JP4578166B2 - Curable resin composition and moisture curable adhesive composition containing the same - Google Patents

Description

  The present invention relates to a curable resin composition and a moisture curable adhesive composition containing the curable resin composition, and more specifically, a cured product obtained by blending a specific curable resin with a Lewis acid and / or a complex thereof as a curing catalyst. The present invention relates to a curable resin composition having a very high speed and a moisture curable adhesive composition containing the same.

Conventionally, organotin compounds such as dibutyltin dilaurate, dibutyltin diacetate, and dioctyltin dilaurate have been widely used as curing catalysts for curable resins having hydrolyzable silyl groups in the molecule. When the silylated urethane resin described in Patent Document 1 below is used as the curable resin having a decomposable silyl group, a curable resin composition having a relatively high curing rate can be obtained by blending an organic tin compound. Obtainable.
As a curing catalyst for a curable resin having a hydrolyzable silyl group in the molecule, an organic acid and an amine compound are well known in addition to the organic tin compound.
Lewis acid compounds such as metal halides such as aluminum chloride or boron halide compounds such as boron trichloride are well-known as curing catalysts for heat-curable epoxy resins (for example, Patent Documents 2 and 3 below), An example of using this as a curing catalyst for a curable resin having a hydrolyzable silyl group in the molecule such as modified silicone or silylated urethane resin has not been reported yet.

Japanese Patent No. 3030020 Japanese Patent Laid-Open No. 02-251274 Japanese Patent Laid-Open No. 02-228376

When a large amount of an organotin compound is blended as a curing catalyst for a curable resin having a hydrolyzable silyl group in the molecule to obtain a curable resin composition with a faster curing rate, the storage stability decreases. Or the content of the tin compound, which is a heavy metal, increases another risk of increasing the danger and harmfulness. In addition, when a curable resin composition containing a large amount of an organic tin compound or the like is used as an adhesive or a sealing agent for a plastic having a hydrolyzable group in a molecule such as polyurethane or polyester, the curability Organotin compounds in the composition may degrade these plastics. Moreover, even if a large amount of such an organic tin compound is blended, there is a limit to the curing rate to be increased. If a large amount is blended, a phenomenon that the curing rate is rather slow due to a dilution effect or a plastic effect occurs.
Furthermore, even if an organic acid or an amine compound is used as a curing catalyst for a curable resin having a silicon-containing characteristic group in the molecule, a fast curing rate cannot be obtained. For this reason, these are actually used as promoters.
The present invention has been made to solve the above-mentioned problems, and the object of the present invention is to provide a curable resin composition having a very high curing rate and a moisture curable adhesive composition containing the same. There is.

但し、Ｘはヒドロキシル基又は加水分解性基を、Ｒ ¹ は炭素数１〜２０個の置換若しくは非置換の有機基を、ｎは０，１又は２を、それぞれ示す。 In order to achieve the above object, the present invention comprises the following first to tenth inventions.
That is, the first invention is a silicon-containing characteristic group comprising at least one group selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the following formula (1) in the molecule (however, Characterized in that it contains a curable resin (A) that is liquid at room temperature containing at least a silicon-containing characteristic group where n = 0 in formula (1), and a Lewis acid and / or its complex (B). This is a moisture curable resin composition at 23 ° C.

However, X is a hydroxyl group or a hydrolyzable group, R ¹ is a C 1-20 substituted or unsubstituted organic group having a carbon, n represents 0, 1 or 2, respectively.

但し、Ｘはヒドロキシル基又は加水分解性基を、Ｒ ¹ は炭素数１〜２０個の置換若しくは非置換の有機基を、ｎは０，１又は２を、それぞれ示す。 According to a second aspect of the present invention, a silicon-containing characteristic group comprising at least one group selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the following formula (1) in the molecule, 1 type selected from urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group and tertiary amino group A curable resin composition comprising the curable resin (A) containing the above bond and / or group and a Lewis acid and / or a complex (B) thereof.

