WO2022202132A1

WO2022202132A1 - Silane-crosslinkable-polymer-containing composition

Info

Publication number: WO2022202132A1
Application number: PCT/JP2022/008396
Authority: WO
Inventors: 美伸大西
Original assignee: 株式会社カネカ
Priority date: 2021-03-26
Filing date: 2022-02-28
Publication date: 2022-09-29
Also published as: JPWO2022202132A1

Abstract

Provided is a composition including a silane-crosslinkable polymer (A) represented by formula (1): (HO)_x-Y-[O-CO-NH-CR¹ ₂-SiR_aX_3-a]_p-x, and a silane-crosslinkable polymer (B) that has no branch points and only one silyl group terminal per molecule and that is represented by formula (2): -SiR² _cX_3-c, the silane-crosslinkable polymer (B) content being 5-200 parts by weight, where the silane-crosslinkable polymer (A) is designated as 100 parts by weight. Y is a polymer chain having a branch point at at least one location, R is a hydrocarbon group, R¹ and R² each are a hydrogen atom or a hydrocarbon group, X is a hydroxyl group or a hydrolyzable group, p is an integer ranging from 3 to 10, x is an integer ranging from 0 to p-1, and a and c each are 0, 1, or 2.

Description

Composition containing silane crosslinkable polymer

The present invention provides an organic organic compound having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and having a silyl group capable of forming a crosslink by forming a siloxane bond (hereinafter also referred to as a "hydrolyzable silyl group"). Compositions containing polymeric silane-crosslinkable polymers.

As an organic polymer having a hydrolyzable silyl group (hereinafter referred to as a silane crosslinkable polymer), an organic polymer whose main chain skeleton is a polyoxyalkylene polymer or a polyisobutylene polymer has already been industrially produced and used as a sealant. , adhesives, paints, etc. (see Patent Documents 1 and 2).

A composition containing a silane crosslinkable polymer is usually cured using a condensation catalyst such as an organic tin compound having a carbon-tin bond, typified by dibutyltin bis(acetylacetonate). However, in recent years, the toxicity of organic tin compounds has been pointed out due to the tightening of regulations on chemical substances mainly in Europe, and the demand for alternative technologies is increasing.

On the other hand, by using a linear organic polymer in which a heteroatom such as oxygen, nitrogen, sulfur, etc. having a lone pair is bonded to the α-position carbon bonded to a hydrolyzable silyl group, an organic tin compound can be obtained. It is known that a composition having a high curing speed can be obtained even if it is not used (see Patent Document 3).

In addition, by combining a linear organic polymer having such a specific terminal structure with a silane crosslinkable polymer having only one hydrolyzable silyl group in one molecule, curing of the sealant formulation It has been reported that the later modulus can be lowered (see Patent Document 4).

JP-A-52-73998 JP-A-10-245482 Japanese translation of PCT publication No. 2005-514504 WO2015/024773

In general, sealant applications require high curing speed, excellent curability and adhesiveness, low modulus to some extent, flexibility, and high restorability, even without the use of organic tin compounds. There are many things.

By using an organic polymer with a specific terminal structure, a high curing speed can be achieved even without using an organic tin compound. If it is lowered, curability and restorability may become disadvantageous.

In this regard, when the author verified the method and formulation described in Patent Document 4, there was room for improvement in terms of curability and restorability.

An object of the present invention is to provide a silane-crosslinkable polymer-containing composition that exhibits good curability and high restorability even in the low modulus range, in view of the above-mentioned current situation.

As a result of intensive studies by the present inventors, a composition containing a silane-crosslinkable polymer having one or more branched chains and a silane-crosslinkable polymer having only one silyl group terminal in one molecule and having no branch point The present inventors have found that good curability and high restorability can be obtained even in a low modulus region by using the material, resulting in the present invention.

That is, the present invention provides a silane crosslinkable polymer (A) represented by the following formula (1)
(HO) _x _—Y— [O—CO—NH—CR ¹² —SiR _a X ₃ _-a ] px (1)
(In Formula (1), Y is a polymer chain having at least one or more branch points, R is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ¹ is each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X is a hydroxyl group or a hydrolyzable group; p is an integer of 3 to 10; is an integer from 0 to p-1, and a may be the same or different and is 0, 1 or 2.)
And a silane crosslinkable polymer (B) having no branch point and having only one terminal silyl group in one molecule represented by the following formula (2)
—SiR ² _c X _3-c (2) (in formula (2), X is the same as defined above, and each R ² is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; Yes, and c is 0, 1 or 2.)
and wherein the content of the silane-crosslinkable polymer (B) is 5 parts by weight or more and 200 parts by weight or less when the silane-crosslinkable polymer (A) is 100 parts by weight.
Preferably, p is 3 in formula (1) of the silane-crosslinkable polymer (A) represented by formula (1).
Moreover, preferably, the polymer skeleton of the silane-crosslinkable polymers (A) and (B) is a polyoxyalkylene polymer.
Moreover, preferably, the silyl group of the silane-crosslinkable polymer (B) is represented by the following formula (3) or (4).
—O—CO—NH—(CH ₂ ) ₃ —SiX ₃ (3)
(X is the same as described above.)
—O—(CH ₂ ) ₃ —SiX ₃ (4)
(X is the same as described above.)
Also preferably, the content of the silane-crosslinkable polymer (B) is 5 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the silane-crosslinkable polymer (A).
Further, preferably, when the total of the silane crosslinkable polymer (A) and the silane crosslinkable polymer (B) is 100 parts by weight, it further contains 0.1 to 20 parts by weight of an aminosilane compound (C). composition.

The present invention can provide a silane-crosslinkable polymer-containing composition that exhibits good curability and high restorability even in the low modulus region.

Embodiments of the present invention are described in detail below.
<<Silane crosslinkable polymer (A)>>
The silane-crosslinkable polymer (A) has a structure represented by the following formula (1).
(HO) _x _—Y— [O—CO—NH—CR ¹² —SiR _a X ₃ _-a ] px (1)

In formula (1), Y is a polymer chain having at least one or more branch points, R is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R ¹ are each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, X is a hydroxyl group or a hydrolyzable group, p is an integer of 3 to 10, and x is is an integer from 0 to p−1, a may be the same or different and is 0, 1 or 2;

Y is a polymer chain having at least one or more branch points, is not particularly limited, and various polymer skeletons described later can be used. A polymer chain having a branch point refers to a branched polymer skeleton having a branch point in the polymer skeleton composed of a plurality of repeating units. The number of branch points and the number of branches at each branch point are not limited, but the number of terminals determined by branching is preferably 3 to 10, more preferably 3 to 8, and even more preferably 3 to 6. , more preferably 3 to 5, and most preferably 3.

Each R independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro, alkoxy groups such as methoxy, and amino groups such as N,N-diethylamino. . When two or more R are present, they may be the same or different.

Specific examples of R include unsubstituted groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, 2-ethylhexyl and n-dodecyl groups. Alkyl group; chloromethyl group, methoxymethyl group, substituted alkyl group such as N,N-diethylaminomethyl group; vinyl group, isopropenyl group, unsaturated hydrocarbon group such as allyl group; cycloalkyl group such as cyclohexyl group; phenyl aryl groups such as toluyl group and 1-naphthyl group; and aralkyl groups such as benzyl group. Preferred are substituted or unsubstituted alkyl groups, more preferred are methyl groups, ethyl groups, chloromethyl groups and methoxymethyl groups, still more preferred are methyl groups and methoxymethyl groups, and particularly preferred are methyl groups. is the base.

Each R ¹ is independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro, alkoxy groups such as methoxy, and amino groups such as N,N-diethylamino. . It is particularly preferred that R ¹ is a hydrogen atom. Moreover, a plurality of R ¹ may be the same or different.

　X represents a hydroxyl group or a hydrolyzable group. Examples of X include hydroxyl group, hydrogen, halogen, alkoxy group, acyloxy group, ketoximate group, amino group, amide group, acid amide group, aminooxy group, mercapto group and alkenyloxy group. The above alkoxy group and the like may have a substituent. An alkoxy group is preferred because it is moderately hydrolyzable and easy to handle, methoxy, ethoxy, n-propoxy and isopropoxy are more preferred, methoxy and ethoxy are still more preferred, and methoxy is particularly preferred. When there are multiple X's, they may be the same or different.

p is an integer of 3 to 10, preferably 3 to 8, more preferably 3 to 6, even more preferably 3 to 5, and particularly preferably 3.

x is an integer from 0 to p−1, preferably 0 to 2, more preferably 0 to 1. From the viewpoint of curability, x is most preferably 0.

"a" in the formula (1) represents 0, 1, or 2. Preferably 0 or 1. In particular, a is preferably 1 from the viewpoint of storage stability.

