group are used in combination in order to improve the weather resistance and adhesion of the polyoxyalkylene polymer having a reactive silicon group (see Patent Document 2). The curable composition is used as a high-weather-resistance sealant, an industrial adhesive.

[0005] On the other hand, as a (meth)acrylate-based polymer having a reactive silicon group, a polymer using a monomer having a reactive silicon group and a polymerizable unsaturated group, and a macromonomer having a polymerizable unsaturated group as a constituent monomer has been reported (see Patent Document 3).

[0006] PRIOR ART DOCUMENTS

[0007] PATENT DOCUMENTS

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 52-73998

[0009] Patent Document 2: Japanese Patent Application Laid-Open No. 59-122541

[0010] Patent Document 3: International Publication No. 2017 / 057719 SUMMARY

[0011] PROBLEMS TO BE SOLVED BY THE INVENTION

[0012] For a polymer having a reactive silicon group, it is desirable that the molecular weight distribution is narrow and the viscosity is low so that the handling before curing is easy, and that good physical properties are exhibited after curing.

[0013] In view of the above circumstances, an object of the present application is to provide a (meth)acrylate copolymer having a reactive silicon group, which has a narrow molecular weight distribution and a low viscosity, and which exhibits a good physical property after curing, and a curable composition comprising the copolymer.

[0014] Method for solving the problem

[0015] The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that the above problems can be solved by using a specific monomer as a monomer component constituting a (meth)acrylate polymer having a reactive silicon group, and using a chain transfer agent, thereby completing the present application.

[0016] That is, a first aspect of the present application relates to a (meth)acrylate copolymer (B) having a reactive silicon group represented by General Formula (1),

[0017] -SiR 5 c X 3-c (1)

[0018] (In the formula, R 5 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, X represents a hydroxyl group or a hydrolyzable group, and c represents 0 or 1.)

[0019] wherein the monomer component constituting the copolymer contains:

[0020] a (meth)acrylate (b1),

[0021] a (meth)acrylate polymer (b2) having more than one (meth)acryloyl group in a molecule, and

[0022] a chain transfer agent (b3) having a mercapto group,

[0023] and the above monomer component further contains a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group, and / or

[0024] the chain transfer agent (b3) having a mercapto group further has a reactive silicon group.

[0025] It is preferable that the (meth)acrylate polymer (b2) accounts for 0.2 mol% or more and 5.0 mol% or less of the above monomer component.

[0026] It is preferable that the chain transfer agent (b3) having a mercapto group accounts for 0.4 mol% or more and 15 mol% or less of the above monomer component.

[0027] It is preferable that the number average molecular weight of the (meth)acrylate polymer (b2) is 500 or more and 50,000 or less.

[0028] The weight average molecular weight of the (meth)acrylate-based copolymer (B) is preferably 80,000 or less.

[0029] The molecular weight distribution of the (meth)acrylate-based copolymer (B) is preferably 3.0 or more and 11.0 or less.

[0030] The molar ratio of the (meth)acrylate-based polymer (b2) to the chain transfer agent having a mercapto group (b3) is preferably 0.12 or more.

[0031] A second aspect of the present application relates to a (meth)acrylate-based copolymer (B) having a reactive silicon group represented by general formula (1),

[0032] wherein the copolymer contains a structure in which two first molecular chains are bonded via one second molecular chain, both ends of the second molecular chain being bonded to non-terminal portions of the first molecular chains,

[0033] the first molecular chain and the second molecular chain each being composed of a molecular chain of the (meth)acrylate-based copolymer,

[0034] the reactive silicon group being bonded to the first molecular chain,

[0035] the first molecular chain having a structure represented by -S-R at any terminal end, where S represents a sulfur atom and R represents a hydrocarbon group optionally having the reactive silicon group.

[0036] It is preferable that the monomer component constituting the first molecular chain contain at least one monomer selected from the group consisting of a methacrylate, isobornyl acrylate, dicyclopentyl acrylate and dicyclopentyl acrylate, and the monomer component constituting the second molecular chain contain an acrylate.

[0037] It is more preferable that, in the monomer component constituting the first molecular chain, the proportion of at least one monomer selected from the group consisting of a methacrylate, isobornyl acrylate, dicyclopentyl acrylate and dicyclopentyl acrylate be 60% by weight or more,

[0038] In the monomer component constituting the second molecular chain, the proportion of the acrylate is 60% by weight or more.

[0039] The sulfur atom concentration in the (meth)acrylate-based copolymer (B) is preferably 700 ppm or more and 20,000 ppm or less.

[0040] A third aspect of the present application relates to a curable composition containing the above (meth)acrylate-based copolymer (B).

[0041] The above curable composition can further contain a polyoxyalkylene-based polymer (A) having a reactive silicon group represented by general formula (1).

[0042] The polyoxyalkylene-based polymer (A) preferably has a terminal structure represented by General Formula (2),

[0043] [Chemical Formula 1]

[0044]

[0045] wherein R 1 , R 3 each independently is a divalent bonding group having 1 to 6 carbon atoms, and R 1 , R 3 each adjacent carbon atom bonded to each other is any of carbon, oxygen, and nitrogen, and R 2 , R 4 each independently is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 1 to 10, and R 5 is a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, and c represents 0 or 1.

[0046] A fourth aspect of the present application relates to a cured product, which is a cured product of the curable composition described above.

[0047] A fifth aspect of the present application relates to a method for producing a (meth)acrylate-based copolymer (B) having a reactive silicon group represented by General Formula (1),

[0048] The method comprises:

[0049] a step of copolymerizing a monomer component,

[0050] The monomer component described above contains:

[0051] a (meth)acrylate (b1),

[0052] a (meth)acrylate-based polymer (b2) having more than one (meth)acryloyl group in a molecule, and

[0053] a chain transfer agent (b3) having a mercapto group,

[0054] and the monomer component described above further contains a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group, and / or

[0055] The chain transfer agent (b3) having a mercapto group further has a reactive silicon group.

[0056] Effects of the Invention

[0057] According to the present invention, reactive silicone-based (meth)acrylate copolymers with narrow molecular weight distribution, low viscosity, and good physical properties (e.g., elongation, strength, etc.) after curing, as well as curable compositions comprising such copolymers, are available. The reactive silicone-based (meth)acrylate copolymers of the present invention comprise block copolymers, which, although having a narrow molecular weight distribution and a high average molecular weight, can reduce viscosity to a low level.

[0058] The reactive silicon-based (meth)acrylate copolymers of the present invention can also be combined with reactive silicon-based polyoxyethylene polymers to form curable compositions. These curable compositions can produce cured products with high tensile strength and adhesive strength.

[0059] The curable composition of a preferred embodiment of the present invention exhibits high thixotropy, thus providing good workability during application. Detailed Implementation

[0060] The embodiments of the present invention will be described in detail below, but the present invention is not limited to these embodiments.

[0061] <<Reactive Silicon-Based (Meth)acrylate Copolymer (B)>>

[0062] (Meth)acrylate copolymers (B) have reactive silicon groups represented by general formula (1) at the ends of the molecular chains and / or the side chains (non-end sites).

[0063] -SiR 5 c X 3-c (1)

[0064] (where R is in the formula) 5 A hydrocarbon group consisting of 1 to 20 carbon atoms, either substituted or unsubstituted. X represents a hydroxyl group or a hydrolyzable group. c represents 0 or 1.

[0065] R 5 The hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. As R 5 Specific examples include methyl, ethyl, chloromethyl, methoxymethyl, N,N-diethylaminomethyl, etc., with methyl and ethyl being preferred.

[0066] Examples of X include: hydroxyl, hydrogen, halogen, alkoxy, acyloxy, ketooxime ester, amino, amide, acid amide, aminooxy, mercapto, alkenyloxy, etc. Among these, alkoxy groups such as methoxy and ethoxy are more preferred due to their hydrolytic stability and ease of processing, and methoxy and ethoxy are particularly preferred.

[0067] As the reactive silicon group possessed by the (meth)acrylate-based copolymer (B), specifically, mention can be made of trimethoxysilyl group, triethoxysilyl group, tris(2-propenyloxy)silyl group, triacetyloxy silyl group, dimethoxymethylsilyl group, diethoxymethylsilyl group, dimethoxyethylsilyl group, (chloromethyl)dimethoxysilyl group, (chloromethyl)diethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group, (N,N-diethylaminomethyl)diethoxysilyl group, and the like, but is not limited thereto. Among these, methyldimethoxysilyl group, trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group are preferred since they exhibit high reactivity and cured products having good mechanical properties can be obtained, and trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group, (methoxymethyl)dimethoxysilyl group, (methoxymethyl)diethoxysilyl group, (N,N-diethylaminomethyl)dimethoxysilyl group are more preferred since cured products having high rigidity can be obtained, and trimethoxysilyl group, triethoxysilyl group, (chloromethyl)dimethoxysilyl group are further preferred.

[0068] The reactive silicon group equivalent of the (meth)acrylate-based copolymer (B) is not particularly limited, and is preferably 0.06 mmol / g or greater, more preferably 0.08 mmol / g or greater, and further preferably 0.1 mmol / g or greater. In addition, the above-mentioned reactive silicon group equivalent is preferably 1.0 mmol / g or less, more preferably 0.5 mmol / g or less, and particularly preferably 0.3 mmol / g or less, from the aspect of inhibiting the decrease in elongation of the cured product.

[0069] The reactive silicon group equivalent of the (meth)acrylate-based copolymer (B) in the case where the polyoxyalkylene-based polymer (A) and the (meth)acrylate-based copolymer (B) are used in combination is not particularly limited, and is preferably 0.2 mmol / g or greater, more preferably 0.5 mmol / g or greater, and further preferably 0.6 mmol / g or greater. In addition, the above-mentioned reactive silicon group equivalent is preferably 2.0 mmol / g or less, more preferably 1.0 mmol / g or less, from the aspect of inhibiting the decrease in elongation of the cured product. In addition, in order to obtain a cured product that is high in rigidity and high in flexibility, the above-mentioned reactive silicon group equivalent is particularly preferably 0.5 mmol / g or greater and 1.0 mmol / g or less.

[0070] The (meth)acrylate-based copolymer (B) is a polymer formed by copolymerizing a monomer component of at least a (meth)acrylate (bl), a (meth)acrylate-based polymer having more than one (meth)acryloyl group in a molecule (b2), and a chain transfer agent having a mercapto group (b3). Note that, in the present application, "(meth)acrylic acid" means "acrylic acid and / or methacrylic acid".

[0071] The (meth)acrylate-based copolymer (B) has a reactive silicon group by satisfying either or both of the following two conditions.

[0072] Condition 1: The above monomer component further contains a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group.

[0073] Condition 2: The chain transfer agent having a mercapto group (b3) further has a reactive silicon group.

[0074] In order to obtain a cured product having high elongation, it is preferable that the reactive silicon group introduced by Condition 2 be more than the reactive silicon group introduced by Condition 1. Specifically, the equivalent of the reactive silicon group introduced by Condition 1 is preferably 0.01 mmol / g or more, more preferably 0.03 mmol / g or more, and further preferably 0.05 mmol / g or more. In addition, the above equivalent of the reactive silicon group is preferably 1.0 mmol / g or less, and more preferably 0.5 mmol / g or less. The equivalent of the reactive silicon group introduced by Condition 2 is preferably 0.2 mmol / g or more, more preferably 0.3 mmol / g or more, and further preferably 0.5 mmol / g or more. In addition, the above equivalent of the reactive silicon group is preferably 1.5 mmol / g or less, and more preferably 1.0 mmol / g or less.

[0075] In order to obtain a cured product having high strength, it is preferable that a reactive silicon group be introduced by both Condition 1 and Condition 2. Specifically, the equivalent of the reactive silicon group introduced by Condition 1 is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and further preferably 0.3 mmol / g or more. In addition, the above equivalent of the reactive silicon group is preferably 1.8 mmol / g or less, and more preferably 1.0 mmol / g or less. The equivalent of the reactive silicon group introduced by Condition 2 is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and further preferably 0.3 mmol / g or more. In addition, the above equivalent of the reactive silicon group is preferably 1.5 mmol / g or less, and more preferably 1.0 mmol / g or less.

[0076] ((meth)acrylate (bl))

[0077] As the (meth)acrylate (b1), there is no particular limitation, and for example, mention can be made of methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, phenyl (meth)acrylate, benzoyl (meth)acrylate, benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, an oxirane adduct of (meth)acrylic acid, 2,2,2-trifluoroethyl (meth)acrylate, 3,3,3-trifluoropropyl (meth)acrylate, 3,3,4,4,4-pentafluorobutyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, trifluoromethyl (meth)acrylate, perfluoroethyl (meth)acrylate, bis(trifluoromethyl)methyl (meth)acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth)acrylate, 2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl (meth)acrylate, 2-perfluorohexadecylethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, chloroethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, glycidyl (meth)acrylate, 2-aminoethyl (meth)acrylate, and the like. One kind alone can be used, or two or more kinds in combination can be used.

[0078] As the (meth)acrylate (b1), an alkyl (meth)acrylate is preferable.

[0079] In order to obtain a cured product having high strength, it is preferable that the (meth)acrylate (b1) contain an alkyl (meth)acrylate having 1 to 4 carbon atoms in the alkyl group in an amount of 40% by mass or more, more preferably 45% by mass or more, and further preferably 50% by mass or more, relative to the total amount of the monomer components constituting the (meth)acrylate-based copolymer (B).

[0080] In order to form a hard polymer, the (meth)acrylate (b1) preferably contains at least one monomer selected from the group consisting of methyl acrylate, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate in an amount of 60% by mass or more.

[0081] From the viewpoint of being able to balance softness and high rigidity, the content of the (meth)acrylate (b1) is preferably 40% by weight or more, more preferably 45% by weight or more, further preferably 50% by weight or more, more further preferably 55% by weight or more, and still further preferably 60% by weight or more, relative to the total amount of the monomer components constituting the (meth)acrylate copolymer (B). In addition, from the viewpoint of durability of adhesion, it is preferably 50% by weight or more, more preferably 55% by weight or more, and further preferably 60% by weight or more, relative to the entire monomers constituting the (meth)acrylate copolymer (B). In order to ensure compatibility with the polyoxyalkylene polymer (A), it is preferably 60% by weight or more, and more preferably 70% by weight or more.

[0082] (meth)acrylate polymer (b2) having more than one (meth)acryloyl group in one molecule

[0083] The (meth)acrylate polymer (b2) is itself a polymer, and by having a (meth)acryloyl group, it is able to copolymerize with other monomers such as the (meth)acrylate (b1), and the (meth)acrylate polymer (b2) is one of the monomers constituting the (meth)acrylate copolymer (B). Furthermore, the (meth)acrylate polymer (b2) has more than one (meth)acryloyl group in one molecule, and thus is able to function as a so-called multifunctional macromonomer. The main chain skeleton (second molecular chain described later) of the (meth)acrylate polymer (b2) is able to form a structure in the (meth)acrylate copolymer (B) that crosslinks two molecular chains (first molecular chain described later) composed of polymers of the (meth)acrylate (b1) or the like. Hereinafter, the (meth)acrylate polymer (b2) is also referred to as a multifunctional macromonomer (b2).

[0084] The main chain skeleton of the polyfunctional macromonomer (b2) is a (meth) acrylate-based polymer. As the monomer constituting the main chain skeleton of the polyfunctional macromonomer (b2), there is no particular limitation, and various (meth) acryl-based monomers can be used. As the (meth) acryl-based monomer, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzoyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, an oxirane adduct of (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 3,3,3-trifluoropropyl (meth) acrylate, 3,3,4,4,4-pentafluorobutyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, trifluoromethyl (meth) acrylate, perfluoroethyl (meth) acrylate, bis(trifluoromethyl)methyl (meth) acrylate, 2-trifluoromethyl-2-perfluoroethyl ethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluorohexadecylethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-aminoethyl (meth) acrylate, and the like can be cited.