However, X is a hydroxyl group or a hydrolyzable group, R ¹ is a C 1-20 substituted or unsubstituted organic group having a carbon, n represents 0, 1 or 2, respectively.

The third invention relates to one or more groups selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the above formula (1) (provided that n = 0 in the above formula (1)). The ratio is 10 to 100% per silicon-containing characteristic group consisting of one or more groups selected from the group consisting of hydrolyzable silyl groups and silanol groups represented by the above formula (1) in the curable resin. A curable resin composition according to the first or second invention.
The fourth invention is selected from the group consisting of the curable resin composition of any one of the first to third inventions and a hydrolyzable silyl group and silanol group represented by the above formula (1) in the molecule. A silicon-containing characteristic group composed of one or more groups and an aminosilane compound (C) containing an amino group in the molecule, and / or a hydrolyzable silyl group and silanol group represented by the above formula (1) in the molecule A curable resin composition comprising a silicon-containing characteristic group composed of one or more groups selected from the group consisting of a mercaptosilane compound (D) containing a mercapto group in the molecule.

A fifth invention is the curable resin according to any one of the first to fourth inventions, wherein the Lewis acid of the Lewis acid and / or its complex (B) is a Lewis acid selected from metal chlorides. It is a composition.
The sixth invention is the curable resin composition according to any one of the first to fourth inventions, wherein the Lewis acid and / or its complex (B) is boron trifluoride and / or its amine complex. It is a thing.
7th invention contains 0.001 weight part-10 weight part of said Lewis' acid and / or its complex (B) per 100 weight part of said curable resins (A). The curable resin composition of any one of the inventions.

8th invention contains 0.001 weight part-10 weight part of the said Lewis' acid and / or its complex (B) per 100 weight part of said curable resins, and also the said Lewis acid and / or its complex ( The curable resin composition according to any one of the first to seventh inventions, which contains 0.01 to 10 parts by weight of a curing catalyst (E) other than B).
A ninth invention is the curable resin composition of the eighth invention, wherein the curing catalyst (E) is a dioctyltin-based catalyst.
A tenth invention is a moisture curable adhesive composition characterized by containing the curable resin composition of any one of the first to ninth inventions.

In the curable resin composition according to the first invention, the curable resin (A) containing a silicon-containing characteristic group with n = 0 in the above formula (1) is used in the molecule. Is extremely fast. The trifunctional silicon-containing characteristic group is represented by the formula: —SiR ¹ (X) ₂ (wherein X is the same as X above, and R ¹ is a substituted or unsubstituted group having 1 to 20 carbon atoms. It is known to give a curable resin a faster curability compared to a bifunctional silicon-containing characteristic group represented by (an organic group), but it can be used with a Lewis acid and / or its complex (B). Synergistically increasing the curability by the cooperative action is a finding found by the present inventor and is not known. The reason why the curability is enhanced synergistically is, for example, when boron trifluoride is taken as an example of the Lewis acid, boron trifluoride interacts with the hydrolyzable silyl group or silanol group in the silicon-containing characteristic group. By acting, it is presumed that the ability to remove hydrolyzable groups or OH groups in hydrolyzable silyl groups or silanol groups increases, and as a result, the coupling reaction between silyl groups is promoted. .

  The curable resin composition according to the second invention comprises, as a curable resin, a silicon-containing material comprising at least one group selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the above formula (1). Characteristic group and urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group and tertiary in the molecule Containing a curable resin (A) having one or more bonds and / or groups selected from amino groups (hereinafter, this specific bond and / or group may be referred to as "polar element part"); Since a Lewis acid and / or its complex (B) is contained as a curing catalyst, the curing rate is extremely fast. In particular, when the curable resin (A) containing at least one bond and / or group selected from the group consisting of a urethane bond, a substituted urea bond and a tertiary amino group is used as the polar element part, the curing is performed. A curable resin composition having an extremely high speed can be obtained. This is because the Lewis acid and / or its complex (B) is localized in the vicinity of the curable resin component from a molecular point of view due to electronic coordination with these specific bonds and / or groups. As a result, it is assumed that the reaction of the silicon-containing characteristic group is more activated.