<<Silane crosslinkable polymer (B)>>
The silane-crosslinkable polymer (B) is a polymer having no branch point and having only one terminal silyl group represented by the following formula (2) per molecule. A polymer having no branch point refers to a polymer skeleton composed of a plurality of repeating units having no branch point and having a linear polymer skeleton.
—SiR ² _c X _3-c (2)

In formula (2), X is the same as defined above, each R ² is independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and c is 0, 1 or 2.

Each R ² independently represents a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 8, even more preferably 1 to 6, even more preferably 1 to 3, and particularly preferably 1 or 2. When the hydrocarbon group has a substituent, the substituent is not particularly limited, and examples thereof include halogen groups such as chloro, alkoxy groups such as methoxy, and amino groups such as N,N-diethylamino. . When two or more R ² are present, they may be the same or different.

Specific examples of R ² include the groups described in the above specific examples of R. Preferred are substituted or unsubstituted alkyl groups, more preferred are methyl groups, ethyl groups, chloromethyl groups and methoxymethyl groups, still more preferred are methyl groups and methoxymethyl groups, and particularly preferred are methyl groups. is the base.

"c" in the formula (2) represents 0, 1, or 2. From the viewpoint of reactivity and restorability, c is preferably 0 or 1, and most preferably 0.

From the viewpoint of ease of synthesis and resilience, it is preferable that the silyl group contained in the silane-crosslinkable polymer (B) is represented by the following formula (3) or (4). Especially preferred.
—O—CO—NH—(CH ₂ ) ₃ —SiX ₃ (3)
(X is the same as described above.)
—O—(CH ₂ ) ₃ —SiX ₃ (4)
(X is the same as described above.)

<<Production method of silane crosslinkable polymers (A) and (B)>>
The method for producing the silane-crosslinkable polymers (A) and (B) is not particularly limited, but may include the following steps.
Step (I): A step of producing an organic polymer having a polymer skeleton composed of a plurality of repeating units and containing hydroxyl groups.
Step (II): A step of subjecting an organic polymer containing a hydroxyl group to a urethanization reaction with a compound containing a hydrolyzable silyl group and an isocyanate group.
Moreover, the method for producing the silane-crosslinkable polymer (B) is not particularly limited, but may include the following steps.
Step (III): The hydroxyl group of the organic polymer containing a hydroxyl group is reacted with an alkali metal salt, and then reacted with a carbon-carbon unsaturated bond-containing halide to convert it to a carbon-carbon unsaturated bond-containing group, A step of subjecting the carbon-carbon unsaturated bond to a hydrosilylation reaction with a hydrosilane compound containing a hydrolyzable silyl group.

The order of performing steps (I) to (III) is preferably step (I) followed by step (II), or step (I) followed by step (III). Further, by using a hydroxyl group-containing organic polymer produced by a method other than step (I), step (II) or step (III) can be performed alone.

Each step will be described below.
[Step (I)]
<Organic polymer containing hydroxyl group>
The position at which the hydroxyl group contained in the organic polymer is bonded to the polymer skeleton is not particularly limited, but it is preferably the terminal of the polymer skeleton.

The polymer skeleton of the silane-crosslinkable polymer (A) is not particularly limited as long as it has one or more branched chains, and various polymer skeletons can be used. Moreover, the polymer skeleton of the silane-crosslinkable polymer (A) corresponds to the polymer chain represented by Y in the formula (1).

The polymer skeleton of the silane-crosslinkable polymer (B) is not particularly limited as long as it is a linear polymer skeleton having no branch points, and various polymer skeletons can be used.

The types of polymer backbones of the silane-crosslinkable polymers (A) and (B) may be the same or different.

Specific examples of the types of polymer skeletons of the silane crosslinkable polymers (A) and (B) include polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxytetramethylene, polyoxyethylene-polyoxypropylene co- polymers, and polyoxyalkylene polymers such as polyoxypropylene-polyoxybutylene copolymers; ethylene-propylene copolymers, polyisobutylene, copolymers of isobutylene and isoprene, polychloroprene, polyisoprene, Copolymers of isoprene or butadiene with acrylonitrile and/or styrene, polybutadiene, copolymers of isoprene or butadiene with acrylonitrile and styrene, and hydrogenated polyolefins obtained by hydrogenating these polyolefin polymers Saturated hydrocarbon-based polymers such as polymers; polyester-based polymers; (meth)acrylic acid esters obtained by radical polymerization of (meth)acrylic acid ester-based monomers such as ethyl (meth)acrylate and butyl (meth)acrylate and vinyl-based polymers such as polymers obtained by radically polymerizing monomers such as (meth)acrylic acid-based monomers, vinyl acetate, acrylonitrile, and styrene; polysulfide-based polymer; polyamide-based polymer; polycarbonate-based polymer; diallyl phthalate-based polymer; Each of the above polymers may be mixed in block form, graft form, or the like. Among these, saturated hydrocarbon-based polymers, polyoxyalkylene-based polymers, and (meth)acrylic acid ester-based polymers have relatively low glass transition temperatures, and the obtained cured products have excellent cold resistance. are preferred, polyoxyalkylene-based polymers are more preferred, and polyoxypropylene is particularly preferred.

The organic polymer may be a polymer having one type of polymer skeleton, or a mixture of two or more types of polymers having different polymer skeletons. The mixture may be a mixture of polymers produced separately, or a mixture produced at the same time so as to have an arbitrary composition.

When obtaining the silane-crosslinkable polymers (A) and (B), the number average molecular weight of the organic polymer is not particularly limited, but the polystyrene equivalent molecular weight in GPC is preferably 3,000 to 100,000, and more preferably. is 3,000 to 50,000, more preferably 3,000 to 30,000. When the number average molecular weight is 3,000 or more, the relative amount of hydrolyzable silyl groups with respect to the whole polymer is within an appropriate range, which is desirable in terms of production cost. Moreover, when the number average molecular weight is 100,000 or less, it is easy to achieve a desired viscosity from the viewpoint of workability. The number average molecular weight can be determined in terms of polystyrene by GPC measurement. The preferred range of the number average molecular weights of the silane-crosslinkable polymers (A) and (B) is also the same as the range of the number average molecular weight of the organic polymer explained above.

Although the molecular weight distribution (Mw/Mn) of the organic polymer is not particularly limited, it is preferably narrow. Specifically, it is preferably less than 2.0, more preferably 1.6 or less, still more preferably 1.5 or less, and particularly preferably 1.4 or less. Moreover, from the viewpoint of improving mechanical properties such as durability and elongation of the cured product, it is preferably 1.2 or less. The molecular weight distribution (Mw/Mn) can be calculated from the number-average molecular weight and the weight-average molecular weight obtained in terms of polystyrene by GPC measurement. The preferred range of the molecular weight distribution of the silane-crosslinkable polymers (A) and (B) is also the same as the range of the molecular weight distribution of the organic polymer explained above.

<Method for Producing Organic Polymer Containing Hydroxyl Group>
(Polyoxyalkylene polymer)
As one aspect of the method for producing an organic polymer containing a hydroxyl group, when the polymer skeleton of the silane-crosslinkable polymer (A) and/or (B) is a polyoxyalkylene polymer, the organic polymer containing the hydroxyl group As a production method, it can be produced by polymerizing an epoxy compound with an initiator having a hydroxyl group by a conventionally known method. As a result, a hydroxyl-terminated polyoxyalkylene polymer is obtained. Although the specific polymerization method is not particularly limited, a polymerization method using a double metal cyanide complex catalyst such as a zinc hexacyanocobaltate glyme complex is preferable because a polymer with a small molecular weight distribution (Mw/Mn) can be obtained. .

When obtaining the silane crosslinkable polymer (A), the number of terminal hydroxyl groups of the polyoxyalkylene polymer having one or more branched chains is preferably 3 to 10, more preferably 3 to 8, and 3 to 6. More preferably, 3 to 5 is even more preferred, and 3 is most preferred. It is preferable to use a polyoxyalkylenetriol having three terminal hydroxyl groups, that is, specifically a polyoxyalkylenetriol.

When obtaining the silane crosslinkable polymer (A), examples of the hydroxyl-containing initiator include compounds having 3 or more active hydrogen atoms in one molecule, and hydroxyl groups having 3 to 10 hydroxyl groups in one molecule. Compounds and/or unsaturated alcohols are preferred. Specifically, compounds with 3 hydroxyl groups such as glycerin and polyoxypropylene triol with a molecular weight of 100 to 4000, compounds with 4 hydroxyl groups such as pentaerythritol, and compounds with 6 hydroxyl groups such as sorbitol and dipentaerythritol. , sucrose, and other compounds having eight hydroxyl groups.