[0085] In addition, the above-mentioned (meth)acrylic monomer can also be used in combination with other monomers that exhibit copolymerizability. As the other monomers, for example, styrene-based monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrene sulfonic acid, fluorine-containing vinyl monomers such as perfluoroethylene, perfluoropropylene, and vinylidene chloride, maleic acid and its derivatives such as maleic acid, maleic anhydride, maleic acid monoalkyl ester, and maleic acid dialkyl ester, fumaric acid and its derivatives such as fumaric acid, fumaric acid monoalkyl ester, and fumaric acid dialkyl ester, maleimide-based monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearyl maleimide, phenylmaleimide, and cyclohexylmaleimide, vinyl ester-based monomers such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate, olefin-based monomers such as ethylene and propylene, conjugated diene-based monomers such as butadiene and isoprene, (meth)acrylamide, (meth)acrylonitrile, and vinyl-based monomers such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol, and butyl vinyl ether can be mentioned. The other monomers can be used singly or in combination of two or more.

[0086] The main chain skeleton of the polyfunctional macromonomer (b2) is preferably composed of a soft polymer. Specifically, the monomer component forming the main chain skeleton of the polyfunctional macromonomer (b2) preferably contains 60% by weight or more of an acrylate ester (excluding isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate).

[0087] The (meth)acryloyl group possessed by the polyfunctional macromonomer (b2) is preferably represented by the following general formula (7).

[0088] CH2=C(R 8 )-COO-Z (7)

[0089] (in the formula, R 8 represents hydrogen or a methyl group. Z represents the main chain skeleton of the polyfunctional macromonomer (b2)).

[0090] The polyfunctional macromonomer (b2) has an average of more than one (meth)acryloyl group in one molecule. The number of (meth)acryloyl groups in one molecule of the polyfunctional macromonomer (b2) is preferably an average of 1.1 to 5, more preferably 1.3 to 4, further preferably 1.6 to 2.5, and particularly preferably 1.8 to 2.0. Note that the polyfunctional macromonomer (b2) can have only acryloyl groups, only methacryloyl groups, or both acryloyl groups and methacryloyl groups as the (meth)acryloyl groups.

[0091] The polyfunctional macromonomer (b2) can have a (meth)acryloyl group at either or both of the molecular chain terminal and side chain of the (meth)acrylate-based polymer. From the viewpoint of excellent mechanical properties, it is preferred to have a (meth)acryloyl group at the molecular chain terminal. It is particularly preferred that the polyfunctional macromonomer (b2) has a (meth)acryloyl group at both terminals of the molecular chain of the (meth)acrylate-based polymer, respectively.

[0092] The method of introducing a (meth)acryloyl group to the polyfunctional macromonomer (b2) is not particularly limited, and for example, the following methods can be used. The following methods can be used in combination.

[0093] (iv) a method of reacting a copolymer obtained by copolymerizing a monomer having a reactive functional group (V group) (e.g., acrylic acid, 2-hydroxyethyl acrylate) with a (meth)acryl-based monomer, with a compound having a functional group reactive with the V group and a (meth)acryloyl group (e.g., 2-isocyanatoethyl (meth)acrylate).

[0094] (v) a method of introducing a (meth)acryloyl group at the molecular chain terminal (preferably both terminals of the molecular chain, respectively) after polymerizing a (meth)acryl-based monomer by a living radical polymerization method.

[0095] Among these methods, the method of (v) is preferred because a (meth)acryloyl group can be introduced at the molecular chain terminal. Examples of the "living radical polymerization method" include a method using a cobalt porphyrin complex as shown in J. Am. Chem. Soc., 1994, Vol. 116, p. 7943; a method using a nitroxide radical as shown in Japanese Patent Application Laid-Open No. 2003-500378; atom transfer radical polymerization (ATRP method) using an organic halide, a halogenosulfonyl compound, or the like as an initiator and a transition metal complex as a catalyst as shown in Japanese Patent Application Laid-Open No. 11-130931, and the like. The atom transfer radical polymerization method is most preferred because a (meth)acryloyl group can be easily introduced at the molecular chain terminal.

[0096] Alternatively, a (meth)acrylate-based polymer can be obtained using a metallocene catalyst as shown in Japanese Patent Application Laid-Open No. 2001-040037 and a thiol compound having at least one reactive silicon group in the molecule.

[0097] The number average molecular weight of the multifunctional macromonomer (b2) is not particularly limited, and is preferably 500 or more, more preferably 1000 or more, and further preferably 2000 or more, from the viewpoint of balancing the adhesiveness of the curable composition and the ease of handling of (b2). In addition, it is preferably 100,000 or less, more preferably 50,000 or less, further preferably 40,000 or less, more further preferably 30,000 or less, particularly preferably 15,000 or less, and most preferably 10,000 or less. In addition, the number average molecular weight of the multifunctional macromonomer (b2) is preferably 8,000 or less, more preferably 6,000 or less, and further preferably 5,000 or less, from the viewpoint of improving the strength of the cured product and improving the thixotropy of the curable composition.

[0098] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the multifunctional macromonomer (b2) is not particularly limited, and a narrow distribution is preferred, and specifically, it is preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, more further preferably 1.4 or less, and particularly preferably 1.3 or less.

[0099] The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the multifunctional macromonomer (b2) are values measured by GPC (polystyrene conversion), and the detailed measurement method is described in the Examples.

[0100] The (meth)acrylate-based copolymer (B) has a molecular chain composed of a polymer of the (meth)acrylate (b1) or the like, and a molecular chain from the main chain skeleton of the multifunctional macromonomer (b2). The multifunctional macromonomer (b2) has more than one (meth)acryloyl group as a polymerizable group in one molecule, and therefore, the (meth)acrylate-based copolymer (B) has a structure in which more than one molecular chain composed of a polymer of the (meth)acrylate (b1) or the like is bonded to one molecular chain of the multifunctional macromonomer (b2). The molecular chain of the multifunctional macromonomer (b2) can be introduced to the end of the molecular chain composed of a polymer of the (meth)acrylate (b1) or the like, or to the side chain of the molecular chain, but the latter is preferred from the viewpoint of adhesiveness.

[0101] In particular, in the case where the multifunctional macromonomer (b2) has a (meth)acryloyl group at each of the two ends of the molecular chain of the (meth)acrylate-based polymer, an H-type structure in which a molecular chain composed of a polymer of the (meth)acrylate (b1) or the like is bonded to each of the two ends of the molecular chain of the multifunctional macromonomer (b2) can be formed. Here, the molecular chain of the multifunctional macromonomer (b2) corresponds to the horizontal bar of H, and the molecular chain composed of a polymer of the (meth)acrylate (b1) or the like corresponds to the two vertical bars contained in H.

[0102] The content of the multifunctional macromonomer (b2) relative to the total amount of the monomer components constituting the (meth)acrylate-based copolymer (B) is preferably 1 to 60% by weight, more preferably 5 to 50% by weight, and further preferably 10 to 40% by weight. Among them, in the case where a cured product of the (meth)acrylate-based copolymer (B) having a high Young's modulus is intended, the content of the multifunctional macromonomer (b2) is preferably less than 35% by weight. On the other hand, in the case where a cured product of the (meth)acrylate-based copolymer (B) having a low Young's modulus is intended, the content of the multifunctional macromonomer (b2) is preferably 35% by weight or more. In addition, the content of the multifunctional macromonomer (b2) is preferably 0.2% by mole or more and 5.0% by mole or less, more preferably 0.6% by mole or more and 2.3% by mole or less, and further preferably 0.8% by mole or more and 2.1% by mole or less, in the monomer components constituting the (meth)acrylate-based copolymer (B). If the above range is satisfied, the gelation at the time of synthesizing the (meth)acrylate-based copolymer (B) can be suppressed, and the effects brought by the multifunctional macromonomer (b2) can be achieved.

[0103] The number of the multifunctional macromonomer (b2) contained in one molecule of the (meth)acrylate-based copolymer (B) is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.05 or more, on average. In addition, it is preferably 2.0 or less, more preferably 1.5 or less, and further preferably 1.3 or less.

[0104] (Chain transfer agent (b3) having a mercapto group)

[0105] By including the chain transfer agent (b3) having a mercapto group in the monomer components constituting the (meth)acrylate-based copolymer (B), even if the multifunctional macromonomer (b2) is used, the molecular weight distribution of the (meth)acrylate-based copolymer (B) can be made narrow, and the gelation at the time of synthesizing the (meth)acrylate-based copolymer (B) can be suppressed. In addition, the polymer molecule into which one molecule of the multifunctional macromonomer (b2) is introduced in one molecule of the (meth)acrylate-based copolymer (B) can be preferentially synthesized.

[0106] The chain transfer agent (b3) having a mercapto group can not have a reactive silicon group, but preferably further has a reactive silicon group. By making the chain transfer agent (b3) having a mercapto group have a reactive silicon group, the reactive silicon group can be introduced to the end of the molecular chain constituted by the polymer of the (meth)acrylate (b1) or the like.

[0107] As the chain transfer agent having a mercapto group (b3), there is no particular limitation, and examples thereof include 3-mercaptopropyl dimethoxymethyl silane, 3-mercaptopropyl trimethoxysilane, (mercaptomethyl)dimethoxymethyl silane, (mercaptomethyl)trimethoxysilane, n-dodecyl mercaptan, t-dodecyl mercaptan, lauryl mercaptan, and the like.

[0108] The content of the chain transfer agent having a mercapto group (b3) is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.3% by mass or more and 7% by mass or less, further preferably 0.5% by mass or more and 5% by mass or less, relative to the total amount of the monomer components constituting the (meth)acrylate-based copolymer (B). In addition, the content of the chain transfer agent having a mercapto group (b3) is preferably 0.1% by mole or more and 15% by mole or less, more preferably 0.4% by mole or more and 10% by mole or less, further preferably 0.5% by mole or more and 9% by mole or less, particularly preferably 0.5% by mole or more and 8% by mole or less, in the monomer components constituting the (meth)acrylate-based copolymer (B). If the above range is satisfied, the effects brought by the chain transfer agent having a mercapto group (b3) can be achieved.

[0109] The content of the chain transfer agent having a mercapto group (b3) is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 20% by mass or less, further preferably 5% by mass or more and 15% by mass or less, relative to the total amount of the monomer components constituting the (meth)acrylate-based copolymer (B), in the case where the polyoxyalkylene-based polymer (A) is used in combination with the (meth)acrylate-based copolymer (B). In addition, the content of the chain transfer agent having a mercapto group (b3) is preferably 0.4% by mole or more and 18% by mole or less, more preferably 0.4% by mole or more and 15% by mole or less, further preferably 2% by mole or more and 15% by mole or less, particularly preferably 4% by mole or more and 12% by mole or less, in the monomer components constituting the (meth)acrylate-based copolymer (B). If the above range is satisfied, the effects brought by the chain transfer agent having a mercapto group (b3) can be achieved.

[0110] Since the grafting rate of the multifunctional macromonomer (b2) is increased, it is preferable to adjust the content of the multifunctional macromonomer (b2) and the content of the chain transfer agent having a mercapto group (b3) in such a manner that the molar ratio of the (meth)acrylate-based polymer (b2) to the chain transfer agent having a mercapto group (b3) is 0.12 or more. The above molar ratio is more preferably 0.15 or more, further preferably 0.20 or more.

[0111] (Monomer (b4) having a reactive silicon group and a polymerizable unsaturated group)

[0112] The monomer (b4) having a reactive silicon group and a polymerizable unsaturated group is an arbitrary monomer, and can not be used, but is preferably used. By using the monomer (b4), a reactive silicon group can be introduced to a side chain (non-terminal site) of a molecular chain of the polymer composed of the (meth)acrylate (b1) or the like.

[0113] As the monomer (b4) having a reactive silicon group and a polymerizable unsaturated group, for example, there can be mentioned: 3-(meth)acryloyloxypropyltrimethoxysilane, 3- (meth)acryloyloxypropyltriethoxysilane, 3-(meth)acryloyloxypropyldimethoxymethylsilane, (meth)acryloyloxymethyltrimethoxysilane, (meth)acryloyloxymethyl- dimethoxymethylsilane, and the like, compounds having a (meth)acryloyloxy group and a reactive silicon group; vinyltrimethoxysilane, vinyltriethoxysilane, and the like, compounds having a vinyl group and a reactive silicon group, and the like. These compounds can be used alone, or two or more kinds thereof can be used in combination.

[0114] In the case where the monomer (b4) is used, the content of the monomer (b4) is preferably 0.1% by mass or more and 50% by mass or less, more preferably 0.3% by mass or more and 30% by mass or less, further preferably 0.5% by mass or more and 20% by mass or less, relative to the total amount of the monomer components constituting the (meth)acrylate-based copolymer (B). In addition, from the viewpoint of improving the thixotropy of the curable composition and obtaining a cured product having a high elongation, the content of the monomer (b4) is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less.

[0115] The monomer components constituting the (meth)acrylate-based copolymer (B) can not contain other monomers than the arbitrary monomers of (b1) to (b4) described in detail above, or can contain the other monomers. As such other monomers, there can be mentioned (meth)acrylic monomers other than the (meth)acrylate (b1), and monomers other than the (meth)acrylic monomers. Specifically, the other monomers exemplified for the multifunctional macromonomer (b2) can also be used.

[0116] The polymerization method of (b1) to (b4) for forming the (meth)acrylate-based copolymer (B) is not particularly limited, and can be a general radical polymerization. According to the present embodiment, although it is a radical polymerization, control of polymerization can be achieved, the (meth)acrylate-based copolymer (B) as a block copolymer can be manufactured, and has the advantage that the molecular weight distribution can be made narrow.

[0117] As the polymerization initiator which can be used in the above radical polymerization, for example, azo compounds such as 2,2'-azobis(2-methylbutyronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis[N-(2-propionyl)-2-methylpropionamide], 1,1'-azobis(cyclohexane-1-carbonitrile) and the like; diacyl peroxides such as benzoyl peroxide, isobutyryl peroxide, isononyl peroxide, decanoyl peroxide, lauroyl peroxide, p-chlorobenzoyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide and the like; peroxydicarbonates such as diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di(1-methylheptyl) peroxydicarbonate, di(3-methoxybutyl) peroxydicarbonate, dicyclohexyl peroxydicarbonate and the like; peroxyesters such as tert-butyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxyisobutyrate, tert-butyl peroxyneopentanoate, tert-butyl peroxydiadipate, cumyl peroxyneodecanote and the like; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide and the like; dialkyl peroxides such as di-tert-butyl peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane and the like; hydroperoxides such as cumene hydroperoxide, tert-butyl hydroperoxide and the like; and peroxides such as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane and the like. These polymerization initiators can be used singly or in combination of two or more.

[0118] As the solvent which can be used in the above radical polymerization, for example, aromatic solvents such as toluene, xylene, styrene, ethylbenzene, p-dichlorobenzene, di(2-ethylhexyl) phthalate, di-n-butyl phthalate and the like; hydrocarbon compounds such as hexane, heptane, octane, cyclohexane, methylcyclohexane and the like; carboxylic acid ester compounds such as butyl acetate, n-propyl acetate, isopropyl acetate and the like; ketone compounds such as methyl isobutyl ketone, methyl ethyl ketone and the like; dialkyl carbonate compounds such as dimethyl carbonate, diethyl carbonate and the like; alcohol compounds such as n-propanol, 2-propanol, n-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, amyl alcohol and the like; and the like. Among them, alcohol compounds are preferred because the molecular weight distribution is narrowed. Aromatic solvents are preferred because the solubility is high. Aliphatic hydrocarbon solvents are preferred because the odor is low. The molecular weight distribution is affected by the amount of the chain transfer agent (b3) added and the solvent. In the case where the amount of the chain transfer agent (b3) added is 3% by weight or less, the kind of the solvent has a large effect, and in the case where a (meth)acrylate copolymer having a narrow molecular weight distribution is desired, isobutyl alcohol is preferably used.

[0119] The number average molecular weight of the (meth)acrylate-based copolymer (B) is not particularly limited, and is preferably 500 to 50,000, more preferably 500 to 30,000, particularly preferably 1,000 to 10,000, in terms of polystyrene-equivalent molecular weight determined by GPC. Among them, the number average molecular weight is preferably 7,000 or less, since a (meth)acrylate-based copolymer (B) having a low viscosity can be obtained.

[0120] In addition, since the viscosity is low and good adhesion is exerted at the time of mixing with the polyoxyalkylene-based polymer (A), the number average molecular weight of the (meth)acrylate-based copolymer (B) is preferably 3,500 or less.

[0121] The weight average molecular weight of the (meth)acrylate-based copolymer (B) is not particularly limited, and is preferably 500 to 80,000, more preferably 3,000 to 70,000, particularly preferably 5,000 to 65,000, in terms of polystyrene-equivalent molecular weight determined by GPC. Among them, it is preferably 30,000 or more, since good mechanical properties are exerted. In addition, since a cured product having a low viscosity and high strength is obtained at the time of mixing with the polyoxyalkylene-based polymer (A), the weight average molecular weight of the (meth)acrylate-based copolymer (B) is preferably 15,000 or less.

[0122] The molecular weight distribution of the (meth)acrylate-based copolymer (B) is not particularly limited, and is preferably 3.0 or more and 11.0 or less, more preferably 3.2 or more and 10.0 or less, further preferably 3.4 or more and 8.0 or less, from the viewpoint of making the (meth)acrylate-based copolymer (B) have a low viscosity. The molecular weight distribution of the (meth)acrylate-based copolymer (B) can be calculated from the number average molecular weight and the weight average molecular weight determined by GPC.

[0123] The (meth)acrylate-based copolymer (B) has a reactive silicon group by using a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group, or by using a chain transfer agent (b3) having a reactive silicon group other than a mercapto group. Both methods can be used in combination. By using a monomer (b4) having a reactive silicon group and a polymerizable unsaturated group, a reactive silicon group can be introduced randomly to the side chain of a molecular chain composed of a polymer of a (meth)acrylate (b1) or the like. In addition, by using a chain transfer agent (b3) having a reactive silicon group other than a mercapto group, a reactive silicon group can be introduced to the terminal of a molecular chain composed of a polymer of a (meth)acrylate (b1) or the like.

[0124] However, in order to further introduce a reactive silicon group to the (meth)acrylate-based copolymer (B), the following method can also be used in combination.

[0125] (vi) a method in which a monomer having a reactive functional group (V group) is copolymerized with (meth)acrylate (bl) or the like, and then a compound having a functional group reactive with the V group and a reactive silicon group is reacted with the resulting copolymer. Specifically, a method in which 2-hydroxyethyl acrylate is copolymerized and then an isocyanate silane compound having a reactive silicon group is reacted, a method in which glycidyl acrylate is copolymerized and then an amino silane compound having a reactive silicon group is reacted, and the like can be exemplified.

[0126] (vii) a method in which a terminal functional group of a (meth)acrylate-based copolymer synthesized by a living radical polymerization method is modified to introduce a reactive silicon group. A (meth)acrylate-based copolymer obtained by a living radical polymerization method is easy to introduce a functional group to the polymer terminal, and by modifying it, a reactive silicon group can be introduced to the polymer terminal.

[0127] As the compound having a functional group reactive with the V group and a reactive silicon group used in the method (vi), for example, isocyanate silane compounds such as 3-isocyanatepropyldimethoxymethylsilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, isocyanatemethyldimethoxymethylsilane, isocyanatemethyltrimethoxysilane, isocyanatemethyltriethoxysilane; epoxy silane compounds such as 3-glycidoxypropyldimethoxymethylsilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, glycidoxy-methyldimethoxymethylsilane, glycidoxy-methyltrimethoxysilane, glycidoxy-methyltriethoxysilane; amino silane compounds such as 3-aminopropyldimethoxymethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, aminomethyldimethoxymethylsilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, N-cyclohexylaminomethyldimethoxymethylsilane, N-cyclohexylaminomethyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, and the like can be exemplified.

[0128] In the method (vii), any modification reaction can be utilized, and for example, a method using a compound having a reactive group capable of reacting with a terminal functional group obtained by a living radical polymerization and a reactive silicon group; a method in which a double bond is introduced to the polymer terminal using a compound having a reactive group capable of reacting with a terminal functional group and a double bond, and then a reactive silicon group is introduced by hydrosilylation or the like can be exemplified.

[0129] The preferred (meth)acrylate-based copolymer (B) having a reactive silicon group can contain a triblock copolymer. The triblock copolymer can have the structure described below.

[0130] That is, in the (meth)acrylate-based copolymer (B) containing a reactive silicon group, a structure in which 2 first molecular chains are bonded via 1 second molecular chain is included. Both the first molecular chain and the second molecular chain are composed of molecular chains of the (meth)acrylate-based copolymer.

[0131] The first molecular chain is a molecular chain formed by copolymerization of (b1), (b2), (b3), and (b4). The reactive silicon group is bonded to the first molecular chain. In the case where the chain transfer agent (b3) having a mercapto group has a reactive silicon group, the reactive silicon group is bonded to the terminal of the first molecular chain, and in the case where the monomer (b4) having a reactive silicon group and a polymerizable unsaturated group is used, the reactive silicon group is bonded to a non-terminal site of the first molecular chain.

[0132] On the other hand, the second molecular chain corresponds to the main chain skeleton of the (meth)acrylate-based polymer in the multifunctional macromonomer (b2).

[0133] The bonding mode of the 2 first molecular chains and the 1 second molecular chain is different from that of a general ABA-type triblock copolymer, and is a form in which both terminals of the second molecular chain are bonded to non-terminal sites of the first molecular chains. That is, the triblock copolymer includes a structure of H type, in which case, 2 vertical bars in H correspond to the 2 first molecular chains, and 1 horizontal bar in H corresponds to the 1 second molecular chain.

[0134] However, the (meth)acrylate-based copolymer (B) containing a reactive silicon group is not limited to the triblock copolymer of H type, and can contain a block copolymer having another structure in addition to the triblock copolymer of H type. As such a block copolymer having another structure, for example, a block copolymer having a structure in which 3 first molecular chains are bonded via 2 second molecular chains, and the like can be given.

[0135] The first molecular chain and the second molecular chain are bonded via an ester bond from the (meth)acryloyl group in the multifunctional macromonomer (b2) (i.e., an ester bond corresponding to the ester bond in the above formula (7)).

[0136] A polymer in which the above first molecular chain is composed of a hard polymer and the above second molecular chain is composed of a soft polymer is preferred because a cured product having high strength and high elongation can be obtained. Here, the hard polymer refers to a polymer having a high glass transition temperature, and the soft polymer refers to a polymer having a low glass transition temperature. Specifically, the monomer components ((b1) and (b4)) constituting the first molecular chain preferably contain at least one monomer selected from the group consisting of a methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate. The proportion of the above monomer in the monomer components constituting the first molecular chain is preferably 60% by weight or more, and more preferably 70% by weight or more.

[0137] In addition, the monomer component constituting the second molecular chain (monomer component forming the main chain skeleton of the (meth)acrylate-based polymer in (b2)) preferably contains an acrylate ester (excluding isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate). The proportion of the above-described acrylate ester in the monomer component constituting the second molecular chain is preferably 60% by weight or more, and more preferably 70% by weight or more.

[0138] The above-described first molecular chain is a molecular chain formed by reacting a chain transfer agent having a mercapto group (b3), and thus can have a structure represented by -S-R at any terminal of the first molecular chain as a substituent from (b3). In the above formula, S represents a sulfur atom, and R represents a hydrocarbon group optionally having a reactive silicon group. The above-described hydrocarbon group can include an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, or the like. The above-described reactive silicon group is the reactive silicon group represented by the above-described general formula (1). Specific examples of R include a reactive silicon group-containing methyl group, a reactive silicon group-containing propyl group, a n-dodecyl group, a t-dodecyl group, a lauryl group, and the like.

[0139] The (meth)acrylate-based copolymer (B) having a reactive silicon group can have a substituent from the chain transfer agent having a mercapto group (b3), and thus can contain a sulfur atom. The sulfur atom concentration in the (meth)acrylate-based copolymer (B) is preferably 700 ppm or more and 20,000 ppm or less, and more preferably 1,000 ppm or more and 15,000 ppm or less.

[0140] <Curable composition>

[0141] One embodiment of the present application relates to a curable composition containing the (meth)acrylate-based copolymer (B) having a reactive silicon group described in detail above. The curable composition can contain only the (meth)acrylate-based copolymer (B) as the polymer having a reactive silicon group, and can contain the polyoxyalkylene-based polymer (A) having a reactive silicon group in addition to the (meth)acrylate-based copolymer (B).

[0142] <Curable composition>

[0143] <Reactive silicon group>

[0144] The polyoxyalkylene-based polymer (A) has a reactive silicon group represented by the above-described general formula (1) shown above. The reactive silicon group possessed by the polyoxyalkylene-based polymer (A) can be the same as or different from the reactive silicon group possessed by the (meth)acrylate-based copolymer (B).

[0145] R 5The number of carbon atoms of the hydrocarbon group is preferably from 1 to 10, more preferably from 1 to 5, further preferably from 1 to 3. As R 5 Specific examples of R include, for example, methyl, ethyl, chloromethyl, methoxymethyl, N,N-diethylaminomethyl, preferably methyl, ethyl, chloromethyl, methoxymethyl, more preferably methyl, methoxymethyl.

[0146] As X, for example, a hydroxyl group, a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amido group, an acid amido group, an aminooxy group, a mercapto group, an alkenyloxy group, and the like can be given. Among these, from the viewpoint of hydrolysis stability and ease of handling, an alkoxy group such as a methoxy group, an ethoxy group, and the like is more preferable, and a methoxy group, an ethoxy group, and the like are particularly preferable.

[0147] As the reactive silicon group possessed by the polyoxyalkylene-based polymer (A), for example, a trimethoxysilyl group, a triethoxysilyl group, a tri(2-propenyloxy)silyl group, a triacetyloxy silyl group, a dimethoxymethylsilyl group, a diethoxymethylsilyl group, a dimethoxyethylsilyl group, a (chloromethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, a (N,N-diethylaminomethyl)dimethoxysilyl group, a (N,N-diethylaminomethyl)diethoxysilyl group, and the like can be given, but are not limited thereto. Among these, a methyldimethoxysilyl group, a trimethoxysilyl group, a triethoxysilyl group, a (chloromethyl)dimethoxysilyl group, a (methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilyl group, and a (N,N-diethylaminomethyl)dimethoxysilyl group are preferable because they exhibit high reactivity and a cured product having good mechanical properties can be obtained, a trimethoxysilyl group, a triethoxysilyl group, and a (chloromethyl)dimethoxysilyl group are more preferable because a cured product having high rigidity can be obtained, and a trimethoxysilyl group and a triethoxysilyl group are further preferable.

[0148] The polyoxyalkylene-based polymer (A) can have, on average, one or less reactive silicon groups at one terminal position, or can have, on average, more than one reactive silicon groups at one terminal position.

[0149] The following describes the polyoxyalkylene polymer (A) having an average of more than one reactive silicon group at one terminal position. Having an average of more than one reactive silicon group at one terminal position means that the polyoxyalkylene polymer (A) contains a polyoxyalkylene having two or more reactive silicon groups at one terminal position. That is, the polyoxyalkylene polymer (A) can contain only a polyoxyalkylene having two or more reactive silicon groups at one terminal position, or can contain both a polyoxyalkylene having two or more reactive silicon groups at one terminal position and a polyoxyalkylene having one reactive silicon group at one terminal position. In addition, as the plurality of terminal positions possessed by one molecule of the polyoxyalkylene, there can be both a terminal position having two or more reactive silicon groups and a terminal position having one reactive silicon group. Furthermore, the polyoxyalkylene polymer (A) has an average of more than one reactive silicon group at one terminal position in total, but can also contain a polyoxyalkylene having a terminal position having no reactive silicon group.

[0150] The above terminal position having two or more reactive silicon groups can be represented by the following general formula (2), for example.

[0151] [Chemical Formula 2]

[0152]

[0153] (In the formula, R 1 , R 3 are each independently a bivalent linking group of carbon atoms number 1 to 6, and are bonded to each carbon atom adjacent to R 1 , R 3 The atoms of R 2 , R 4 are each independently hydrogen or a hydrocarbon group of carbon atoms number 1 to 10. n is an integer of 1 to 10. R 5 , X, c have the same meanings as described above in formula (1).

[0154] As R 1 , R 3 , there can be a bivalent organic group of carbon atoms number 1 to 6, or a hydrocarbon group optionally containing an oxygen atom. The number of carbon atoms of the hydrocarbon group is preferably 1 to 4, more preferably 1 to 3, and further preferably 1 to 2. As a specific example of R 1 , for example, CH2OCH2, CH2O, CH2, and preferably CH2OCH2 can be given. As a specific example of R 3 , for example, CH2, CH2CH2, and preferably CH2 can be given.

[0155] As R 2 , R 4the number of carbon atoms of the hydrocarbon group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2. As R 2 , R 4 , R 1 , R 3 , and R 2 , for example, a hydrogen atom, a methyl group, and an ethyl group can be given, and a hydrogen atom and a methyl group are preferred, and a hydrogen atom is more preferred.

[0156] According to a particularly preferred mode, R 1 of the terminal site represented by General Formula (2) is CH2OCH2, R 3 is CH2, R 2 is CH2, and R 4 is a hydrogen atom. n is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, further preferably 1 or 2. Among them, n is not limited to one value, and a plurality of values can be mixed.

[0157] The polyoxyalkylene polymer (A) can have an average of 1.0 or less of the reactive silicon group at one terminal site, but preferably has an average of more than 1.0 of the reactive silicon group at one terminal site. The average number is more preferably 1.1 or more, further preferably 1.5 or more, and more further preferably 2.0 or more. Also, it is preferably 5 or less, and more preferably 3 or less.

[0158] The number of terminal sites having more than one reactive silicon group contained in one molecule of the polyoxyalkylene polymer (A) is preferably an average of 0.5 or more, more preferably 1.0 or more, further preferably 1.1 or more, and more further preferably 1.5 or more. Also, it is preferably 4 or less, and more preferably 3 or less.

[0159] The polyoxyalkylene polymer (A) can have a reactive silicon group other than at the terminal site, but when it has only at the terminal site, a rubber-like cured product having a high elongation and showing a low elastic modulus is easily obtained, and thus is preferred.

[0160] From the viewpoint of the strength of the cured product, the average number of the reactive silicon group per 1 molecule of the polyoxyalkylene polymer (A) is preferably more than 1.0, more preferably 1.2 or more, further preferably 1.3 or more, more further preferably 1.5 or more, and particularly preferably 1.7 or more. In addition, from the viewpoint of the elongation of the cured product, it is preferably 6.0 or less, more preferably 5.5 or less, and most preferably 5.0 or less.

[0161] <Main chain structure>

[0162] The main chain skeleton of the polyoxyalkylene polymer (A) is not particularly limited, and for example, polyoxyethylene, polyoxypropylene, polyoxybutylene, polytetrahydrofuran, polyoxyethylene-polyoxypropylene copolymer, polyoxypropylene-polyoxybutylene copolymer, and the like can be given. Among them, polyoxypropylene is preferred.