When obtaining the silane crosslinkable polymer (B), examples of the initiator having a hydroxyl group include compounds having one active hydrogen atom in one molecule, specifically butanol, allyl alcohol, low molecular weight poly Oxypropylene monoallyl ethers and low-molecular-weight polyoxypropylene monoalkyl ethers can be mentioned.

Although the epoxy compound is not particularly limited, examples thereof include alkylene oxides such as ethylene oxide and propylene oxide, and glycidyl ethers such as methyl glycidyl ether and butyl glycidyl ether. Propylene oxide is preferred.

((Meth)acrylic acid ester polymer)
As another aspect of the method for producing an organic polymer containing a hydroxyl group, when the polymer skeleton of the silane-crosslinkable polymer (A) and/or (B) is a (meth)acrylic acid ester polymer, the organic polymer containing the hydroxyl group As a method for producing the polymer, (I) a compound having a polymerizable unsaturated group and a hydroxyl group (for example, 2-hydroxyethyl acrylate) is copolymerized with a monomer having a (meth)acrylic structure to obtain a polymer. Method (II) After obtaining a polymer by polymerizing a monomer having a (meth)acrylic structure by a living radical polymerization method such as atom transfer radical polymerization, any position in the resulting polymer (preferably a molecule chain end), and the like.

(Saturated hydrocarbon polymer)
As another aspect of the present embodiment, when the polymer skeleton of the silane-crosslinkable polymer (A) and/or (B) is a saturated hydrocarbon-based polymer, a method for producing the above-mentioned hydroxyl-containing organic polymer As, after obtaining a polymer by polymerizing an olefinic compound having 2 to 6 carbon atoms such as ethylene, propylene, 1-butene, and isobutylene as a main monomer, any position ( (Preferably, a method of introducing a hydroxyl group at the end of the molecular chain).

[Step (II)]
<Urethane reaction>
The silane-crosslinkable polymer (A) and/or (B) can also be obtained by urethanizing an organic polymer having a hydroxyl group and a compound containing a hydrolyzable silyl group and an isocyanate group. A silyl group-containing isocyanate compound may be used alone or in combination of two or more.

The amount of the silyl group-containing isocyanate compound to be used can be appropriately determined in consideration of the amount of hydroxyl groups possessed by the organic polymer and the desired amount of hydrolyzable silyl groups to be introduced, and is not particularly limited. , preferably 0.1 to 10 molar equivalents, more preferably 0.3 to 5 molar equivalents, and even more preferably 0.5 to 3 molar equivalents, relative to the hydroxyl groups of the organic polymer.

When obtaining the silane-crosslinkable polymer (A) using step (II), the silyl group-containing isocyanate compound contains an isocyanate group capable of undergoing a urethanization reaction with the hydroxyl group of the organic polymer and a hydrolyzable silyl group. It is a compound that exists in the same molecule. The silyl group-containing isocyanate compound can be represented by the following formula (5).
OCN-CR ¹² -SiR _a X ₃ _-a (5)
(R, R ¹ , X, and a in formula (5) are the same as described above for formula (1).)

Specific examples of the silyl group-containing isocyanate compounds include (isocyanatomethyl)trimethoxysilane, (isocyanatomethyl)triethoxysilane, (isocyanatomethyl)dimethoxymethylsilane, (isocyanatomethyl)diethoxymethylsilane, and the like. .

When the silane-crosslinkable polymer (B) is obtained using step (II), the silyl group-containing isocyanate compound contains an isocyanate group capable of undergoing a urethanization reaction with the hydroxyl group of the organic polymer and a hydrolyzable silyl group. It is a compound that exists in the same molecule. As specific examples of the silyl group-containing isocyanate compound, the silyl group-containing isocyanate compounds mentioned as specific examples in the case of obtaining the silane-crosslinkable polymer (A) can be used. In addition to these, for example, (3-isocyanatopropyl)trimethoxysilane, (3-isocyanatopropyl)dimethoxymethylsilane, (3-isocyanatopropyl)triethoxysilane, (3-isocyanatopropyl)diethoxymethylsilane, etc. is mentioned.

In particular, when obtaining a silane-crosslinkable polymer (B) containing a silyl group represented by the formula (3), a silyl group-containing isocyanate compound represented by the following formula (6) can be used.
OCN-(CH ₂ ) ₃ -SiX ₃ (6)
(X in formula (6) is the same as described above for formula (1).)

Specific examples of such silyl group-containing isocyanate compounds include (3-isocyanatopropyl)trimethoxysilane and (3-isocyanatopropyl)triethoxysilane.

The urethanization reaction may be carried out without using a urethanization catalyst, but may be carried out in the presence of a urethanization catalyst for the purpose of improving the reaction rate or improving the reaction rate. Examples of such urethanization catalysts include conventionally known urethanization catalysts listed in Polyurethanes: Chemistry and Technology, Part I, Table 30, Chapter 4, Saunders and Frisch, Interscience Publishers, New York, 1963. A catalyst can be used. Specific examples thereof include base catalysts such as organic tin compounds, bismuth compounds, and organic amines, but are not limited to these.

As the urethanization catalyst, an organic tin compound is preferable because of its high activity. Specifically, tin octoate, tin stearate, dibutyltin dioctoate, dibutyltin dioleyl maleate, dibutyltin dibutyl maleate, dibutyltin dilaurate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl Distannoxane, dibutyltin diacetate, dibutyltin diacetylacetonate, dibutyltin bis(o-phenylphenoxide), dibutyltin oxide, dibutyltin bis(triethoxysilicate), dibutyltin distearate, dibutyltin bis(isononyl-3-mercaptopropionate) ), dibutyltin bis(isooctyl mercaptopropionate), dibutyltin bis(isooctylthioglycolate), dioctyltin oxide, dioctyltin dilaurate, dioctyltin diacetate, dioctyltin diversatate and the like. Furthermore, a urethanization catalyst with low activity to a hydrolyzable silyl group is preferred, and from this point of view, an organic tin compound containing a sulfur atom is preferred. Particularly preferred are dibutyltin bis(isooctyl mercaptopropionate) and dibutyltin bis(isooctylthioglycolate).

As the urethanization catalyst, an organic bismuth compound is preferable in that it has good activity and maintains good storage stability of the silyl group-containing organic polymer. Bismuth-containing catalysts, for example, are manufactured by Borchers GmbH under the trade names of Borchi (R) Kat 22, Borchi (R) Kat 24, Borchi (R) Kat 320, Borchi (R) Kat 315 EU, Borchi (R) Catalyst with Kat VP 0243, Borchi (R) Kat VP 0244, product name manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Bismuth (III) 2-ethylhexanoate 2-ethylhexanoate solution (Bi: 25%), 2- Bismuth(III) ethylhexanoate, 70-75% in xylenes (~24% Bi) (99.99+%-Bi) PURATREM, etc., are not particularly limited as long as they promote the urethanization reaction.

The amount of the urethanization catalyst to be added can be appropriately set by those skilled in the art, but from the viewpoint of reaction activity, it is preferably 1 to 1000 ppm, more preferably 10 to 100 ppm, relative to 100 parts by weight of the organic polymer. Within this range, in addition to obtaining sufficient reaction activity, the physical properties of the produced silane-crosslinkable polymer can be maintained well.

The urethanization reaction can be carried out without using a solvent, but for the purpose of uniformly dissolving the organic polymer, the silyl group-containing isocyanate compound, and the urethanization catalyst, the temperature control of the reaction system, In order to easily realize the addition of the urethanization catalyst, an organic solvent may be added.

When an organic solvent is used, its type is not particularly limited and may be selected as appropriate. Hydrogen, aliphatic halogenated hydrocarbons such as dichloroethane and chloroform, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene and isopropylbenzene, aromatic halogenated hydrocarbons such as chlorobenzene and chlorotoluene, tetrahydrofuran (THF ), ether solvents such as tetrahydropyran (THP), and the like. As the organic solvent, only one type may be used, or two or more types may be used in combination.

The temperature during the urethanization reaction can be appropriately set by those skilled in the art, but it is preferably 50°C or higher and 120°C or lower, more preferably 70°C or higher and 100°C or lower. The reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed. Specifically, the reaction time is preferably from 15 minutes to 5 hours, more preferably from 30 minutes to 3 hours.

[Step (III)]
<Step including hydrosilylation reaction>
The silane crosslinkable polymer (B) is obtained by reacting a portion of the hydroxyl groups of an organic polymer having hydroxyl groups (also referred to as the hydroxyl groups of the organic polymer) with an alkali metal salt, followed by adding a carbon-carbon unsaturated bond-containing halogen It can also be obtained by reacting with a compound to convert to a carbon-carbon unsaturated bond-containing group, and then subjecting the carbon-carbon unsaturated bond to a hydrosilylation reaction with a hydrolyzable silyl group-containing hydrosilane compound.