[0163] The number average molecular weight of the polyoxyalkylene polymer (A) is preferably from 3000 to 100000, more preferably from 3000 to 50000, and particularly preferably from 3000 to 30000, in terms of polystyrene-equivalent molecular weight by GPC. When the number average molecular weight is less than 3000, the amount of introduced reactive silicon groups becomes large, and from the viewpoint of manufacturing cost, it can sometimes become inappropriate. When it exceeds 100000, it becomes high in viscosity, and from the viewpoint of operability, there is a tendency to become inappropriate.

[0164] As the molecular weight of the polyoxyalkylene polymer (A), a terminal group-conversion molecular weight can also be used, which is obtained by titration analysis of the terminal group concentration of the organic polymer precursor before introduction of the reactive silicon group, based on the principles of the hydroxyl value measurement method according to JIS K 1557 and the iodine value measurement method according to JIS K 0070, and taking into account the structure of the organic polymer (degree of branching determined according to the polymerization initiator used). The terminal group-conversion molecular weight of the polyoxyalkylene polymer (A) can also be obtained as follows: a calibration curve of the number average molecular weight of the organic polymer precursor determined by conventional GPC measurement and the above terminal group-conversion molecular weight is prepared, and the number average molecular weight determined by GPC of the polyoxyalkylene polymer (A) is converted to the terminal group-conversion molecular weight.

[0165] The molecular weight distribution (Mw / Mn) of the polyoxyalkylene polymer (A) is not particularly limited, and is preferably narrow, preferably less than 2.0, more preferably 1.6 or less, further preferably 1.5 or less, and particularly preferably 1.4 or less. The molecular weight distribution of the polyoxyalkylene polymer (A) can be obtained from the number average molecular weight and the weight average molecular weight determined by GPC.

[0166] In addition, the main chain structure of the polyoxyalkylene polymer (A) can be linear or branched.

[0167] <Method for synthesizing polyoxyalkylene polymer (A)>

[0168] Next, the method for synthesizing the polyoxyalkylene polymer (A) will be described.

[0169] The polyoxyalkylene polymer (A) having an average of one or less reactive silicon group at one terminal site can be obtained by introducing one carbon-carbon unsaturated bond to an average of one terminal of a hydroxyl-terminated polymer obtained by polymerization, and then reacting it with a compound containing a reactive silicon group capable of reacting with the carbon-carbon unsaturated bond. As the carbon-carbon unsaturated bond is introduced to the polymer, the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond described later can be used. As such halogenated hydrocarbon compound, in addition to the halogenated hydrocarbon compound having a carbon-carbon double bond such as allyl chloride described later, a halogenated hydrocarbon compound having a carbon-carbon triple bond such as propargyl chloride can also be used.

[0170] The polyoxyalkylene polymer (A) having an average of more than one reactive silicon group at one terminal site can be obtained by introducing two or more carbon-carbon unsaturated bonds to an average of one terminal of a hydroxyl-terminated polymer obtained by polymerization, and then reacting it with a compound containing a reactive silicon group capable of reacting with the carbon-carbon unsaturated bond. Hereinafter, the above-described preferred synthesis method will be described.

[0171] (Polymerization)

[0172] For the polyoxyalkylene polymer (A), a method in which a complex metal cyanide complex catalyst such as zinc hexacyanocobaltate glycol dimethyl ether complex is used, and an epoxy compound is polymerized with an initiator having a hydroxyl group is preferred.

[0173] As the initiator having a hydroxyl group, a compound having one or more hydroxyl groups such as ethylene glycol, propylene glycol, glycerol, pentaerythritol, a low molecular weight polyoxypropylene glycol, a polyoxypropylene triol, allyl alcohol, a polypropylene monoallyl ether, a polypropylene monoalkyl ether, and the like can be mentioned.

[0174] As the epoxy compound, an alkylene oxide such as an oxirane, an oxetane, a glycidyl ether such as methyl glycidyl ether, allyl glycidyl ether, and the like can be mentioned. Among these, an oxetane is preferred.

[0175] (Introduction of carbon-carbon unsaturated bond)

[0176] As the method of introducing two or more carbon-carbon unsaturated bonds to one terminal, a method in which an alkali metal salt is allowed to act on a hydroxyl-terminated polymer, and then an epoxy compound having a carbon-carbon unsaturated bond is first reacted, and then a halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is reacted is preferred. By using this method, the molecular weight and the molecular weight distribution of the polymer main chain can be controlled by the polymerization conditions, and furthermore, the introduction of the reactive group can be carried out efficiently and stably.

[0177] As the alkali metal salt, sodium hydroxide, sodium methoxide, sodium ethoxide, potassium hydroxide, potassium methoxide, potassium ethoxide are preferred, and sodium methoxide, potassium methoxide are more preferred. Sodium methoxide is particularly preferred from the viewpoint of availability.

[0178] As the temperature at which the alkali metal salt is allowed to act, 50°C or higher and 150°C or lower, and more preferably 110°C or higher and 140°C or lower are preferred. As the time at which the alkali metal salt is allowed to act, 10 minutes or longer and 5 hours or shorter, and more preferably 30 minutes or longer and 3 hours or shorter are preferred.

[0179] As the epoxy compound having a carbon-carbon unsaturated bond, a compound represented by General Formula (3) can be particularly suitably used:

[0180] [Chemical Formula 3]

[0181]

[0182] (R 1 , R 2 are the same as described above). Specifically, from the viewpoint of reactivity, allyl glycidyl ether, methacryloyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, butadiene monoxide, and 1,4-cyclopentadiene monoepoxide are preferred, and allyl glycidyl ether is particularly preferred.

[0183] The amount of the epoxy compound having a carbon-carbon unsaturated bond to be added can be any amount in consideration of the amount of introduction of the carbon-carbon unsaturated bond into the polymer, reactivity. In particular, the molar ratio with respect to the hydroxyl group possessed by the hydroxyl-terminated polymer is preferably 0.2 or higher, and more preferably 0.5 or higher. Furthermore, it is preferably 5.0 or lower, and more preferably 2.0 or lower.

[0184] As the reaction temperature at which the epoxy compound having a carbon-carbon unsaturated bond is allowed to undergo ring-opening addition reaction with the polymer containing a hydroxyl group, 60°C or higher and 150°C or lower, and more preferably 110°C or higher and 140°C or lower are preferred.

[0185] As the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond, chloroethylene, allyl chloride, methallyl chloride, bromoethylene, bromopropylene, methallyl bromide, iodoethylene, allyl iodide, methallyl iodide, and the like can be given, and from the viewpoint of ease of handling, the use of allyl chloride, methallyl chloride is preferred.

[0186] The amount of the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond to be added is not particularly limited, and the molar ratio with respect to the hydroxyl group possessed by the hydroxyl-terminated polymer is preferably 0.7 or higher, and more preferably 1.0 or higher. Furthermore, it is preferably 5.0 or lower, and more preferably 2.0 or lower.

[0187] The temperature when reacting the halogenated hydrocarbon compound having a carbon-carbon unsaturated bond is preferably 50°C or higher and 150°C or lower, and more preferably 110°C or higher and 140°C or lower. The reaction time is preferably 10 minutes or longer and 5 hours or shorter, and more preferably 30 minutes or longer and 3 hours or shorter.

[0188] (Introduction of a reactive silicon group)

[0189] The method of introducing a reactive silicon group is not particularly limited, and a publicly known method can be used. The following examples are shown for the method of introduction.

[0190] (i) A method of adding a hydrosilane compound to a polymer having a carbon-carbon unsaturated bond by a hydrosilylation reaction.

[0191] (ii) A method of reacting a polymer having a carbon-carbon unsaturated bond with a compound having both a group capable of forming a bond with a carbon-carbon unsaturated bond and a reactive silicon group (also referred to as a silane coupling agent). As the group capable of forming a bond with a carbon-carbon unsaturated bond, a mercapto group or the like can be given, but is not limited thereto.

[0192] (iii) A method of reacting a reactive group-containing polymer with a silane coupling agent. As the combination of the reactive group of the reactive group-containing polymer and the silane coupling agent, a hydroxyl group and an isocyanate group, a hydroxyl group and an epoxy group, an amino group and an isocyanate group, an amino group and a thioisocyanate group, an amino group and an epoxy group, an amino group and an α,β-unsaturated carbonyl group (a reaction using Michael addition), a carboxyl group and an epoxy group, an unsaturated bond and a mercapto group, or the like can be given, but is not limited thereto.

[0193] The method of (i) is preferred because the reaction is simple, the amount of the introduced reactive silicon group can be adjusted, and the physical properties of the obtained reactive silicon group-containing polyoxyalkylene-based polymer (A) are stable. The methods of (ii) and (iii) are preferred because the options for the reaction are many, and the introduction rate of the reactive silicon group can be easily increased.

[0194] As the hydrosilane compound that can be used in the method of (i), there is no particular limitation, and examples that can be given include trimethoxysilane, triethoxysilane, tris(2-propenyloxy)silane, triacetyloxy silane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyethylsilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, (methoxymethyl)dimethoxysilane, (methoxymethyl)diethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane, (N,N-diethylaminomethyl)diethoxysilane, and the like.

[0195] The amount of the hydrosilane compound is preferably 0.05 to 10, in terms of the molar ratio of the hydrosilane compound to the carbon-carbon unsaturated bond in the polymer as a precursor (mole of hydrosilane / mole of carbon-carbon unsaturated bond), from the viewpoint of reactivity, and more preferably 0.3 to 2, from the viewpoint of economy.

[0196] The hydrosilylation reaction is accelerated by various catalysts. As the hydrosilylation catalyst, a publicly known catalyst such as various complexes of cobalt, nickel, iridium, platinum, palladium, rhodium, ruthenium, etc. can be used. Catalysts such as platinum supported on a carrier such as alumina, silica, carbon black, chloroplatinic acid, chloroplatinic acid complexes containing chloroplatinic acid and an alcohol, an aldehyde, a ketone, etc., platinum-olefin complexes [e.g., Pt(CH2=CH2)2(PPh3), Pt(CH2=CH2)2Cl2], platinum-vinylsiloxane complexes [Pt{(vinyl)Me2SiOSiMe2(vinyl)}, Pt{Me(vinyl)SiO}4], platinum-phosphine complexes [Ph(PPh3)4, Pt(PBu3)4], platinum-phosphite complexes [Pt{P(OPh)3}4], etc. can be used. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum vinylsiloxane complexes are preferably used.

[0197] As the silane coupling agent which can be used in the method of (ii) or (iii) above, for example, the following can be mentioned: mercapto silanes such as 3-mercaptopropyltrimethoxysilane, 3- mercaptopropyldimethoxymethylsilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltriethoxysilane, mercaptomethyldimethoxymethylsilane and the like which react with unsaturated bonds; isocyanate silanes such as 3-isocyanatopropyltrimethoxysilane, 3- isocyanatopropyldimethoxymethylsilane, 3-isocyanatopropyltriethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltriethoxysilane, isocyanatomethyldimethoxymethylsilane and the like which react with hydroxyl groups; epoxy silanes such as 3- glycidoxypropyltrimethoxysilane, 3-glycidoxypropyldimethoxymethylsilane, 3- glycidoxypropyltriethoxysilane, glycidoxy-methyltrimethoxysilane, glycidoxy- methyltriethoxysilane, glycidoxy-methyldimethoxymethylsilane and the like which react with hydroxyl groups, amino groups or carboxyl groups; amino silanes such as 3- aminopropyltrimethoxysilane, 3-aminopropyldimethoxymethylsilane, 3- aminopropyltriethoxysilane, 3-(2-aminoethyl)propyltrimethoxysilane, 3-(2- aminoethyl)propyldimethoxymethylsilane, 3-(2-aminoethyl)propyltriethoxysilane, 3-(N- ethylamino)-2-methylpropyltrimethoxysilane, 3-naphthoylpropyltrimethoxysilane, 3- naphthoylpropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl- 3-aminopropyltrimethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N- cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl] ethylenediamine, bis(3-(trimethoxysilyl)propyl)amine and the like which react with isocyanate groups or thioisocyanate groups; and hydroxyalkyl silanes such as 3-hydroxypropyltrimethoxysilane, hydroxymethyltriethoxysilane and the like which react with isocyanate groups or thioisocyanate groups.

[0198] In a range not impairing the effects of the invention, the main chain of the polymer (A) can contain an ester bond or an amide segment represented by the general formula (4):

[0199] -NR 6 -C(=O)- (4)

[0200] (in the formula, R 6 represents an organic group having 1 to 10 carbon atoms or a hydrogen atom).

[0201] The cured product obtained from the curable composition containing the polymer (A) containing an ester bond or an amide segment sometimes has high hardness and strength due to the action of hydrogen bonding or the like. However, the polymer (A) containing an amide segment or the like can be cracked by heat or the like. In addition, the curable composition containing the polymer (A) containing an amide segment or the like has a tendency to increase in viscosity. In view of the advantages and disadvantages as described above, as the polymer (A), a polyoxyalkylene containing an amide segment or the like can be used, and a polyoxyalkylene not containing an amide segment or the like can be used.

[0202] As the amide segment represented by the above general formula (4), for example, an amide segment formed by the reaction of an isocyanate group with a hydroxyl group, the reaction of an amino group with a carbonate, the reaction of an isocyanate group with an amino group, the reaction of an isocyanate group with a mercapto group, or the like can be given. In addition, an amide segment formed by the reaction of the above amide segment containing an active hydrogen atom with an isocyanate group is also included in the amide segment represented by general formula (4).

[0203] As the method for producing the polymer (A) containing an amide segment, for example, a method in which an excess of a polyisocyanate compound is reacted with a polyoxyalkylene having an active hydrogen group-containing group at a terminal, and after the synthesis of a polymer having an isocyanate group at a terminal or at the same time as the synthesis, the Z group of a silicon compound represented by general formula (5) is reacted with all or a part of the isocyanate group of the synthesized polymer can be given:

[0204] Z-R 7 -SiR 5 c X 3-c (5)

[0205] (In the formula, R 5 , X and c are the same as the above meanings. R 7 is a divalent organic group, and is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms. Z is a hydroxyl group, a carboxyl group, a mercapto group, a primary amino group or a secondary amino group.).

[0206] As the silicon compound represented by the above general formula (5), there are no particular limitations, and examples thereof include: amino group-containing silanes such as γ-aminopropyl dimethoxymethyl silane, γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl trimethoxysilane, N-(β-aminoethyl)-γ-aminopropyl dimethoxymethyl silane, (N-phenyl)-γ-aminopropyl trimethoxysilane, N-ethylamino isobutyl trimethoxysilane, and the like; hydroxyl group-containing silanes such as γ-hydroxypropyl trimethoxysilane, and the like; mercapto group-containing silanes such as γ-mercaptopropyl trimethoxysilane, mercaptomethyl triethoxysilane, and the like; and the like. In addition, various α,β-unsaturated carbonyl compounds and Michael addition reactants of primary amino group-containing silanes or various (meth)acryl group-containing silanes and Michael addition reactants of primary amino group-containing compounds can also be used as the silicon compound represented by the above general formula (5), as described in Japanese Patent Application Publication No. 6-211879 (U.S. Patent No. 5364955), Japanese Patent Application Publication No. 10-53637 (U.S. Patent No. 5756751), Japanese Patent Application Publication No. 10-204144 (EP 0831108), Japanese Patent Application Publication No. 2000-169544, Japanese Patent Application Publication No. 2000-169545.

[0207] In addition, as the method for producing the polymer (A) containing an amide segment, for example, a method in which a reactive silicon group-containing isocyanate compound represented by general formula (6) is reacted with a terminal group having a polyoxyalkylene group having an active hydrogen group can be given:

[0208] O = C = N-R 7 -SiR 5 c X 3-c (6)

[0209] (In the formula, R 7 , R 5 , X, and c are the same as the above meanings.)