The silyl group of the silane-crosslinkable polymer (B) obtained using step (III) is not particularly limited, but is particularly preferably represented by the following formula (4).
—O—(CH ₂ ) ₃ —SiX ₃ (4)
(X in formula (4) is the same as described above for formula (1).)

Such a silyl group can be obtained by using allyl chloride or the like as the carbon-carbon unsaturated bond-containing halide, and trichlorosilane, trimethoxysilane, triethoxysilane, or triisopropyl It can be formed by using penyloxysilane or the like.

(Reaction with alkali metal salt)
In converting the hydroxyl group of the organic polymer to a group containing a carbon-carbon unsaturated bond, first, the hydroxyl group-containing organic polymer is reacted with an alkali metal salt to convert the hydroxyl group of the organic polymer into a metaloxy group. Conversion is preferred. A double metal cyanide complex catalyst can also be used instead of the alkali metal salt. A metaloxy group-containing organic polymer is formed in the above manner.

Although the alkali metal salt is not particularly limited, examples thereof include sodium hydroxide, sodium alkoxide, potassium hydroxide, potassium alkoxide, lithium hydroxide, lithium alkoxide, cesium hydroxide, and cesium alkoxide. Sodium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium hydroxide, potassium methoxide, potassium ethoxide, and potassium tert-butoxide are preferred from the viewpoint of ease of handling and solubility, and sodium methoxide and sodium tert. -butoxide is more preferred. From the standpoint of availability, sodium methoxide is particularly preferred, and from the standpoint of reactivity, sodium tert-butoxide is particularly preferred. The alkali metal salt may be dissolved in a solvent before being subjected to the reaction.

The amount of the alkali metal salt used is not particularly limited, but in order to increase the reaction rate, the molar ratio to the hydroxyl group of the organic polymer is preferably 0.5 or more, more preferably 0.6 or more, and 0.7. More preferably 0.8 or more is even more preferable. The molar ratio is preferably 1.2 or less, more preferably 1.1 or less.

In order to efficiently proceed with the reaction that converts the hydroxyl groups of the organic polymer into metaloxy groups, it is preferable to remove moisture and substances having hydroxyl groups other than the organic polymer from the reaction system in advance. For removal, known methods may be used, such as heat evaporation, vacuum devolatilization, spray vaporization, thin film evaporation, azeotropic devolatilization, and the like.

The temperature at which the alkali metal salt is allowed to act can be appropriately set by those skilled in the art, but is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 145°C or lower. The time for which the alkali metal salt is allowed to act is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

(Reaction with carbon-carbon unsaturated bond-containing halide)
By reacting a carbon-carbon unsaturated bond-containing halide to the metaloxy group-containing organic polymer, the metaloxy group of the metaloxy group-containing organic polymer is converted into a carbon-carbon unsaturated bond-containing group. can be converted. The halide reacts with the metaloxy group to form an ether bond through a halogen substitution reaction. This forms an organic polymer with carbon-carbon unsaturation.

Specific examples of the carbon-carbon unsaturated bond-containing halide include, but are not limited to, vinyl chloride, allyl chloride, methallyl chloride, vinyl bromide, allyl bromide, methallyl bromide, vinyl iodide, allyl iodide, iodine and methallyl chloride. Allyl chloride and methallyl chloride are preferred for ease of handling.

The amount of the halide containing a carbon-carbon unsaturated bond to be added is not particularly limited, but the molar ratio of the organic halide to the metaloxy group possessed by the organic polymer is preferably 0.7 or more, preferably 1.0. The above is more preferable. Moreover, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

The temperature at which the metaloxy group-containing organic polymer is reacted with the carbon-carbon unsaturated bond-containing halide is preferably 50°C or higher and 150°C or lower, more preferably 110°C or higher and 140°C or lower. The reaction time is preferably 10 minutes or more and 5 hours or less, more preferably 30 minutes or more and 3 hours or less.

(Reaction with Hydrolyzable Silyl Group-Containing Hydrosilane Compound)
Specific examples of hydrolyzable silyl group-containing hydrosilane compounds include trichlorosilane, dichloromethylsilane, chlorodimethylsilane, dichlorophenylsilane, (chloromethyl)dichlorosilane, (dichloromethyl)dichlorosilane, bis(chloromethyl)chlorosilane, ( Halosilanes such as methoxymethyl)dichlorosilane, (dimethoxymethyl)dichlorosilane, bis(methoxymethyl)chlorosilane; trimethoxysilane, triethoxysilane, dimethoxymethylsilane, diethoxymethylsilane, dimethoxyphenylsilane, ethyldimethoxysilane, methoxy dimethylsilane, ethoxydimethylsilane, (chloromethyl)methylmethoxysilane, (chloromethyl)dimethoxysilane, (chloromethyl)diethoxysilane, bis(chloromethyl)methoxysilane, (methoxymethyl)methylmethoxysilane, (methoxymethyl) Dimethoxysilane, bis(methoxymethyl)methoxysilane, (methoxymethyl)diethoxysilane, (ethoxymethyl)diethoxysilane, (3,3,3-trifluoropropyl)dimethoxysilane, (N,N-diethylaminomethyl)dimethoxysilane Silane, (N,N-diethylaminomethyl)diethoxysilane, [(chloromethyl)dimethoxysilyloxy]dimethylsilane, [(chloromethyl)diethoxysilyloxy]dimethylsilane, [(methoxymethyl)dimethoxysilyloxy]dimethylsilane , [(methoxymethyl)diemethoxysilyloxy]dimethylsilane, [(diethylaminomethyl)dimethoxysilyloxy]dimethylsilane, [(3,3,3-trifluoropropyl)dimethoxysilyloxy]dimethylsilane and other alkoxysilanes; Acyloxysilanes such as diacetoxymethylsilane and diacetoxyphenylsilane; ketoximate silanes such as bis(dimethylketoximate)methylsilane and bis(cyclohexylketoximate)methylsilane; ) diisopropenyloxysilane, (methoxymethyl)diisopropenyloxysilane and other isopropenyloxysilanes (deacetone type).

The amount of the hydrosilane compound containing a hydrolyzable silyl group is not particularly limited, but the molar ratio of the organic halide to the carbon-carbon unsaturated bond of the organic polymer is preferably 0.6 or more. 0.8 or more is more preferable. Moreover, the molar ratio is preferably 5.0 or less, more preferably 2.0 or less.

The hydrosilylation reaction is preferably carried out in the presence of a hydrosilylation catalyst in order to promote the reaction. As the hydrosilylation catalyst, metals such as cobalt, nickel, iridium, platinum, palladium, rhodium and ruthenium, and complexes thereof can be used. Specifically, platinum supported on a carrier such as alumina, silica, carbon black; chloroplatinic acid; chloroplatinic acid complexes composed of chloroplatinic acid and alcohols, aldehydes, ketones, etc.; Pt( _CH2 = _CH2 ) ₂ (PPh3), Pt( _CH2 ₌ _CH2 ) _2Cl2 ]; platinum _- vinylsiloxane complexes [e.g. Pt {(vinyl) _Me2SiOSiMe2 ₍ vinyl)}, Pt{ Me(vinyl)SiO} ₄ ]; platinum-phosphine complexes [eg Ph(PPh ₃ ) ₄ , Pt(PBu ₃ ) ₄ ]; platinum-phosphite complexes [eg Pt{P(OPh) ₃ } ₄ ]; be done. From the viewpoint of reaction efficiency, platinum catalysts such as chloroplatinic acid and platinum-vinylsiloxane complexes are preferred.

The hydrosilylation reaction can be carried out without using a solvent, but for the purpose of uniformly dissolving the organic polymer, hydrosilane compound, and hydrosilylation catalyst, temperature control of the reaction system, hydrosilylation catalyst In order to easily realize the addition of, it may be carried out by adding an organic solvent.

The temperature during the hydrosilylation reaction is not particularly limited and can be appropriately set by those skilled in the art. However, for the purpose of reducing the viscosity of the reaction system and improving the reactivity, heating conditions are preferred, specifically 50° C. to 150° C. °C, more preferably 70°C to 120°C. The reaction time may also be appropriately set, but it is preferable to adjust the reaction time together with the temperature conditions so that an unintended condensation reaction between polymers does not proceed. Specifically, the reaction time is preferably 30 minutes or more and 5 hours or less, more preferably 3 hours or less.