[0210] As the reactive silicon group-containing isocyanate compound represented by the above general formula (6), there are no particular limitations, and examples thereof include: γ-trimethoxysilylpropyl isocyanate, γ-triethoxysilylpropyl isocyanate, γ-methyldimethoxysilylpropyl isocyanate, γ-methyldiethoxysilylpropyl isocyanate, γ-(methoxymethyl)dimethoxysilylpropyl isocyanate, trimethoxysilylmethyl isocyanate, triethoxysilylmethyl isocyanate, dimethoxysilylmethyl isocyanate, diethoxysilylmethyl isocyanate, (methoxymethyl)dimethoxysilylmethyl isocyanate, and the like.

[0211] In the case where the polymer (A) contains an amide segment, the average number of amide segments per 1 molecule of the polymer (A) (average value) is preferably from 1 to 10, more preferably from 1.5 to 5, particularly preferably from 2 to 3. When the number is less than 1, sometimes the curability is insufficient, and on the contrary, when the number is more than 10, there is a possibility that the polymer (A) becomes high in viscosity and becomes difficult to handle. In order to reduce the viscosity of the curable composition and improve the handleability, it is preferable that the polymer (A) does not contain an amide segment.

[0212] In Japanese Patent Application Publication No. S59-122541, Japanese Patent Application Publication No. S63-112642, Japanese Patent Application Publication No. H6-172631, Japanese Patent Application Publication No. Hl l-116763, and the like, a method of mixing a polyoxyalkylene polymer (A) and a (meth)acrylate copolymer (B) is proposed. In addition to this, a method of synthesizing the (meth)acrylate copolymer (B) by copolymerizing monomer components constituting the (meth)acrylate copolymer (B) in the presence of a polyoxypropylene polymer (A) having a reactive silicon group can be used.

[0213] The weight ratio of the polyoxyalkylene polymer (A) : the (meth)acrylate copolymer (B) is preferably from 95 : 5 to 50 : 50. If it is within this range, a cured product high in tensile strength and adhesive strength can be obtained. The weight ratio of (A) : (B) is more preferably from 80 : 20 to 50 : 50, further preferably from 70 : 30 to 50 : 50.

[0214] < Silanol Condensation Catalyst (C) >>

[0215] For the purpose of promoting the reaction of condensing the reactive silicon groups of the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B), and chain extending or crosslinking the polymers, the curable composition of one embodiment of the present application preferably contains a silanol condensation catalyst (C).

[0216] As the silanol condensation catalyst (C), for example, an organotin compound, a carboxylic acid metal salt, an amine compound, a carboxylic acid, a metal alkoxide, and the like can be given.

[0217] As specific examples of the organotin compound, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin bis(maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dioctyltin bis(acetylacetonate), dioctyltin dilaurate, dioctyltin di-stearate, dioctyltin diacetate, dioctyltin oxide, a reaction product of dibutyltin oxide with an ester compound, a reaction product of dioctyltin oxide with an ester compound, a reaction product of dibutyltin oxide with phthalate, and the like can be given.

[0218] As specific examples of the carboxylic acid metal salt, there are carboxylic acid tin, carboxylic acid bismuth, carboxylic acid titanium, carboxylic acid zirconium, carboxylic acid iron, and the like. As the carboxylic acid metal salt, the following carboxylic acids can be combined with various metals.

[0219] As specific examples of the amine compound, there are octylamine, 2- ethylhexylamine, laurylamine, stearylamine, and the like; pyridine, 1,8- diazabicyclo[5,4,0]undec-7-ene (DBU), 1,5-diazabicyclo[4,3,0]non-5 (DBN), and the like; guanidine, phenylguanidine, diphenylguanidine, and the like; butylbiguanide, 1-o-tolylbiguanide, 1-phenylbiguanide, and the like; amino-containing silane coupling agents; ketimine compounds, and the like.

[0220] As specific examples of the carboxylic acid, there are acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, tertiary carbonic acid, and the like.

[0221] As specific examples of the metal alkoxide, there are titanium tetrabutoxide, titanium tetra(acetylacetone), titanium bis(ethylacetoacetate)diisopropoxide, and the like; aluminum tris(acetylacetone), ethyl aluminum diisopropyl acetoacetate, and the like; zirconium tetra(acetylacetone), and the like.

[0222] In the case of using the silanol condensation catalyst (C), as the amount thereof, 0.001 to 20 parts by weight, more preferably 0.01 to 15 parts by weight, particularly preferably 0.01 to 10 parts by weight, relative to 100 parts by weight of the (meth)acrylate polymer (B), or relative to 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B), is preferable.

[0223] <Other additives>

[0224] In the curable composition of one embodiment of the present application, in addition to the polyoxyalkylene polymer (A), the optional (meth)acrylate polymer (B), and the optional silanol condensation catalyst (C), a filler, an adhesion-improving agent, an anti-sagging agent, an antioxidant, a light stabilizer, an ultraviolet absorber, another resin, or the like can be contained as an additive. In addition, the curable composition of one embodiment of the present application can contain various additives as needed, with the purpose of adjusting various physical properties of the composition or the cured product thereof. As examples of such additives, for example, there are a plasticizer, a solvent, a diluent, a photocurable substance, an oxygen-curable substance, a surface property modifier, a silicate, a curing property modifier, a radical inhibitor, a metal deactivator, an ozone deterioration preventive, a phosphorus-based peroxide decomposer, a lubricant, a pigment, a mildew preventive, a flame retardant, a foaming agent, and the like.

[0225] <Filler>

[0226] The curable composition of one embodiment of the present application can contain a filler. As such a filler, heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, wet-process silica, silicic anhydride, hydrous silicic acid, alumina, carbon black, iron oxide, aluminum powder, zinc oxide, active zinc flower, PVC powder, PMMA powder, glass fiber, a filament, and the like can be given.

[0227] The amount of the filler is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, relative to 100 parts by weight of the (meth)acrylate-based polymer (B), or relative to 100 parts by weight of the total of the polyoxyalkylene-based polymer (A) and the (meth)acrylate-based polymer (B).

[0228] For the purpose of lightening (low specific gravity) of the composition, an organic hollow sphere or an inorganic hollow sphere can be added.

[0229] <Thickening agent>

[0230] The curable composition of one embodiment of the present application can contain a thickening agent. As the thickening agent, a silane coupling agent, a reactant of a silane coupling agent, or the like can be used.

[0231] As specific examples of the silane coupling agent, amino group-containing silanes such as γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, and the like; isocyanate group-containing silanes such as γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatemethyltrimethoxysilane, α-isocyanatemethyldimethoxymethylsilane, and the like; mercapto group-containing silanes such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, and the like; epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and the like; and the like can be given. In addition, reactants of various silane coupling agents can be used.

[0232] The amount of the silane coupling agent is preferably 0.1 to 20 parts by weight, particularly preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the (meth)acrylate-based polymer (B), or relative to 100 parts by weight of the total of the polyoxyalkylene-based polymer (A) and the (meth)acrylate-based polymer (B).

[0233] <Anti-sag agent>

[0234] In the curable composition of one embodiment of the present application, a sag-preventing agent can be contained as needed in order to prevent sagging and to make the workability good. The sag-preventing agent is not particularly limited and examples thereof include polyamide waxes, hydrogenated castor oil derivatives, metal soaps such as calcium stearate, aluminum stearate, and barium stearate, and the like. These sag-preventing agents can be used alone or in combination with two or more kinds.

[0235] The amount of the sag-preventing agent is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the (meth)acrylate polymer (B), or with respect to 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B).

[0236] <Antioxidant>

[0237] The curable composition of one embodiment of the present application can contain an antioxidant (anti-aging agent). If an antioxidant is used, the weather resistance of the cured product can be improved. Examples of the antioxidant include hindered phenols, monophenols, diphenols, polyphenols, and the like. Specific examples of the antioxidant are described in Japanese Patent Application Publication No. 4-283259 and Japanese Patent Application Publication No. 9-194731.

[0238] The amount of the antioxidant is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the (meth)acrylate polymer (B), or with respect to 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B).

[0239] <Light stabilizer>

[0240] The curable composition of one embodiment of the present application can contain a light stabilizer. If a light stabilizer is used, photo-oxidative degradation of the cured product can be prevented. Examples of the light stabilizer include benzotriazole compounds, hindered amine compounds, and benzoic acid ester compounds, and a hindered amine compound is particularly preferable.

[0241] The amount of the light stabilizer is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight of the (meth)acrylate polymer (B), or with respect to 100 parts by weight of the total of the polyoxyalkylene polymer (A) and the (meth)acrylate polymer (B).

[0242] <Ultraviolet absorber>

[0243] The curable composition of one embodiment of the present application can contain an ultraviolet absorber. If an ultraviolet absorber is used, the surface weather resistance of the cured product can be improved. As the ultraviolet absorber, for example, benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, metal chelate-based compounds, and the like can be given. The benzotriazole-based compounds are particularly preferred. As specific examples, commercially available products such as Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, and Tinuvin 571 (all of which are manufactured by BASF) can be given.

[0244] The amount of the ultraviolet absorber is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, relative to 100 parts by weight of the (meth)acrylate-based polymer (B), or relative to 100 parts by weight of the total of the polyoxyalkylene-based polymer (A) and the (meth)acrylate-based polymer (B).

[0245] The curable composition of one embodiment of the present application is preferably prepared in the form of a one-component type in which all the components are previously compounded and stored in a sealed state, and cured by moisture in the air after application.

[0246] In the case where the curable composition is of the one-component type, since all the components are previously compounded, it is preferred that the components containing moisture are previously dehydrated and dried, or dehydrated by reduced pressure or the like in the compounding kneading.

[0247] As the method of dehydrating and drying, in the case of a solid such as powder, a heat drying method is preferred, and in the case of a liquid, a reduced pressure dehydration method or a dehydration method using synthetic zeolite, activated alumina, silica gel, quicklime, magnesium oxide, or the like is preferred. Alternatively, a small amount of an isocyanate compound can be compounded and dehydrated by reacting the isocyanate group with water. A 3-ethyl-2-methyl-2-(3-methylbutyl)-1,3- oxazolidine or the like oxazolidine compound can be used.

[0248] In addition to the above-mentioned dehydrating and drying method, the storage stability can be further improved by adding a lower alcohol such as methanol or ethanol, or an alkoxysilane compound. As the alkoxysilane compound, for example, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, and the like can be given.

[0249] The amount of the dehydrating agent, particularly the above-mentioned alkoxysilane compound, is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the (meth)acrylate-based polymer (B), or relative to 100 parts by weight of the total of the polyoxyalkylene-based polymer (A) and the (meth)acrylate-based polymer (B).

[0250] The method for producing the curable composition of one embodiment of the present application is not particularly limited. For example, a conventional method such as kneading the above components using a mixer, a roll, a kneader, or the like at ordinary temperature or under heating, or dissolving and mixing the above components using a small amount of an appropriate solvent can be employed.

[0251] The curable composition of one embodiment of the present application can be used as a sealing material, an adhesive, a mold material (mold material for molding), a shock absorbing material, a vibration absorbing material, a soundproofing material, a foaming material, a paint, a spray material, a coating waterproofing agent, or the like for a building / ship / car / road, or the like.

[0252] The cured product obtained by curing the curable composition of one embodiment of the present application has good adhesion to various adherends, and thus the curable composition is more preferably used as a sealing material or an adhesive.

[0253] The curable composition of one embodiment of the present application can be used in various applications such as an electrical / electronic part material such as a solar cell back sealing material, an electrical insulation material such as an insulating coating material for an electric wire / cable, an elastic adhesive, a contact type adhesive, a spray type sealing material, a crack repair material, an adhesive for tiling, a powder paint, a cast material, a medical rubber material, a medical adhesive, a medical device sealing material, a food packaging material, a sealing material for a joint of an exterior material such as an adhesive sheet, a coating material, a primer, an electroconductive material for electromagnetic wave shielding, a thermally conductive material, a hot melt material, a potting agent for electrical / electronics, a film, a gasket, various molding materials, a wired glass, a rust / waterproof sealing material for an edge (cut portion) of a laminated glass, an automobile part, a motor part, various mechanical parts, and a liquid sealant.

[0254] The cured product of the curable composition of one embodiment of the present application can be tightly adhered to a wide range of substrates such as glass, ceramics, wood, metal, and resin molded products by being used alone or in combination with a primer, and thus the curable composition can also be used as a sealing composition or an adhesive composition.

[0255] The curable composition of one embodiment of the present application can also be used as an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for sticking stone, an adhesive for ceiling processing, an adhesive for floor processing, an adhesive for wall processing, an adhesive for vehicle panels, an adhesive for electrical / electronic / precision equipment assembly, a sealing material for direct glazing, a sealing material for laminated glass, a sealing material for SSG process, or a sealing material for construction joints of buildings.

[0256] Examples

[0257] Hereinafter, the present application will be specifically described with examples. The present application is not limited by the examples.

[0258] (Number average molecular weight and weight average molecular weight)

[0259] The number average molecular weight and the weight average molecular weight in the examples are GPC molecular weights measured under the following conditions.

[0260] Liquid delivery system: HLC-8220 GPC manufactured by Tosoh

[0261] Chromatographic column: TSK-GEL H manufactured by Tosoh

[0262] Solvent: THF

[0263] Molecular weight: polystyrene conversion

[0264] Measurement temperature: 40°C

[0265] (Sulfur atom concentration)

[0266] The sulfur atom concentration is a theoretical value calculated from the total amount of monomer components used for producing the (meth)acrylate-based copolymer (B) and the amount of chain transfer agent (b3) having a mercapto group.

[0267] (Synthetic Example 1)

[0268] Polyoxypropylene having a number average molecular weight of about 2000 was polymerized by the zinc hexacyanocobaltate glycol dimethyl ether complex catalyst to obtain polyoxypropylene having a number average molecular weight of 28500 (terminal group conversion molecular weight 17700), a molecular weight distribution Mw / Mn = 1.21, and hydroxyl groups at both terminals. With respect to the hydroxyl groups of the obtained hydroxyl-terminated polyoxypropylene, 1.0 molar equivalent of sodium methoxide was prepared as a 28% methanol solution and added. After distilling off the methanol by vacuum devolatilization, 1.0 molar equivalent of allyl glycidyl ether was added with respect to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and a reaction was performed at 130°C for 2 hours. Then, 0.28 molar equivalent of a methanol solution of sodium methoxide was added, the methanol was removed, and 1.79 molar equivalent of allyl chloride was further added to convert the terminal hydroxyl groups to allyl groups. With respect to 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, hexane 300 parts by weight and water 300 parts by weight were mixed and stirred, the water was removed by centrifugal separation, then water 300 parts by weight was further mixed in the obtained hexane solution and stirred, the water was again removed by centrifugal separation, and the hexane was removed by vacuum devolatilization. By the above operation, polyoxypropylene having a terminal structure having two or more carbon-carbon unsaturated bonds was obtained. It was found that the average number of carbon-carbon unsaturated bonds introduced at one terminal position was 2.0.

[0269] With respect to 100 parts by weight of the obtained polyoxypropylene having an average of 2.0 carbon-carbon unsaturated bonds at one terminal position, 36 ppm of divinyl disiloxane platinum complex (3% by weight in isopropyl alcohol solution with respect to platinum) was added, and 2.2 parts by weight of trimethoxysilane was slowly added dropwise while stirring. After allowing the mixed solution to react at 90°C for 2 hours, the unreacted trimethoxysilane was distilled off under reduced pressure, and thus a linear polyoxypropylene polymer having a reactive silicon group (A-1) having an average of 1.6 trimethoxysilyl groups at one terminal position, an average of 3.2 silicon groups per 1 molecule, and a number average molecular weight of 28500 was obtained.

[0270] (Synthetic Example 2)

[0271] Polyoxypropylene glycol having a number average molecular weight of about 2000 was used as an initiator, and polymerization of propylene oxide was carried out using a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of 28500 (end group conversion molecular weight: 17700), a molecular weight distribution Mw / Mn = 1.21, and hydroxyl groups at both ends. With respect to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, 1.2 molar equivalents of sodium methoxide was prepared as a 28% methanol solution and added. After distilling off the methanol by vacuum devolatilization, 1.5 molar equivalents of 3-chloro-l-propene was added with respect to the hydroxyl groups of the hydroxyl-terminated polyoxypropylene, and a reaction was carried out at 130°C for 2 hours. With respect to 100 parts by weight of the obtained unpurified allyl-terminated polyoxypropylene, 300 parts by weight of n-hexane and 300 parts by weight of water were mixed and stirred, and the water was removed by centrifugal separation. Further, 300 parts by weight of water was mixed in the obtained hexane solution and stirred, and the water was again removed by centrifugal separation. Then, the hexane was removed by vacuum devolatilization.

[0272] With respect to 100 parts by weight of the obtained polyoxypropylene, 36 ppm of a divinyl disiloxane platinum complex (3% by weight of isopropyl alcohol solution in terms of platinum) was added, and 1.0 part by weight of dimethoxymethylsilane was slowly added dropwise while stirring. After allowing the mixed solution to react at 90°C for 2 hours, the unreacted dimethoxymethylsilane was distilled off under reduced pressure, whereby a linear reactive silicon group-containing polyoxypropylene polymer (A-2) having an average of 1.6 silicon groups per 1 molecule of silicon and a number average molecular weight of 28500 was obtained.

[0273] (Synthetic Example 3)

[0274] In a reactor made in a deoxidized state, 0.42 parts by weight of copper bromide and 20.0 parts by weight of butyl acrylate were added, and heated and stirred. 8.8 parts by weight of acetonitrile as a polymerization solvent and 9.4 parts by weight of diethyl 2,5-dibromoadipate as an initiator were added and mixed, and at the stage of adjusting the temperature of the mixed solution to about 80°C, pentamethyldiethylene triamine (hereinafter referred to as triamine) was added, and the polymerization reaction was started. Next, 80.0 parts by weight of butyl acrylate was added dropwise, and the polymerization reaction was carried out. During the polymerization, the triamine was appropriately added, and the polymerization rate was adjusted. The total amount of the triamine used during the polymerization was 0.15 parts by weight. At the time when the monomer conversion (polymerization rate) was about 95% or more, the volatile components were removed by vacuum devolatilization, and a polymer concentrate was obtained.

[0275] The above concentrate was diluted with toluene, a filtration aid and an adsorbent (Kyoward 700SEN: Kyowa Chemical Industry Co., Ltd.), and hydrotalcite (Kyoward 500SH: Kyowa Chemical Industry Co., Ltd.) were added, and heated and stirred to about 80 to 100°C, and then the solid components were removed by filtration. The filtrate was concentrated under reduced pressure, and a polymer crude product was obtained.

[0276] To the polymer crude, potassium acrylate 11.2 parts by weight, 4-hydroxy-TEMPO 100 ppm, dimethylacetamide 100 parts by weight as a solvent were added, and the mixture was reacted at 70°C for 3 hours. After the solvent was distilled off under reduced pressure, a polymer concentrate was obtained. The concentrate was diluted with toluene, and the solid components were removed by filtration. The filtrate was concentrated under reduced pressure to obtain a multifunctional macromonomer (b2-1) having acryloyl groups at both terminals (i.e., having two acryloyl groups in one molecule of the polymer) with a number average molecular weight of 4030 (GPC molecular weight) and a molecular weight distribution (Mw / Mn) of 1.23.

[0277] (Synthetic Example 4)

[0278] To the reactor in which deoxidation was performed, copper bromide 0.42 parts by weight, and butyl acrylate 20.0 parts by weight were added, and heated and stirred. Acetonitrile 8.8 parts by weight as a polymerization solvent, and diethyl 2,5-dibromoadipate 4.7 parts by weight as an initiator were added and mixed, and at the stage at which the temperature of the mixture was adjusted to about 80°C, pentamethyldiethylene triamine (hereinafter referred to as triamine) was added, and the polymerization reaction was started. Next, butyl acrylate 80.0 parts by weight was added successively, and the polymerization reaction was performed. During the polymerization, the triamine was added as necessary, and the polymerization rate was adjusted. The total amount of the triamine used during the polymerization was 0.15 parts by weight. At the time when the monomer conversion (polymerization rate) was about 95% or more, the volatile components were removed by distillation under reduced pressure, and a polymer concentrate was obtained.

[0279] The above concentrate was diluted with toluene, and a filtration aid, an adsorbent (Kyoward 700SEN: Kyowa Chemical Industry Co., Ltd.), and hydrotalcite (Kyoward 500SH: Kyowa Chemical Industry Co., Ltd.) were added, and heated and stirred to about 80 to 100°C, and then the solid components were removed by filtration. The filtrate was concentrated under reduced pressure to obtain a polymer crude.

[0280] To the polymer crude, potassium acrylate 11.2 parts by weight, 4-hydroxy-TEMPO 100 ppm, dimethylacetamide 100 parts by weight as a solvent were added, and the mixture was reacted at 70°C for 3 hours. After the solvent was distilled off under reduced pressure, a polymer concentrate was obtained. The concentrate was diluted with toluene, and the solid components were removed by filtration. The filtrate was concentrated under reduced pressure to obtain a multifunctional macromonomer (b2-1) having acryloyl groups at both terminals (i.e., having two acryloyl groups in one molecule of the polymer) with a number average molecular weight of 4030 (GPC molecular weight) and a molecular weight distribution (Mw / Mn) of 1.23.

[0281] (Synthetic Example 5)

[0282] In a reactor made deoxidized, 0.42 parts by weight of copper bromide, 20.0 parts by weight of butyl acrylate were added, and heated and stirred. 8.8 parts by weight of acetonitrile as a polymerization solvent, 3.1 parts by weight of diethyl 2,5-dibromoadipate as an initiator were added and mixed, and at the stage of adjusting the temperature of the mixture to about 80°C, pentamethyldiethylene triamine (hereinafter referred to as triamine) was added, and the polymerization reaction was started. Next, 80.0 parts by weight of butyl acrylate was added successively, and the polymerization reaction was carried out. During the polymerization, the triamine was added as appropriate, and the polymerization rate was adjusted. The total amount of the triamine used during the polymerization was 0.15 parts by weight. At the time when the monomer conversion (polymerization rate) was about 95% or more, the volatile components were removed by pressure reduction devolatilization, and a polymer concentrate was obtained.

[0283] The above concentrate was diluted with toluene, a filtration aid, an adsorbent (Kyoward 700SEN: Kyowa Chemical Industry Co., Ltd.), and hydrotalcite (Kyoward 500SH: Kyowa Chemical Industry Co., Ltd.) were added, and heated and stirred to about 80 to 100°C, and then the solid components were removed by filtration. The filtrate was concentrated under reduced pressure, and a crude purified polymer was obtained.

[0284] The crude purified polymer, 3.8 parts by weight of potassium acrylate, 100 ppm of 4-hydroxy-TEMPO, and 100 parts by weight of dimethylacetamide as a solvent were added, and reacted at 70°C for 3 hours, and then the solvent was distilled off under reduced pressure, and a polymer concentrate was obtained. The concentrate was diluted with toluene, and the solid components were removed by filtration. The filtrate was concentrated under reduced pressure, and a multifunctional macromonomer (b2-3) having an acryloyl group at both terminals (i.e., having two acryloyl groups in one molecule of the polymer) having a number average molecular weight of 11410 (GPC molecular weight) and a molecular weight distribution (Mw / Mn) of 1.27 was obtained.

[0285] (Synthetic Example 6)

[0286] Into a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this was added dropwise a mixed solution obtained by dissolving 59.0 parts by weight of butyl acrylate, 10.0 parts by weight of stearyl methacrylate, 30.0 parts by weight of the multifunctional macromonomer (b2-1) prepared in Synthesis Example 3, 1.0 part by weight of 3-methacryloyloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol, over a period of 5 hours. Further polymerization was carried out at 105°C for 2 hours, to obtain an isobutyl alcohol solution (60% by weight of solid content) of the (meth)acrylate-based copolymer (B-1) having a reactive silicon group having a number average molecular weight of 2280 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of the solution was 0.069 mmol / g, the reactive silicon group equivalent was 0.38 mmol / g, and the sulfur atom content was 10941 ppm.

[0287] (Synthesis Example 7)

[0288] Into a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this was added dropwise a mixed solution obtained by dissolving 59.0 parts by weight of butyl acrylate, 10.0 parts by weight of stearyl methacrylate, 85.0 parts by weight of the multifunctional macromonomer (b2-1) prepared in Synthesis Example 3, 1.0 part by weight of 3-methacryloyloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol, over a period of 5 hours. Further polymerization was carried out at 105°C for 2 hours, to obtain an isobutyl alcohol solution (60% by weight of solid content) of the (meth)acrylate-based copolymer (B-2) having a reactive silicon group having a number average molecular weight of 3720 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of the solution was 0.13 mmol / g, the reactive silicon group equivalent was 0.25 mmol / g, and the sulfur atom content was 7185 ppm.

[0289] (Synthesis Example 8)

[0290] In a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this was added dropwise a mixed solution obtained by dissolving 59.0 parts by weight of butyl acrylate, 10.0 parts by weight of stearyl methacrylate, 85.0 parts by weight of the multifunctional macromonomer (b2-1) produced in Synthesis Example 3, 1.0 part by weight of 3-methacryloyloxypropyltrimethoxysilane, 13.0 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol over 5 hours. Further polymerization was carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (60% by weight of solid content) of the (meth)acrylate-based copolymer (B-3) having a reactive silicon group having a number average molecular weight of 2350 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of the solution was 0.13 mmol / g, the reactive silicon group equivalent was 0.42 mmol / g, and the sulfur atom content was 12574 ppm.

[0291] (Synthesis Example 9)

[0292] In a four-necked flask equipped with a stirrer, 53.2 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this was added dropwise a mixed solution obtained by dissolving 40.8 parts by weight of methyl methacrylate, 16.6 parts by weight of butyl acrylate, 0.3 parts by weight of 2-ethylhexyl acrylate, 0.3 parts by weight of stearyl methacrylate, 39.6 parts by weight of the multifunctional macromonomer (b2-3) produced in Synthesis Example 5, 0.3 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, 2.1 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.29 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 9.4 parts by weight of isobutyl alcohol over 5 hours. Further, 0.09 parts by weight of 2,2'-azobis(2-methylbutyronitrile) was dissolved in 2.9 parts by weight of isobutyl alcohol and added, and further polymerization was carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (60% by weight of solid content) of the (meth)acrylate-based copolymer (B-4) having a reactive silicon group having a number average molecular weight of 5830 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of the solution was 0.035 mmol / g, the reactive silicon group equivalent was 0.12 mmol / g, and the sulfur atom content was 3429 ppm.

[0293] (Synthesis Example 10)

[0294] In a four-necked flask equipped with a stirrer, 53.2 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this was added dropwise a mixed solution obtained by dissolving 51.5 parts by weight of methyl methacrylate, 21.0 parts by weight of butyl acrylate, 0.4 parts by weight of 2-ethylhexyl acrylate, 0.4 parts by weight of stearyl methacrylate, 25.0 parts by weight of the multifunctional macromonomer (b2-3) prepared in Synthesis Example 5, 0.4 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, 1.3 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.37 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 11.9 parts by weight of isobutyl alcohol over 5 hours. Further, 0.11 parts by weight of 2,2'-azobis(2-methylbutyronitrile) was dissolved in 3.6 parts by weight of isobutyl alcohol and added, and polymerization was further carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60%) of the (meth)acrylate-based copolymer (B-5) containing a reactive silicon group having a number average molecular weight of 9700 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of this solution was 0.022 mmol / g, the reactive silicon group equivalent was 0.082 mmol / g, and the sulfur atom content was 2123 ppm.

[0295] (Synthesis Example 11)

[0296] In a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this was added dropwise a mixed solution obtained by dissolving 50.0 parts by weight of methyl methacrylate, 7.0 parts by weight of butyl acrylate, 12.0 parts by weight of stearyl methacrylate, 30 parts by weight of the multifunctional macromonomer (b2-1) prepared in Synthesis Example 3, 1.0 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol over 5 hours. Polymerization was further carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60%) of the (meth)acrylate-based copolymer (B-6) containing a reactive silicon group having a number average molecular weight of 2450 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of this solution was 0.069 mmol / g, the reactive silicon group equivalent was 0.38 mmol / g, and the sulfur atom content was 10941 ppm.

[0297] (Synthesis Example 12)

[0298] In a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this was added dropwise a mixed solution obtained by dissolving 50.0 parts by weight of methyl methacrylate, 7.0 parts by weight of butyl acrylate, 12.0 parts by weight of stearyl methacrylate, 30 parts by weight of the multifunctional macromonomer (b2-2) prepared in Synthesis Example 4, 1.0 part by weight of 3-methacryloyloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol over 5 hours. Further polymerization was carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60%) of the (meth)acrylate-based copolymer (B-7) containing a reactive silicon group having a number average molecular weight of 2,280 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of this solution was 0.033 mmol / g, the reactive silicon group equivalent was 0.38 mmol / g, and the sulfur atom content was 10941 ppm.

[0299] (Synthesis Example 13)

[0300] In a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this was added dropwise a mixed solution obtained by dissolving 50.0 parts by weight of methyl methacrylate, 7.0 parts by weight of butyl acrylate, 12.0 parts by weight of stearyl methacrylate, 30 parts by weight of the multifunctional macromonomer (b2-2) prepared in Synthesis Example 4, 1.0 part by weight of 3-methacryloyloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol over 5 hours. Further polymerization was carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60%) of the (meth)acrylate-based copolymer (B-7) containing a reactive silicon group having a number average molecular weight of 2,280 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of this solution was 0.033 mmol / g, the reactive silicon group equivalent was 0.38 mmol / g, and the sulfur atom content was 10941 ppm.

[0301] (Synthesis Example 14)

[0302] In a four-necked flask equipped with a stirrer, 53.2 parts by weight of isobutyl alcohol was charged, and warmed to 105°C under nitrogen atmosphere. To this, a mixed solution obtained by dissolving 51.5 parts by weight of methyl methacrylate, 21.4 parts by weight of butyl acrylate, 0.4 part by weight of 2-ethylhexyl acrylate, 0.4 part by weight of stearyl methacrylate, 25.0 parts by weight of the multifunctional macromonomer (b2-3) prepared in Synthesis Example 5, 1.3 parts by weight of 3-mercaptopropyltrimethoxysilane, and 0.37 part by weight of 2,2'-azobis(2-methylbutyronitrile) in 11.9 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Further, 0.11 part by weight of 2,2'-azobis(2-methylbutyronitrile) was dissolved in 3.6 parts by weight of isobutyl alcohol and added, and polymerization was further carried out at 105°C for 2 hours, to obtain an isobutyl alcohol solution (solid content 60%) of the (meth)acrylate-based copolymer containing a reactive silicon group (B-9) having a number average molecular weight of 9460 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of this solution was 0.022 mmol / g, the reactive silicon group equivalent was 0.066 mmol / g, and the sulfur atom content was 2119 ppm.

[0303] (Synthesis Example 15)

[0304] In a four-necked flask equipped with a stirrer, 53.2 parts by weight of isobutyl alcohol was charged, and warmed to 105°C under nitrogen atmosphere. To this, a mixed solution obtained by dissolving 51.5 parts by weight of methyl methacrylate, 18.8 parts by weight of butyl acrylate, 0.4 part by weight of 2-ethylhexyl acrylate, 0.4 part by weight of stearyl methacrylate, 25.0 parts by weight of the multifunctional macromonomer (b2-3) prepared in Synthesis Example 5, 2.6 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, 1.4 parts by weight of n-dodecyl mercaptan, and 0.37 part by weight of 2,2'-azobis(2-methylbutyronitrile) in 11.9 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Further, 0.11 part by weight of 2,2'-azobis(2-methylbutyronitrile) was dissolved in 3.6 parts by weight of isobutyl alcohol and added, and polymerization was further carried out at 105°C for 2 hours, to obtain an isobutyl alcohol solution (solid content 60%) of the (meth)acrylate-based copolymer containing a reactive silicon group (B-10) having a number average molecular weight of 9320 (GPC molecular weight). The multifunctional macromonomer equivalent of the solid content of this solution was 0.022 mmol / g, the reactive silicon group equivalent was 0.10 mmol / g, and the sulfur atom content was 2282 ppm.