<<Composition containing silane-crosslinkable polymer (A) and silane-crosslinkable polymer (B)>>
According to this embodiment, a composition comprising a silane-crosslinkable polymer (A) and a silane-crosslinkable polymer (B) can be provided. The composition may use only one type of the silane-crosslinkable polymer (A), or may use two or more types in combination. In addition, the composition may use only one type of the silane-crosslinkable polymer (B), or may use two or more types in combination.

In addition, when the composition can be cured to obtain a cured product, the composition is sometimes called a curable composition.

The composition can reduce the modulus of the cured product by reacting the silane crosslinkable polymer (B) with a part of the terminal of the silane crosslinkable polymer (A), and has physical properties suitable for use as a sealant. can be adjusted.

In the composition, when the silane-crosslinkable polymer (A) is 100 parts by weight, the content of the silane-crosslinkable polymer (B) can be appropriately determined according to the desired modulus, curability and restorability. 5 to 200 parts by weight is preferable, 10 to 150 parts by weight is more preferable, and 20 to 100 parts by weight is particularly preferable.

<<Aminosilane Compound (C)>>
Since the silane crosslinkable polymer (A) has a highly active hydrolyzable silyl group, an aminosilane compound (C), which is an amino group-containing silane coupling agent, can also be used as a curing catalyst. Since the aminosilane compound (C) is usually added as an adhesion imparting agent in many cases, the use of the aminosilane compound (C) as a curing catalyst is preferable in that a composition that does not use a commonly used curing catalyst can be produced. . Therefore, when using the aminosilane compound (C), it is preferable not to add other curing catalysts.

Specific examples of the aminosilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltrimethoxysilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl)aminopropyltriethoxysilane, γ-(2-aminoethyl) Aminopropylmethyldiethoxysilane, γ-(2-aminoethyl)aminopropyltriisopropoxysilane, γ-(2-(2-aminoethyl)aminoethyl)aminopropyltrimethoxysilane, γ-(6-aminohexyl) aminopropyltrimethoxysilane, 3-(N-ethylamino)-2-methylpropyltrimethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane , N-benzyl-γ-aminopropyltrimethoxysilane, N-vinylbenzyl-γ-aminopropyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyl Amino group-containing silanes such as trimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane, N,N'-bis[3-(trimethoxysilyl)propyl]ethylenediamine; N-(1,3-dimethylbutyl and ketimine-type silanes such as liden)-3-(triethoxysilyl)-1-propanamine. Only one type of aminosilane compound (C) may be used, or two or more types may be used in combination.

The amount of the aminosilane compound (C) to be blended is 0.1 parts by weight or more and 20 parts by weight or less when the total of the silane crosslinkable polymer (A) and the silane crosslinkable polymer (B) is 100 parts by weight. is preferred, 0.5 to 15 parts by weight is more preferred, and 1 to 10 parts by weight is even more preferred.

<<Other Additives>>
The composition according to the present embodiment contains other additives such as a curing catalyst, a silicon compound, an adhesion imparting agent, a plasticizer, a solvent, a diluent, a silicate, a filler, an anti-sagging agent, an antioxidant, and a light stabilizer. agent, UV absorber, physical property modifier, tackifier resin, epoxy group-containing compound, photo-curing substance, oxygen-curing substance, surface property modifier, epoxy resin, other resins, flame retardant, foaming agent You can Moreover, various additives may be added to the composition according to the present embodiment as necessary for the purpose of adjusting various physical properties of the composition or the cured product. Examples of such additives include curability modifiers, radical inhibitors, metal deactivators, antiozonants, phosphorus peroxide decomposers, lubricants, pigments, antifungal agents, and the like. be done.

<Curing catalyst>
The composition according to the present embodiment contains the aminosilane compound (C) described above and/or other curing catalysts for the purpose of promoting the reaction of hydrolyzing and condensing the hydrolyzable silyl groups, that is, the curing reaction. It is preferable to contain.

As other curing catalysts, conventionally known ones can be used. Specifically, organic tin compounds, carboxylic acid metal salts, amine compounds, carboxylic acids, alkoxy metals, inorganic acids, etc. can be used. .

Specific examples of organotin compounds include dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(butyl maleate), dibutyltin diacetate, dibutyltin oxide, dibutyltin bis(acetylacetonate), dibutyltin oxide and silicate compounds. reaction product with dibutyltin oxide and phthalate ester, dioctyltin diacetate, dioctyltin dilaurate, dioctyltin bis(ethyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(acetylacetonate) phosphate), dioctyltin distearate, dioctyltin oxide, a reaction product of dioctyltin oxide and a silicate compound, and the like. Dioctyltin compounds are preferred due to recent heightened environmental concerns. However, since the silane-crosslinkable polymer (A) can exhibit rapid curing properties, the composition according to the present embodiment does not contain an organic tin compound, and the curing catalyst is generally less active than the organic tin compound. (in particular, amine compounds, etc.). Even if the composition according to the present embodiment contains an amine compound, it can exhibit good curability.

Specific examples of carboxylate metal salts include tin carboxylate, bismuth carboxylate, titanium carboxylate, zirconium carboxylate, iron carboxylate, potassium carboxylate, and calcium carboxylate. As the carboxylic acid group, the following carboxylic acid and various metals can be combined.

Specific examples of amine compounds include amines such as octylamine, 2-ethylhexylamine, laurylamine, stearylamine; pyridine, 1,8-diazabicyclo[5,4,0]undecene-7 (DBU), 1, Nitrogen-containing heterocyclic compounds such as 5-diazabicyclo[4,3,0]nonene-5 (DBN); guanidines such as guanidine, phenylguanidine and diphenylguanidine; biguanides such as phenylbiguanide; and ketimine compounds.

Specific examples of carboxylic acids include acetic acid, propionic acid, butyric acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, linoleic acid, neodecanoic acid, and versatic acid.

Specific examples of alkoxy metals include titanium compounds such as tetrabutyl titanate, titanium tetrakis (acetylacetonate), diisopropoxytitanium bis (ethylacetonate), aluminum tris (acetylacetonate), diisopropoxy aluminum ethylacetate Examples include aluminum compounds such as acetate, and zirconium compounds such as zirconium tetrakis (acetylacetonate).

As other curing catalysts, fluorine anion-containing compounds, photoacid generators, and photobase generators can also be used.

The curing catalyst may be used in combination of two or more different catalysts. For example, the combination of the amine compound and carboxylic acid, or the combination of the amine compound and alkoxy metal provides the effect of improving the reactivity. There is a possibility that it will be

The amount of the curing catalyst is preferably 0.001 to 20 parts by weight, preferably 0.01 to 15 parts by weight, when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. parts are more preferred, and 0.01 to 10 parts by weight are particularly preferred. If the amount of the curing catalyst is less than 0.001 part by weight, the reaction rate may be insufficient. On the other hand, when the amount of the curing catalyst exceeds 20 parts by weight, the reaction rate is too fast, and the usable time of the composition is shortened, resulting in poor workability and poor storage stability. Furthermore, some curing catalysts may exude to the surface of the cured product or contaminate the surface of the cured product after the composition is cured. In such a case, by setting the amount of the curing catalyst to 0.01 to 3.0 parts by weight, it is possible to maintain good surface conditions of the cured product while ensuring curability.

<Filler>
Various fillers can be added to the composition according to the present embodiment. Fillers include ground calcium carbonate, colloidal calcium carbonate, magnesium carbonate, diatomaceous earth, clay, talc, titanium oxide, fumed silica, precipitated silica, crystalline silica, fused silica, anhydrous silicic acid, hydrous silicic acid, carbon black, ferric oxide, fine aluminum powder, zinc oxide, active zinc white, PVC powder, PMMA powder, glass fiber and filament, and the like.

The amount of the filler to be used is preferably 1 to 300 parts by weight, more preferably 10 to 250 parts by weight, when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight.

Organic balloons and inorganic balloons may be added for the purpose of weight reduction (lower specific gravity) of the composition. The balloon is hollow inside with a spherical filler, and is made of inorganic materials such as glass, shirasu, and silica, and organic materials such as phenolic resin, urea resin, polystyrene, and saran. materials.

The amount of the balloon used is preferably 0.1 to 100 parts by weight, more preferably 1 to 20 parts by weight, when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. .

<Adhesion imparting agent>
An adhesion imparting agent can be added to the composition according to the present embodiment. A silane coupling agent or a reactant of the silane coupling agent can be added as the adhesion imparting agent.