[0305] (Synthesis Example 16)

[0306] In a four-necked flask equipped with a stirrer, 47.2 parts by weight of isobutyl alcohol was placed, and the temperature was raised to 105°C under a nitrogen atmosphere. To this, a mixed solution obtained by dissolving 33.9 parts by weight of methyl methacrylate, 0.3 part by weight of butyl acrylate, 14.3 parts by weight of stearyl methacrylate, 38.5 parts by weight of the multifunctional macromonomer (b2-2) produced in Synthesis Example 4, 6.4 parts by weight of 3-methacryloyloxypropyldimethoxymethylsilane, 6.4 parts by weight of 3-mercaptopropyldimethoxymethylsilane, and 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 11.3 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Further, a mixed solution obtained by dissolving 0.2 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 6.8 parts by weight of isobutyl alcohol was added dropwise over 2 hours at 105°C to effect polymerization, whereby an isobutyl alcohol solution (60% by weight of solid content) of a (meth)acrylate-based copolymer (B-11) having a reactive silicon group and a number average molecular weight of 2,650 (GPC molecular weight) was obtained. The equivalent weight of the multifunctional macromonomer in the solid content of the solution was 0.045 mmol / g, the equivalent weight of the reactive silicon group was 0.63 mmol / g, and the sulfur atom content was 11,424 ppm.

[0307] (Synthesis Example 17)

[0308] In a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was placed, and the temperature was raised to 105°C under a nitrogen atmosphere. To this, a mixed solution obtained by dissolving 50.0 parts by weight of butyl acrylate, 10.0 parts by weight of stearyl methacrylate, 30 parts by weight of the multifunctional macromonomer (b2-1) produced in Synthesis Example 3, 10.0 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Further, polymerization was effected at 105°C over 2 hours, whereby an isobutyl alcohol solution (60% by weight of solid content) of a (meth)acrylate-based copolymer (P-1) having a reactive silicon group and a number average molecular weight of 6,950 (GPC molecular weight) was obtained. The equivalent weight of the multifunctional macromonomer in the solid content of the solution was 0.074 mmol / g, the equivalent weight of the reactive silicon group was 0.40 mmol / g.

[0309] (Synthesis Example 18)

[0310] In a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this, a mixed solution obtained by dissolving 89.0 parts by weight of butyl acrylate, 10.0 parts by weight of stearyl methacrylate, 1.0 part by weight of 3-methacryloyloxypropyltrimethoxysilane, 1.8 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Further polymerization was carried out at 105°C for 2 hours, and an isobutyl alcohol solution (solid content 60%) of a (meth)acrylate-based copolymer (P-2) containing a reactive silicon group having a number average molecular weight of 3730 (GPC molecular weight) was obtained. The equivalent weight of the reactive silicon group of the solid content of this solution was 0.13 mmol / g.

[0311] (Synthetic Example 19)

[0312] In a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this, a mixed solution obtained by dissolving 89.0 parts by weight of butyl acrylate, 10.0 parts by weight of stearyl methacrylate, 1.0 part by weight of 3-methacryloyloxypropyltrimethoxysilane, 1.8 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Further polymerization was carried out at 105°C for 2 hours, and an isobutyl alcohol solution (solid content 60%) of a (meth)acrylate-based copolymer (P-2) containing a reactive silicon group having a number average molecular weight of 3730 (GPC molecular weight) was obtained. The equivalent weight of the reactive silicon group of the solid content of this solution was 0.13 mmol / g.

[0313] (Synthetic Example 20)

[0314] Into a four-necked flask equipped with a stirrer, 44.5 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this, a mixed solution obtained by dissolving 40.8 parts by weight of methyl methacrylate, 54.2 parts by weight of butyl acrylate, 0.5 parts by weight of 2-ethylhexyl acrylate, 0.5 parts by weight of stearyl methacrylate, 0.5 parts by weight of 3-methacryloyloxypropyl trimethoxysilane, 1.3 parts by weight of 3-mercaptopropyl trimethoxysilane, and 0.37 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 11.9 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Further, 0.11 parts by weight of 2,2'-azobis(2-methylbutyronitrile) was dissolved in 3.6 parts by weight of isobutyl alcohol and added, and polymerization was further carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60%) of a (meth)acrylate-based copolymer (P-4) containing a reactive silicon group having a number average molecular weight of 9700 (GPC molecular weight). The reactive silicon group equivalent of this solution was 0.20 mmol / g, and the sulfur atom content was 5716 ppm.

[0315] (Synthetic Example 21)

[0316] Into a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this, a mixed solution obtained by dissolving 50.0 parts by weight of methyl methacrylate, 37.0 parts by weight of butyl acrylate, 12.0 parts by weight of stearyl methacrylate, 1.0 parts by weight of 3-methacryloyloxypropyl trimethoxysilane, 7.2 parts by weight of 3-mercaptopropyl trimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Polymerization was further carried out at 105°C for 2 hours to obtain an isobutyl alcohol solution (solid content 60%) of a (meth)acrylate-based copolymer (P-5) containing a reactive silicon group having a number average molecular weight of 2190 (GPC molecular weight). The reactive silicon group equivalent of the solid content of this solution was 0.38 mmol / g.

[0317] (Synthetic Example 22)

[0318] Into a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. A mixed solution obtained by dissolving 50.0 parts by weight of methyl methacrylate, 30.0 parts by weight of butyl acrylate, 10.0 parts by weight of stearyl methacrylate, 10.0 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, 7.2 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol was added dropwise thereto over 5 hours. Further polymerization was carried out at 105°C for 2 hours, whereby an isobutyl alcohol solution (solid content 60%) of a (meth)acrylate copolymer (P-6) containing a reactive silicon group having a number average molecular weight of 2,230 (GPC molecular weight) was obtained. The equivalent weight of the reactive silicon group of the solid content of the solution was 0.72 mmol / g.

[0319] (Synthetic Example 23)

[0320] Into a four-necked flask equipped with a stirrer, 48.0 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. A mixed solution obtained by dissolving 50.0 parts by weight of methyl methacrylate, 30.0 parts by weight of butyl acrylate, 10.0 parts by weight of stearyl methacrylate, 10.0 parts by weight of 3-methacryloyloxypropyltrimethoxysilane, 1.8 parts by weight of 3-mercaptopropyltrimethoxysilane, and 2.5 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 22.7 parts by weight of isobutyl alcohol was added dropwise thereto over 5 hours. Further polymerization was carried out at 105°C for 2 hours, whereby an isobutyl alcohol solution (solid content 60%) of a (meth)acrylate copolymer (P-7) containing a reactive silicon group having a number average molecular weight of 4,100 (GPC molecular weight) was obtained. The equivalent weight of the reactive silicon group of the solid content of the solution was 0.49 mmol / g.

[0321] (Synthetic Example 24)

[0322] Into a reactor made deoxidized, 0.42 parts by weight of copper bromide and 20.0 parts by weight of butyl acrylate were added, and heated and stirred. 8.8 parts by weight of acetonitrile as a polymerization solvent and 5.07 parts by weight of ethyl 2-bromoadipate as an initiator were added and mixed, and at the stage of adjusting the temperature of the mixed solution to about 80°C, pentamethyldiethylene triamine (hereinafter referred to as triamine) was added, and the polymerization reaction was started. Next, 80.0 parts by weight of butyl acrylate was added successively, and the polymerization reaction was carried out. During the polymerization, the triamine was added as necessary, and the polymerization rate was adjusted. The total amount of the triamine used during the polymerization was 0.15 parts by weight. At the time when the monomer conversion (polymerization rate) was about 95% or more, the volatile components were removed by pressure reduction and devolatilization, and a polymer concentrate was obtained.

[0323] The above concentrate was diluted with toluene, a filtration aid, an adsorbent (Kyoward 700 SEN: Kyowa Chemical Industries) and hydrotalcite (Kyoward 500 SH: Kyowa Chemical Industries) were added, and after heating and stirring to about 80 to 100°C, the solid components were removed by filtration. The filtrate was concentrated under reduced pressure to obtain a crude purified polymer.

[0324] The crude purified polymer, potassium acrylate 4.91 parts by weight, 4-hydroxy-TEMPO 100 ppm, and dimethylacetamide 100 parts by weight as a solvent were added, and after reaction at 70°C for 3 hours, the solvent was distilled off under reduced pressure to obtain a polymer concentrate. The concentrate was diluted with toluene, and the solid components were removed by filtration. The filtrate was concentrated under reduced pressure to obtain a macromer (p-2) having an acryloyl group at one end (i.e., a polymer having one acryloyl group in one molecule) having a number average molecular weight of 4040 (GPC molecular weight) and a molecular weight distribution (Mw / Mn) of 1.18.

[0325] (Synthetic Example 25)

[0326] In a four-necked flask equipped with a stirrer, isobutanol 48.0 parts by weight was charged, and warmed to 105°C under a nitrogen atmosphere. To this was added dropwise a mixed solution obtained by dissolving butyl acrylate 50.0 parts by weight, stearyl methacrylate 10.0 parts by weight, the macromer (p-2) having one acryloyl group in one molecule prepared in Synthetic Example 24 30 parts by weight, 3-methacryloyloxypropyltrimethoxysilane 10.0 parts by weight, and 2,2'-azobis(2-methylbutyronitrile) 2.5 parts by weight in isobutanol 22.7 parts by weight over 5 hours. Further polymerization was carried out at 105°C for 2 hours to obtain an isobutanol solution (solid content 60%) of a (meth)acrylate copolymer having a reactive silicon group (P-8) having a number average molecular weight of 1900 (GPC molecular weight). The macromer equivalent of the solid content of the solution was 0.069 mmol / g, and the reactive silicon group equivalent was 0.72 mmol / g.

[0327] (Synthetic Example 26)

[0328] Into a four-necked flask equipped with a stirrer, 47.2 parts by weight of isobutyl alcohol was charged, and the temperature was raised to 105°C under a nitrogen atmosphere. To this, a mixed solution obtained by dissolving 33.9 parts by weight of methyl methacrylate, 38.8 parts by weight of butyl acrylate, 14.3 parts by weight of stearyl methacrylate, 6.4 parts by weight of 3-methacryloyloxypropyl dimethoxymethyl silane, 6.4 parts by weight of 3-mercaptopropyl dimethoxymethyl silane, and 0.3 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 11.3 parts by weight of isobutyl alcohol was added dropwise over 5 hours. Further, a mixed solution obtained by dissolving 0.2 parts by weight of 2,2'-azobis(2-methylbutyronitrile) in 6.8 parts by weight of isobutyl alcohol was polymerized at 105°C for 2 hours, to obtain an isobutyl alcohol solution (solid content 60%) of a (meth)acrylate-based copolymer (P-9) having a reactive silane group having a number average molecular weight of 2300 (GPC molecular weight). The equivalent weight of the reactive silane group of the solid content of this solution was 0.63 mmol / g.

[0329] First, isobutyl alcohol was distilled off from the isobutyl alcohol solutions of the (meth)acrylate-based copolymers (B-1) to (B-3) obtained in Synthesis Examples 6 to 8 and the isobutyl alcohol solutions of the (meth)acrylate-based copolymers (P-1) to (P-3) obtained in Synthesis Examples 17 to 19, and the viscosity of each of the obtained polymers was measured by the following method.

[0330] (Viscosity)

[0331] The viscosity of each of the polymers was measured using a cone-plate (2°) having a diameter of 25 mm as a jig, with a gap set to 60 μm, at a rotation speed of 0.1 sec -1 The results obtained are shown in Table 1.

[0332] [Table 1]

[0333]

[0334] (1) Methyl methacrylate

[0335] (2) n-Butyl acrylate

[0336] (3) Stearyl methacrylate

[0337] (4) 3-Methacryloyloxypropyl trimethoxysilane

[0338] (5) 3-Mercaptopropyl trimethoxysilane

[0339] As shown in Table 1, it is known that the (meth)acrylate copolymers (B-1) to (B-3) in which both the multifunctional macromonomer (b2) which is a (meth)acrylate polymer having more than one (meth)acryloyl group in one molecule and the chain transfer agent (b3) having a mercapto group are copolymerized have narrower molecular weight distribution and lower viscosity than the (meth)acrylate copolymer (P-1) formed without using the chain transfer agent (b3) having a mercapto group.

[0340] On the other hand, it is known that the (meth)acrylate copolymer (P-3) formed using the allyl group-containing polyoxyalkylene polymer (p-1) instead of the (meth)acryloyl group-containing (meth)acrylate polymer (b2-1) has almost no copolymerization of (p-1) depending on the weight average molecular weight (Mw) thereof.

[0341] That is, it is known that the (meth)acrylate copolymers (B-1) to (B-3) have narrower molecular weight distribution and lower viscosity despite the copolymerization of the multifunctional macromonomer (b2).

[0342] For the (meth)acrylate copolymers (B-1) to (B-3), the multifunctional macromonomer (b2) is copolymerized with butyl acrylate or the like to form a block copolymer. On the other hand, the (meth)acrylate copolymer (P-2) does not use the multifunctional macromonomer (b2) and is thus a random copolymer. As shown in Table 1, it is known that the (meth)acrylate copolymers (B-1) to (B-3) have lower viscosity with respect to the weight average molecular weight (Mw) than the (meth)acrylate copolymer (P-2). For example, although the weight average molecular weights of (B-1) and (P-2) are the same degree, the viscosity of (B-1) is about half the viscosity of (P-2).

[0343] (Tensile properties)

[0344] A sheet having a thickness of 100 μm was prepared by mixing Neostan U-20 (dibutyltin dilaurate manufactured by Nitto Echemical Co., Ltd.) as a curing catalyst at 1 part by weight with respect to 100 parts by weight of the solid content of each polymer solution. The obtained sheet was cured and aged for 2 weeks under conditions of 23°C and 50% RH. A long test piece of 70 mm x 10 mm was cut from the obtained sheet, the distance between the grips was set to 40 mm, and the tensile properties were measured at 23°C. The stress at 30% elongation (M30), the strength at break (TB), the elongation at break (EB), and the Young's modulus were measured. The tensile properties were measured using an Autograph (AGS-X) manufactured by Shimadzu Corporation at a tensile speed of 20 mm / min. The obtained results are shown in Table 2.

[0345] [Table 2]

[0346]

[0347] (1) methyl methacrylate

[0348] (2) n-butyl acrylate

[0349] (3) 2-ethylhexyl acrylate

[0350] (4) stearyl methacrylate

[0351] (5) 3-methacryloyloxypropyl trimethoxysilane

[0352] (6) 3-mercaptopropyl trimethoxysilane

[0353] (7) n-dodecyl mercaptan

[0354] As shown in Table 2, the (meth)acrylate copolymer (P-4) produced without using the multifunctional macromonomer (b2) was too soft to produce test pieces, in contrast, the cured products of the (meth)acrylate copolymers (B-4) to (B-5) and (B-9) to (B-10) produced by copolymerizing the multifunctional macromonomer (b2) exhibited good tensile properties.

[0355] Next, the isobutanol solution of the polyoxypropylene polymer (A-1) obtained in Synthesis Example 1, 60 parts by weight, and the (meth)acrylate copolymers (B-6) to (B-8) or (P-5) to (P-8) obtained in Synthesis Examples 11 to 13, 21 to 23, and 25, 40 parts by weight, were mixed so that the solid content concentration reached 40 parts by weight, and the isobutanol was heated to remove the volatile components, and the viscosity of each mixture was measured by the above-described method. The results obtained are shown in Table 3.