Specific examples of silane coupling agents include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane, N-β-aminoethyl-γ- Amino group-containing silanes such as aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, (2-aminoethyl)aminomethyltrimethoxysilane; γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltrimethoxysilane; isocyanate group-containing silanes such as ethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, α-isocyanatomethyltrimethoxysilane, α-isocyanatomethyldimethoxymethylsilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, mercapto group-containing silanes such as γ-mercaptopropylmethyldimethoxysilane; epoxy group-containing silanes such as γ-glycidoxypropyltrimethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; . Condensates of various silane coupling agents such as condensation products of amino group-containing silanes, condensation products of amino group-containing silanes and other alkoxysilanes; reaction products of amino group-containing silanes and epoxy group-containing silanes; Reaction products of various silane coupling agents, such as reaction products of containing silanes and (meth)acrylic group-containing silanes, can also be used. The adhesiveness-imparting agent may be used alone or in combination of two or more.

The amount of the silane coupling agent used is preferably 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, when the total of the silane crosslinkable polymer (A) and the silane crosslinkable polymer (B) is 100 parts by weight. Parts by weight are more preferred.

Since the above amino group-containing silanes can also be used as the aminosilane compound (C), which is a curing catalyst, when no other curing catalyst is used, the amino group-containing silanes (aminosilane compound (C)) are It becomes an additive that functions both as a curing catalyst and as an adhesion-imparting agent.

<Plasticizer>
A plasticizer can be added to the composition according to the present embodiment. Specific examples of plasticizers include dibutyl phthalate, diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl) phthalate, diisodecyl phthalate (DIDP), phthalate compounds such as butylbenzyl phthalate; bis(2-ethylhexyl )-terephthalate compounds such as 1,4-benzenedicarboxylate; non-phthalate compounds such as 1,2-cyclohexanedicarboxylic acid diisononyl ester; dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate, Aliphatic polyvalent carboxylic acid ester compounds such as tributyl acetylcitrate; unsaturated fatty acid ester compounds such as butyl oleate and methyl acetylricinoleate; phenyl alkylsulfonic acid esters; phosphoric acid ester compounds; trimellitic acid ester compounds; Paraffin; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxystearate;

In addition, a polymer plasticizer can be used. Specific examples of polymeric plasticizers include vinyl polymers; polyester plasticizers; polyether polyols such as polyethylene glycol and polypropylene glycol having a number average molecular weight of 500 or more; polyethers such as derivatives converted to polystyrenes; polybutadiene, polybutene, polyisobutylene, butadiene-acrylonitrile, polychloroprene and the like. A plasticizer may be used individually and may use 2 or more types together.

The amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. 20 to 100 parts by weight is more preferable.

<Solvent, diluent>
A solvent or diluent can be added to the composition according to the present invention. Solvents and diluents that can be used include, but are not limited to, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, halogenated hydrocarbons, alcohols, esters, ketones, and ethers. When a solvent or diluent is used, the boiling point of the solvent is preferably 150° C. or higher, more preferably 200° C. or higher, and particularly preferably 250° C. or higher, because of the problem of air pollution when the composition is used indoors. . The above solvents or diluents may be used alone or in combination of two or more.

<Anti-sagging agent>
An anti-sagging agent may be added to the composition according to the present embodiment to prevent sagging and improve workability, if necessary. The anti-sagging agent is not particularly limited, but examples thereof include polyamide waxes; hydrogenated castor oil derivatives; metal soaps such as calcium stearate, aluminum stearate and barium stearate. These anti-sagging agents may be used alone or in combination of two or more.

The amount of anti-sagging agent to be used is preferably 0.1 to 20 parts by weight when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight.

<Antioxidant>
An antioxidant (antiaging agent) can be used in the composition according to the present embodiment. The use of an antioxidant can enhance the weather resistance of the cured product. Examples of antioxidants include hindered phenols, monophenols, bisphenols, and polyphenols. Specific examples of antioxidants are also described in JP-A-4-283259 and JP-A-9-194731.

The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. part is more preferred.

<Light stabilizer>
A light stabilizer can be used in the composition according to this embodiment. The use of a light stabilizer can prevent photo-oxidative deterioration of the cured product. Benzotriazole-based, hindered amine-based, and benzoate-based compounds can be exemplified as light stabilizers, and hindered amine-based compounds are particularly preferred.

The amount of the light stabilizer to be used is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. part is more preferred.

<Ultraviolet absorber>
An ultraviolet absorber can be used in the composition according to this embodiment. The use of an ultraviolet absorber can enhance the surface weather resistance of the cured product. Examples of UV absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, and metal chelate-based compounds. Benzotriazole-based compounds are particularly preferred, and are commercially available under the names Tinuvin P, Tinuvin 213, Tinuvin 234, Tinuvin 326, Tinuvin 327, Tinuvin 328, Tinuvin 329, Tinuvin 571, Tinuvin 1600, Tinuvin B75 (manufactured by BASF).

The amount of the ultraviolet absorber to be used is preferably 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. part is more preferred.

<Physical property modifier>
A physical property modifier for adjusting the tensile properties of the resulting cured product may be added to the composition according to the present embodiment, if necessary. Although the physical property modifier is not particularly limited, for example, alkylalkoxysilanes such as phenoxytrimethylsilane, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane; diphenyldimethoxysilane, phenyltrimethoxysilane. arylalkoxysilanes such as; alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, methyltriisopropenoxysilane, γ-glycidoxypropylmethyldiisopropenoxysilane; trialkylsilylborates such as silyl)borate; silicone varnishes; polysiloxanes; By using the physical property modifier, it is possible to increase the hardness when the composition according to the present embodiment is cured, or conversely decrease the hardness and increase the elongation at break. The physical property modifiers may be used alone or in combination of two or more.

In particular, a compound that produces a compound having a monovalent silanol group in its molecule by hydrolysis has the effect of lowering the modulus of the cured product without exacerbating the stickiness of the surface of the cured product. Compounds that generate trimethylsilanol are particularly preferred. Examples of compounds that generate a compound having a monovalent silanol group in the molecule by hydrolysis include alcohol derivatives such as hexanol, octanol, phenol, trimethylolpropane, glycerin, pentaerythritol, and sorbitol, which are hydrolyzed into silane monovalent groups. Mention may be made of silicon compounds that produce ols. Specific examples include phenoxytrimethylsilane and tris((trimethylsiloxy)methyl)propane.

The amount of the physical property modifier used is preferably 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. part is more preferred.

<Tackifying resin>
A tackifier resin can be added to the composition according to the present embodiment for the purpose of enhancing the adhesiveness or adhesion to a substrate, or for other purposes. As the tackifying resin, there is no particular limitation, and those commonly used can be used.

Specific examples include terpene-based resins, aromatic modified terpene resins, hydrogenated terpene resins, terpene-phenolic resins, phenolic resins, modified phenolic resins, xylene-phenolic resins, cyclopentadiene-phenolic resins, coumarone-indene resins, rosin-based Resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, styrene block copolymers and hydrogenated products thereof, petroleum resins (e.g., C5 hydrocarbon resins, C9 hydrocarbon resins, C5C9 hydrocarbon copolymer resins, etc.), hydrogenated petroleum resins, DCPD resins, and the like. These may be used alone or in combination of two or more.

The amount of the tackifying resin used is preferably 2 to 100 parts by weight, more preferably 5 to 50 parts by weight, when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. is more preferred, and 5 to 30 parts by weight is even more preferred.

<Compound containing an epoxy group>
A compound containing an epoxy group can be used in the composition according to the present embodiment. The use of a compound having an epoxy group can enhance the restorability of the cured product. Examples of compounds having an epoxy group include epoxidized unsaturated fats and oils, epoxidized unsaturated fatty acid esters, alicyclic epoxy compounds, epichlorohydrin derivatives, and mixtures thereof. Specifically, epoxidized soybean oil, epoxidized linseed oil, bis(2-ethylhexyl)-4,5-epoxycyclohexane-1,2-dicarboxylate (E-PS), epoxyoctyl stearate, epoxy butyl stearate and the like. The epoxy compound is preferably used in an amount of 0.5 to 50 parts by weight based on 100 parts by weight of the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B).

<Photocurable substance>
A photocurable substance can be used in the composition according to the present embodiment. When a photocurable substance is used, a film of the photocurable substance is formed on the surface of the cured product, and the stickiness of the cured product and the weather resistance of the cured product can be improved. Many compounds such as organic monomers, oligomers, resins, or compositions containing them are known as this type of compound. Unsaturated acrylic compounds, polyvinyl cinnamates, azide resins, etc., which are monomers, oligomers, or mixtures thereof can be used.

The amount of the photocurable substance used is preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the total amount of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B). 5 to 10 parts by weight is more preferred.