[0356] [Table 3]

[0357]

[0358] (1) methyl methacrylate

[0359] (2) n-butyl acrylate

[0360] (3) stearyl methacrylate

[0361] (4) 3-methacryloyloxypropyl trimethoxysilane

[0362] (5) 3-mercaptopropyl trimethoxysilane

[0363] As shown in Table 3, it is known that the viscosity with respect to the weight average molecular weight (Mw) is lower in the mixture containing the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B) than in the mixture containing the (meth)acrylate copolymer (P) instead of the (meth)acrylate copolymer (B).

[0364] Specifically, it is described that the increase in the viscosity stays at about 1.5 times, although the weight average molecular weight is about 2 times, in the mixture containing the (meth)acrylate copolymers (B-6) to (B-8) as compared with the mixture containing the (meth)acrylate copolymer (P-5) or (P-6) formed without using the multifunctional macromonomer (b2). In addition, the viscosity is about 5 to 6 times or so, which is greatly reduced, in the mixture containing the (meth)acrylate copolymers (B-6) to (B-8) as compared with the mixture containing the (meth)acrylate copolymer (P-7) having a high weight average molecular weight formed without using the multifunctional macromonomer (b2).

[0365] Further, the same is true in the mixture containing the (meth)acrylate copolymers (B-6) to (B-8) as compared with the mixture containing the (meth)acrylate copolymer (P-8) formed by using the monomer (p-2) having only one (meth)acryloyl group within one molecule instead of the multifunctional macromonomer (b2), in that the increase in the viscosity stays at about 1.5 times, although the weight average molecular weight is about 2 times.

[0366] (Example 1)

[0367] The isobutyl alcohol solution of the (meth)acrylate-based copolymer (B-6) obtained in Synthesis Example 11 was mixed with the reactive silicon group-containing polyoxypropylene polymer (A-1) obtained in Synthesis Example 1 in such a manner that the solid content would be 40 parts by weight, and then the isobutyl alcohol was heated and devolatilized. A planetary mixer was used to mix 40 parts by weight of NANOX #30 (heavy calcium carbonate pellets, manufactured by Maruo Calcium Co., Ltd.) as a filler, 30 parts by weight of CCR-S10 (synthetic calcium carbonate, manufactured by Shiraishi Calcium Co., Ltd.) as a filler, 20 parts by weight of ACTICOLL P-23 (polypropylene glycol, manufactured by Mitsui Chemicals, Inc.) as a plasticizer, 2.5 parts by weight of Disparon 6500 (fatty acid amide wax, manufactured by Nippon Gunpowder Co., Ltd.) as a thixotropy imparting agent, 1 part by weight of NOCRAC CD (4,4'-bis(α,α-dimethylbenzyl) diphenylamine, manufactured by Dai-ken New Chemicals Co., Ltd.) as an antioxidant, and 1 part by weight of ADK STAB AO-60 (pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by ADEKA) as an antioxidant in the obtained mixture, and then heated and devolatilized under reduced pressure at 120°C for 1 hour. The obtained composition was cooled, 3 parts by weight of A-171 (vinyl trimethoxysilane, Momentive) as a devolatilizer, 3 parts by weight of KBM-603 (N-(2-aminoethyl)-3-aminopropyl trimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion promoter, and 0.3 parts by weight of Neostan U-810 (dioctyltin dilaurate, manufactured by Nippon Metal Plate Co., Ltd.) as a curing catalyst were mixed, and a one-component curable composition was obtained.

[0368] (viscosity)

[0369] A parallel circular plate disk with a diameter of 25 mm was used as a jig, the distance was set to 0.5 mm, and the rotation speed was set to 0.2 sec -1 or 10 sec -1 The viscosity of the obtained one-component curable composition was measured. The device used was a rheometer (ARES-G2) manufactured by TA Instruments. The viscosity ratio was calculated by (viscosity at 0.2 sec -1 / viscosity at 10 sec -1 The results obtained are shown in Table 4.

[0370] (tensile properties)

[0371] A sheet having a thickness of about 2 mm was produced using the obtained one-component curable composition, and was subjected to curing maturation for 3 days under conditions of 23°C and 50% RH, and then was subjected to curing maturation for 4 days at 50°C. The obtained sheet was punched into a No. 3 dumbbell shape (JIS K 6251), and a tensile strength test was performed under conditions of 23°C and 50% RH, and the stress at 50% elongation (M50) and the strength at break (TB) were measured. The tensile properties were measured using an Autograph (AGS-X) manufactured by Shimadzu Corporation at a tensile speed of 200 mm / min. The results are shown in Table 4.

[0372] (Adhesive strength)

[0373] A steel plate (SS400) used as an adherend was polished using sandpaper #400. The one-component curable composition was applied so as to have an adhesive area of 25 mm x 12.5 mm and a thickness of 0.5 mm, and the adherends were bonded to each other. The time of this bonding was taken as the start time, and maturation was performed for 7 days under conditions of 23°C and 50% RH, and then maturation was performed for 4 days at 50°C, and the test speed was set to 10 mm / min, the adhesive strength was measured, and the failure state was observed. The failure state was confirmed by visual observation, with the cohesive failure (failure at the adhesive portion) taken as CF and the interfacial failure (peeling at the interface between the adhesive and the adherend) taken as AF. In the case where both were mixed, the respective proportions were recorded. For example, in the case where the cohesive failure rate was 50% and the interfacial failure rate was 50%, this was recorded as C50A50. The results are shown in Table 4.

[0374] (Example 2 and Comparative Example 1)

[0375] The compounding shown in Table 4 was changed, and otherwise, the one-component curable composition was produced in the same manner as in Example 1, and the viscosity, the tensile properties, and the adhesive strength were evaluated. The results are shown in Table 4.

[0376] [Table 4]

[0377]

[0378] (1) Heavy calcium carbonate primary particle diameter 1 μm (Marutani Calcium Co., Ltd.)

[0379] (1’) Synthetic calcium carbonate (Shirosi Calcium Co., Ltd.)

[0380] (2) Fatty acid amide wax (Kanemate Corporation)

[0381] (3) Antioxidant (BASF)

[0382] (4) Vinyltrimethoxysilane (Momentive Corporation)

[0383] (5) N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

[0384] (6) dioctyltin dilaurate (Showa Denko K.K.)

[0385] From the comparison of Examples 1 to 2 according to Table 4 and Comparative Example 1, it was found that the composition of the Examples containing the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B) gave a cured product having high tensile strength and shear adhesion strength, as compared with the composition of the Comparative Example containing the (meth)acrylate copolymer (P-5) formed instead of the (meth)acrylate copolymer (B) without using the multifunctional macromonomer (b2).

[0386] Further, it was found that the composition of Example 1 containing the (meth)acrylate copolymer (B-6) having a small amount of 3-methacryloyloxypropyltrimethoxysilane as the monomer (b4) having a reactive silicon group and a polymerizable unsaturated group had a higher viscosity, i.e., higher thixotropy, as compared with the composition of Example 3 described later containing the (meth)acrylate copolymer (B-8) having a larger amount thereof.

[0387] (Example 3 and Comparative Example 2)

[0388] The compounding was changed to that shown in Table 5, and otherwise, a one-component curable composition was produced in the same manner as in Example 1, and evaluation of viscosity, tensile properties, and shear adhesion strength was performed. The results are shown in Table 5.

[0389] [Table 5]

[0390]

[0391] (1) Heavy calcium carbonate primary particle diameter 1 μm (Marutani Calcium Co., Ltd.)

[0392] (1') Synthetic calcium carbonate (Shirosaki Calcium Co., Ltd.)

[0393] (2) Fatty acid amide wax (Kobayashi Chemical Industry Co., Ltd.)

[0394] (3) Antioxidant (BASF)

[0395] (4) Vinyltrimethoxysilane (Momentive Corporation)

[0396] (5) N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

[0397] (6) dioctyltin dilaurate (Showa Denko K.K.)

[0398] From a comparison of Example 3 according to Table 5 with Comparative Example 2, it was found that the composition of Example 3 containing the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B) formed a cured product having high tensile strength and shear bond strength, as compared with the composition of Comparative Example 2 containing the (meth)acrylate copolymer (P-6) formed using no multifunctional macromonomer (b2) in place of the (meth)acrylate copolymer (B).

[0399] (Example 4 and Comparative Example 3)

[0400] The compounding shown in Table 6 was changed, and otherwise, a one-component curable composition was produced in the same manner as in Example 1, and evaluation of the tensile properties was performed. The results are shown in Table 6.

[0401] [Table 6]

[0402]

[0403] (1) Heavy calcium carbonate primary particle diameter 1 μm (Marutani Calcium Co., Ltd.)

[0404] (1') Synthetic calcium carbonate (Shirosi Calcium Co., Ltd.)

[0405] (2) Fatty acid amide wax (Kasuga Chemical Industries Co., Ltd.)

[0406] (3) Antioxidant (BASF)

[0407] (4) Vinyltrimethoxysilane (Momentive Corporation)

[0408] (5) N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.)

[0409] (6) Dioctyltin dilaurate (Nippon Soda Co., Ltd.)

[0410] From a comparison of Example 4 according to Table 6 with Comparative Example 3, it was found that the composition of Example 4 containing the polyoxyalkylene polymer (A) and the (meth)acrylate copolymer (B) formed a cured product having high tensile strength, as compared with the composition of Comparative Example 3 containing the (meth)acrylate copolymer (P-9) formed using no multifunctional macromonomer (b2) in place of the (meth)acrylate copolymer (B).

Claims

1. A (meth)acrylate copolymer (B) having a reactive silicon group represented by general formula (1), -SiR 5 c X 3-c (1) In the formula, R 5 The hydrocarbon group consisting of 1 to 20 carbon atoms, either substituted or unsubstituted, where X represents a hydroxyl group or a hydrolyzable group, and c represents 0 or 1. in, The monomer components constituting the copolymer include: (meth)acrylate (b1), (b2) methacrylate polymers having more than one but less than 2.0 (meth)acryloyl groups within the molecule, and Chain transfer agents with thiol groups (b3), Furthermore, the monomer component further contains monomers (b4) having reactive silicon groups and polymerizable unsaturated groups, and / or The chain transfer agent (b3) with a thiol group further has a reactive silane group. The weight-average molecular weight of the (meth)acrylate copolymer (B) is 500-80000. The (meth)acrylate (b1) contains at least 60% by weight of at least one monomer selected from methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate. The monomer components forming the main chain backbone of the (meth)acrylate polymer (b2) contain more than 60% by weight of acrylates other than isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate. The content of the (meth)acrylate polymer (b2) is 1 to 60% by weight relative to the total amount of monomer components constituting the (meth)acrylate copolymer (b). The content of the thiol-containing chain transfer agent (b3) is 0.1 to 30% by weight relative to the total amount of monomer components constituting the (meth)acrylate copolymer (B).

2. The (meth)acrylate copolymer (B) according to claim 1, wherein, The (meth)acrylate polymer (b2) comprises more than 0.2 mol% and less than 5.0 mol% of the monomer component.

3. The (meth)acrylate copolymer (B) according to claim 1 or 2, wherein, The chain transfer agent (b3) having a thiol group accounts for more than 0.4 mol% and less than 15 mol% of the monomer component.

4. The (meth)acrylate copolymer (B) according to claim 1 or 2, wherein, The number average molecular weight of (meth)acrylate polymers (b2) is above 500 and below 50,000.

5. The (meth)acrylate copolymer (B) according to claim 1 or 2, wherein, The weight-average molecular weight of (meth)acrylate copolymer (B) is 3,000 to 70,000.

6. The (meth)acrylate copolymer (B) according to claim 1 or 2, wherein, The molecular weight distribution of (meth)acrylate copolymer (B) is above 3.0 and below 11.

0.

7. The (meth)acrylate copolymer (B) according to claim 1 or 2, wherein, The molar ratio of (meth)acrylate polymer (b2) to chain transfer agent with thiol group (b3) is 0.12 or more and 0.58 or less.

8. A (meth)acrylate copolymer (B) having a reactive silicon group represented by general formula (1), -SiR 5 c X 3-c (1) In the formula, R 5 The hydrocarbon group consisting of 1 to 20 carbon atoms, either substituted or unsubstituted, where X represents a hydroxyl group or a hydrolyzable group, and c represents 0 or 1. in, The copolymer comprises a structure in which two first molecular chains are bonded together by one second molecular chain, with the two ends of the second molecular chain bonded to the non-terminal portions of the first molecular chain. The first and second molecular chains are each composed of molecular chains of (meth)acrylate copolymers. The reactive silicon group is bonded to the first molecular chain. The first molecular chain has a structure represented by -SR at any end, where S represents a sulfur atom and R represents a hydrocarbon group optionally having the reactive silicon group. The weight-average molecular weight of the (meth)acrylate copolymer (B) is 500-80000. The monomeric component constituting the first molecular chain contains at least 60% by weight of at least one monomer selected from methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate. In the monomer components constituting the second molecular chain, the proportion of acrylates other than isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate is more than 60% by weight. The content of the second molecular chain is 1 to 60% by weight relative to the total amount of (meth)acrylate copolymer (B).

9. The (meth)acrylate copolymer (B) according to claim 8, wherein, The sulfur atom concentration in (meth)acrylate copolymer (B) is above 700 ppm and below 20,000 ppm.

10. A curable composition comprising (meth)acrylate copolymer (B) according to any one of claims 1 to 9.

11. The curable composition according to claim 10, further comprising a polyoxyethylene polymer (A) having a reactive silicon group represented by general formula (1).

12. The curable composition according to claim 11, wherein, Polyoxyolefin polymer (A) has an end structure represented by general formula (2). ， In the formula, R 1 R 3 Each is an independent divalent bonded group with 1 to 6 carbon atoms, and R 1 R 3 Each adjacent carbon atom is bonded to any atom from carbon, oxygen, or nitrogen, R 2 R 4 Each is independently a hydrocarbon group with 1 to 10 carbon atoms, where n is an integer from 1 to 10, and R 5 X is a hydrocarbon group with 1 to 20 carbon atoms, either substituted or unsubstituted, where X is a hydroxyl group or a hydrolyzable group, and c represents 0 or 1.

13. A cured product, which is a cured product of the curable composition according to any one of claims 10 to 12.

14. A method for manufacturing a (meth)acrylate copolymer (B), said (meth)acrylate copolymer (B) having a reactive silicon group represented by general formula (1), -SiR 5 c X 3-c (1) In the formula, R 5 The hydrocarbon group consisting of 1 to 20 carbon atoms, either substituted or unsubstituted, where X represents a hydroxyl group or a hydrolyzable group, and c represents 0 or 1. The method includes: The process of copolymerizing monomer components. The monomeric component contains: (meth)acrylate (b1), (b2) methacrylate polymers having more than one but less than 2.0 (meth)acryloyl groups within the molecule, and Chain transfer agents with thiol groups (b3), Furthermore, the monomer component further contains monomers (b4) having reactive silicon groups and polymerizable unsaturated groups, and / or The chain transfer agent (b3) with a thiol group further has a reactive silane group. The weight-average molecular weight of the (meth)acrylate copolymer (B) is 500-80000. The (meth)acrylate (b1) contains at least 60% by weight of at least one monomer selected from methacrylate, isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate. The monomer components forming the backbone of the (meth)acrylate polymer (b2) contain more than 60% by weight of acrylates other than isobornyl acrylate, dicyclopentenyl acrylate, and dicyclopentyl acrylate. The content of (meth)acrylate polymer (b2) is 1 to 60% by weight relative to the total amount of monomer components constituting (meth)acrylate copolymer (b). The content of the chain transfer agent (b3) with thiol groups is 0.1 to 30% by weight relative to the total amount of monomer components constituting the (meth)acrylate copolymer (B).

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