<Oxygen Curable Substance>
An oxygen-curable substance can be used in the composition according to this embodiment. Examples of oxygen-curable substances include unsaturated compounds that can react with oxygen in the air, and react with oxygen in the air to form a hardened film near the surface of the cured product, which causes the surface to become sticky and dust on the surface of the cured product. and prevent the adhesion of dust. Specific examples of oxygen-curable substances include drying oils such as paulownia oil and linseed oil, various alkyd resins obtained by modifying these compounds; acrylic polymers modified with drying oils, and epoxy resins. , silicone resins; 1,2-polybutadiene, 1,4-polybutadiene, C5-C8 diene polymers obtained by polymerizing or copolymerizing diene compounds such as butadiene, chloroprene, isoprene, 1,3-pentadiene, etc. Examples include liquid polymers. These may be used alone or in combination of two or more.

The amount of the oxygen-curable substance used is preferably 0.1 to 20 parts by weight when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. 5 to 10 parts by weight is more preferred. As described in JP-A-3-160053, oxygen-curable substances are preferably used in combination with photo-curable substances.

<Epoxy resin>
An epoxy resin can be used in combination with the composition according to the present embodiment. A composition containing an epoxy resin is particularly preferred as an adhesive, especially an adhesive for exterior wall tiles. Examples of epoxy resins include bisphenol A type epoxy resins and novolac type epoxy resins.

The amount of the epoxy resin used is preferably in the range of 1 to 10000 parts by weight when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. When the epoxy resin is less than 1 part by weight, it becomes difficult to obtain the effect of improving the impact strength and toughness of the cured epoxy resin. Become.

When an epoxy resin is added, a curing agent that cures the epoxy resin can be used in combination with the composition according to the present embodiment. The epoxy resin curing agent that can be used is not particularly limited, and generally used epoxy resin curing agents can be used.

When using an epoxy resin curing agent, the amount used is preferably in the range of 0.1 to 300 parts by weight with respect to 100 parts by weight of the epoxy resin.

<<Preparation of composition>>
The composition according to the present embodiment can also be prepared as a one-component type in which all the ingredients are preformed and sealed and stored, and cured by moisture in the air after application. It can also be prepared as a two-component type in which components such as the material, plasticizer, and water are blended and the blending materials and the organic polymer composition are mixed before use. From the viewpoint of workability, the one-component type is preferred.

When the composition is of the one-component type, all the ingredients are blended in advance. Therefore, it is recommended that the ingredients containing water be dehydrated and dried before use, or dehydrated by decompression during compounding and kneading. preferable. In addition to the dehydration drying method, methyltrimethoxysilane, phenyltrimethoxysilane, n-propyltrimethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Addition of alkoxysilane compounds such as ethoxysilane and γ-glycidoxypropyltrimethoxysilane further improves the storage stability.

<<Usage>>
The composition according to the present embodiment includes adhesives, sealing materials for buildings, ships, automobiles, roads, etc., adhesives, waterproofing materials, coating film waterproofing materials, molding agents, vibration-proof materials, vibration-damping materials, and soundproofing materials. , can be used as foaming materials, paints, spraying materials. A cured product obtained by curing the composition according to the present embodiment is excellent in flexibility and adhesiveness, and thus can be suitably used as a sealant or an adhesive.

In addition, the composition according to the present embodiment includes electrical and electronic component materials such as solar cell backside sealing materials, electrical and electronic components such as insulating coating materials for electric wires and cables, electrical insulating materials for devices, acoustic insulating materials, Elastic adhesives, binders, contact adhesives, spray sealing materials, crack repairing materials, tiling adhesives, asphalt waterproofing adhesives, powder coatings, casting materials, medical rubber materials, medical adhesives , medical adhesive sheets, sealing materials for medical equipment, dental impression materials, food packaging materials, joint sealing materials for exterior materials such as sizing boards, coating materials, anti-slip coating materials, cushioning materials, primers, conductive materials for shielding electromagnetic waves, Thermally conductive materials, hot-melt materials, potting agents for electrical and electronic devices, films, gaskets, concrete reinforcing materials, adhesives for temporary fixing, various molding materials, and anti-corrosion and anti-corrosion of wired glass and laminated glass edges (cut parts). Used for various applications such as waterproof sealant, automobile parts, large vehicle parts such as trucks and buses, train car parts, aircraft parts, ship parts, electrical parts, liquid sealants used in various machine parts, etc. It is possible. Taking automobiles as an example, it can be used in a wide variety of ways, such as adhesive attachment of plastic covers, trims, flanges, bumpers, windows, interior members, and exterior parts. Furthermore, since it can adhere to a wide range of substrates such as glass, porcelain, wood, metal, resin moldings, etc. alone or with the help of a primer, it can be used as various types of sealing compositions and adhesive compositions. . In addition, the composition according to the present embodiment is an adhesive for interior panels, an adhesive for exterior panels, an adhesive for tiling, an adhesive for masonry, an adhesive for ceiling finishing, an adhesive for floor finishing, and an adhesive for wall finishing. Adhesives, vehicle panel adhesives, electrical, electronic and precision equipment assembly adhesives, adhesives for bonding leather, textiles, fabrics, paper, boards and rubber, reactive post-crosslinking pressure sensitive adhesives, direct It can also be used as a sealing material for glazing, a sealing material for double glazing, a sealing material for the SSG construction method, a sealing material for working joints in buildings, a material for civil engineering, and a material for bridges. Furthermore, it can be used as an adhesive material such as an adhesive tape and an adhesive sheet.

Although the present invention will be described in more detail with reference to examples below, the present invention is not limited to these examples.

The number average molecular weight in the examples is the GPC molecular weight measured under the following conditions.
Liquid delivery system: Tosoh HLC-8220GPC
Column: TSK-GEL H type manufactured by Tosoh Solvent: THF
Molecular weight: Polystyrene equivalent Measurement temperature: 40°C

(Synthesis example 1)
Polyoxypropylene triol having a number average molecular weight of about 4,500 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain a branched polyoxypropylene having a terminal hydroxyl group and a number average molecular weight of 23,300. Oxypropylene (C-1) was obtained.
Subsequently, at 90 ° C., bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) 30 ppm with respect to 100 parts by weight of polymer (C-1), and hydroxyl groups possessed by the polymer 0.95 molar equivalent of (isocyanatomethyl)dimethoxymethylsilane was added to the polymer, and the hydroxyl group of the polymer was subjected to a urethanization reaction. Thus, branched silyl group-containing polyoxypropylene (A-1) was obtained. This corresponds to the silane-crosslinkable polymer (A).

(Synthesis example 2)
Polyoxypropylene glycol having a number average molecular weight of about 4,500 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of 15,000 and having hydroxyl groups at both ends. (C-2) was obtained.
Bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) 30 ppm with respect to 100 parts by weight of polymer (C-2), and 0.95 mol with respect to hydroxyl groups possessed by the polymer An equivalent amount of (isocyanatemethyl)dimethoxymethylsilane is added to carry out a urethanization reaction on the hydroxyl groups of the polymer to obtain linear silyl group-containing polyoxypropylene (A-2) having no branch points. rice field.

(Synthesis Example 3)
Polyoxypropylene glycol having a number average molecular weight of about 4,500 is used as an initiator, and propylene oxide is polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene having a number average molecular weight of 27,900 and having hydroxyl groups at both ends. (C-3) was obtained.
Bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) 30 ppm with respect to 100 parts by weight of polymer (C-3), and 0.95 mol with respect to hydroxyl groups possessed by the polymer An equivalent amount of (isocyanatomethyl)dimethoxymethylsilane is added to carry out a urethanization reaction on the hydroxyl groups of the polymer to obtain linear silyl group-containing polyoxypropylene (A-3) having no branch points. rice field.

(Synthesis Example 4)
Using butanol as an initiator, propylene oxide was polymerized with a zinc hexacyanocobaltate glyme complex catalyst to obtain polyoxypropylene (C-4) having a hydroxyl group at one end and a number average molecular weight of 7,800.
Then, at 90 ° C., bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) 30 ppm with respect to 100 parts by weight of polymer (C-4), and hydroxyl groups possessed by the polymer 0.95 molar equivalent of (isocyanatomethyl)dimethoxymethylsilane was added to the polymer, and the hydroxyl groups of the polymer were subjected to a urethanization reaction. As a result, polyoxypropylene (B-1) having no branch point and having an alkoxysilyl group at one end was obtained.

(Synthesis Example 5)
At 90 ° C., bismuth 2-ethylhexanoate (III) 2-ethylhexanoic acid solution (Bi: 25%) 30 ppm with respect to 100 parts by weight of the polymer (C-4) obtained in Reference Example 1, and the polymer 0.95 molar equivalent of (3-isocyanatopropyl)trimethoxysilane was added to the hydroxyl groups of the polymer, and the hydroxyl groups of the polymer were subjected to a urethanization reaction. As a result, polyoxypropylene (B-2) having an alkoxysilyl group at one end and no branching points was obtained.

(Synthesis Example 6)
A 28% methanol solution of 0.75 molar equivalents of sodium methoxide was added to the hydroxyl group-terminated polyoxypropylene (C-4) obtained in Synthesis Example 4 with respect to the hydroxyl group. After removing methanol by distillation under reduced pressure, allyl chloride was added in an amount of 1.1 molar equivalents relative to the hydroxyl groups of the polymer (C-4), and the mixture was reacted at 130° C. for 1 hour, and allyl chloride was distilled off. left. After that, 0.47 molar equivalent of sodium methoxide was added as a 28% methanol solution to the hydroxyl groups of the polymer (C-4). After removing methanol by distillation under reduced pressure at 130° C., allyl chloride was added in an amount of 2.1 molar equivalents relative to the hydroxyl groups of the polymer (C-4) and reacted at 130° C. for 2 hours. Allyl was distilled off. The obtained unpurified allyl-terminated polyoxypropylene was mixed with n-hexane and water and stirred, and the water was removed by centrifugation. removed. As a result, polyoxypropylene (D-1) having a carbon-carbon unsaturated bond (allyl group) at one end was obtained.
Then, at 90° C., 50 ppm of a platinum divinyldisiloxane complex (3% by weight isopropanol solution in terms of platinum) and 2.07 parts by weight of trimethoxysilane are added to 100 parts by weight of polymer (D-1). Then, a hydrosilylation reaction was carried out on the allyl groups possessed by the polymer (D-1). After reacting at 90° C. until the trimethoxysilane was completely consumed, the volatile components were distilled off. As a result, polyoxypropylene (B-3) having no branch point and having a trimethoxysilyl group at one end was obtained.

(Examples 1 to 3, Comparative Examples 1 to 6, Reference Example 1)
90 parts by weight of DINP (manufactured by J-Plus Co., Ltd.: diisononyl phthalate) and 160 parts by weight of Hakuenka CCR (manufactured by Shiraishi Calcium Co., Ltd.: precipitated calcium carbonate) for a total of 100 parts by weight of the polymers shown in Tables 1 to 3. , Whiten SB (manufactured by Shiraishi Calcium Co., Ltd.: ground calcium carbonate) 54 parts by weight, Typaque R820 (manufactured by Ishihara Sangyo Co., Ltd.: titanium oxide) 5 parts by weight, Disparlon 6500 (manufactured by Kusumoto Chemical Co., Ltd.: fatty acid amide Wax) 2 parts by weight, Tinuvin 770 (manufactured by BASF: bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate) 1 part by weight, and Tinuvin 326 (manufactured by BASF: 2-(3-tert-butyl -2-Hydroxy-5-methylphenyl)-5-chlorobenzotriazole) was mixed with 1 part by weight to obtain 2 parts by weight of A-171 (manufactured by Momentive: vinyltrimethoxysilane) and A-1120 (manufactured by Momentive: 3 parts by weight of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane) were added and mixed. A-1120 (the aforementioned aminosilane) promotes condensation of hydrolyzable silyl groups and accelerates curing of the polymer.

(Skin covering time)
The obtained composition was filled into a mold with a thickness of about 5 mm, and the time when the surface was flattened was set as the curing start time, and the surface was touched with a spatula, and the time when the composition for evaluation stopped adhering to the spatula. Curing time was measured as skinning time. Results are shown in each table.

(Dumbbell tensile properties)
The obtained composition was filled in a mold and cured at 23° C. and 50% RH for 3 days and further at 50° C. for 4 days to prepare a sheet-like cured product having a thickness of about 3 mm. The cured sheet material was punched into a No. 3 dumbbell shape and subjected to a tensile strength test at 23° C. and 50% RH to measure the modulus at 50% or 100% elongation, the strength at break and elongation. The measurement was performed using an autograph (AGS-J) manufactured by Shimadzu Corporation at a pulling speed of 200 mm/min. Results are shown in each table.

(recovery rate)
The obtained composition was filled in a mold and cured at 23° C. and 50% RH for 3 days and further at 50° C. for 4 days to prepare a sheet-like cured product having a thickness of about 3 mm. The sheet-like cured product was punched into a No. 7 dumbbell shape, the dumbbell shape was stretched by 10 mm, both ends were fixed with clips, and the product was allowed to stand at 70° C. and 50% RH for 24 hours. After that, the clip was removed, and it was left to stand on a smooth glass plate in a state where the force causing deformation was removed, and it was confirmed how much the original shape was restored after 24 hours. Taking the elongation of the dumbbell after 24 hours as x (mm), the recovery rate was calculated as follows.
Restoration rate (%) = (10-x)/10 x 100
Results are shown in each table.

As is clear from Table 1, the composition of Example 1 containing the silane-crosslinkable polymer (A) having a branch point and the silane-crosslinkable polymer (B) contains the silane-crosslinkable polymer (A) having a branch point. , the modulus was lowered as compared with the composition of Reference Example 1, which did not contain the silane-crosslinkable polymer (B). Thus, a low modulus can be achieved by combining the silane-crosslinkable polymer (A) having a branch point with the silane-crosslinkable polymer (B) having a silyl group at only one terminal.
The composition of Example 1 exhibits better curability and recovery compared to the compositions of Comparative Examples 1 and 2, which contain a linear crosslinkable polymer having no branch points and a silane crosslinkable polymer (B). showed sex. The silane-crosslinkable polymers having no branch points contained in Comparative Examples 1 and 2 have different molecular weights, and the higher the molecular weight, the fewer the number of silyl terminals that can be introduced. The modulus is lower than that of the composition of Example 1, and the curability and restorability are also lowered due to the lower crosslink density between silyl groups. Generally, for sealant applications, a composition that gives a flexible cured product with a low modulus is desired. However, if the modulus is lowered in this way, curability and restorability tend to be disadvantageous. However, although the modulus of Example 1 was between Comparative Examples 1 and 2, the results of curability and restorability were the best.

Furthermore, as is clear from Tables 2 and 3, the compositions of Examples 2 and 3 containing the silane-crosslinkable polymer (A) having a branch point and the silane-crosslinkable polymer (B) having a specific silyl group have a branch point Comparative Examples 3 to 6 containing a linear silane crosslinkable polymer having no and a silane crosslinkable polymer (B) having a specific silyl group (Example 2 is compared with Comparative Examples 3 and 4, Example 3 compared with Comparative Examples 5 and 6) showed particularly good curability and restorability.

Claims

Silane crosslinkable polymer (A) represented by the following formula (1)
(HO) x —Y— [O—CO—NH—CR 12 —SiR a X 3 -a ] px (1)
(In Formula (1), Y is a polymer chain having at least one or more branch points, R is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and R 1 is each independently a hydrogen atom or a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms; X is a hydroxyl group or a hydrolyzable group; p is an integer of 3 to 10; is an integer from 0 to p-1, and a may be the same or different and is 0, 1 or 2.)
And a silane crosslinkable polymer (B) having no branch point and having only one terminal silyl group in one molecule represented by the following formula (2)
—SiR 2 c X 3-c (2)
(In formula (2), X is the same as described above, R 2 is each independently a substituted or unsubstituted hydrocarbon group having 1 to 20 carbon atoms, and c is 0, 1 or 2. .)
wherein the content of the silane-crosslinkable polymer (B) is 5 parts by weight or more and 200 parts by weight or less when the silane-crosslinkable polymer (A) is 100 parts by weight.
The composition according to claim 1, wherein p in formula (1) of the silane-crosslinkable polymer (A) represented by formula (1) is 3.
The composition according to claim 1 or 2, wherein the polymer skeleton of the silane crosslinkable polymers (A) and (B) is a polyoxyalkylene polymer.
The composition according to any one of claims 1 to 3, wherein the silyl groups of the silane-crosslinkable polymer (B) are represented by the following formula (3).
—O—CO—NH—(CH 2 ) 3 —SiX 3 (3)
(X is the same as described in claim 1 above.)
The composition according to any one of claims 1 to 3, wherein the silyl groups of the silane-crosslinkable polymer (B) are represented by the following formula (4).
—O—(CH 2 ) 3 —SiX 3 (4)
(X is the same as described in claim 1 above.)
The content of the silane-crosslinkable polymer (B) is 5 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the silane-crosslinkable polymer (A), according to any one of claims 1 to 5. The described composition.
Claims 1 to 2, further comprising 0.1 parts by weight or more and 20 parts by weight or less of an aminosilane compound (C) when the total of the silane-crosslinkable polymer (A) and the silane-crosslinkable polymer (B) is 100 parts by weight. 7. The composition of any one of 6.