In the curable resin composition according to the third invention, as a curable resin, the ratio of the silicon-containing characteristic group in which n = 0 in the above formula (1) is 10 per silicon-containing characteristic group in the curable resin. Since a curable resin of ˜100% is used, the curing rate is extremely fast.
The curable resin composition according to the fourth invention contains the curable resin (A) according to any one of the first to third inventions and is hydrolyzable silyl represented by the above formula (1) in the molecule. A silicon-containing characteristic group consisting of one or more groups selected from the group consisting of a group and a silanol group, and an aminosilane compound (C) containing an amino group in the molecule and / or the above formula (1) in the molecule Since it contains a silicon-containing characteristic group consisting of one or more groups selected from the group consisting of a hydrolyzable silyl group and a silanol group, and a mercaptosilane compound (D) containing a mercapto group in the molecule, the curing rate Is extremely fast and has excellent adhesion.
In the curable resin composition according to the fifth invention, a Lewis acid selected from metal chlorides is used as the Lewis acid and / or the Lewis acid of the complex (B) in any one of the first to fourth inventions. The curing rate is very preferable.

Since the curable resin composition according to the sixth invention uses boron trifluoride and / or its amine complex as the Lewis acid and / or its complex (B) in any one of the first to fourth inventions, A cure rate is highly preferred.
The curable resin composition according to the seventh invention is the Lewis acid and / or its complex (B) in any one of the first to sixth inventions, 0.001 weight per 100 parts by weight of the curable resin (A). Since the content is 10 parts by weight to 10 parts by weight, the curing rate is extremely preferable.
The curable resin composition according to an eighth aspect of the present invention is the Lewis acid and / or its complex (B) according to any one of the first to seventh aspects, per 0.00 part by weight of the curable resin (A). And 10 to 10 parts by weight of a curing catalyst (E) other than the Lewis acid and / or its complex (B) is contained in an amount of 0.01 to 10 parts by weight.

Since the curable resin composition according to the ninth invention is a curable resin composition using a dioctyltin-based compound as the curing catalyst (E), the curing rate is extremely preferable. Furthermore, dioctyltin compounds are known to be safer than commonly used dibutyltin compounds, and there are few problems of danger and harm.
Since the moisture-curable adhesive composition according to the tenth invention contains the curable resin composition according to any one of the first to ninth inventions, the curing rate is extremely fast. Any of the curable resin compositions according to any one of the first to ninth inventions exhibits rapid curing, and can be used for a wide variety of applications. In particular, this is a moisture curable adhesive composition. In the case where it is contained in a solvent, an unprecedented fast-curing solventless adhesive can be obtained.

I. The curable resin (A) preferably used in the present invention for the curable resin (A) is selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the above formula (1) in the molecule. The curable resin (A) containing one or more silicon-containing characteristic groups is included.
In the silicon-containing characteristic group in the curable resin (A), the ratio of the silicon-containing characteristic group in which n = 0 in the formula (1) is preferably 10 to 100%, more preferably 20 to 100. %, Particularly preferably 50 to 100%. If it is 10% or less, the effect of synergistically increasing the curability by the cooperative action with the Lewis acid and / or its complex (B) may not be sufficient.
In the above formula (1), X represents a hydroxyl group or a hydrolyzable group. Specific examples of the hydrolyzable group include a halogen group, a hydride group, an alkoxyl group, an acyloxy group, a ketoximate group, an amino group, and an amide group. , Aminooxy group, mercapto group, alkenyloxy group and the like. Among these, an alkoxyl group is most preferable from the viewpoint of high reactivity and low odor.

The curable resin (A) suitably used in the present invention includes a silicon-containing characteristic group consisting of one or more selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the above formula (1). And in the molecule, urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group and tertiary amino group A curable resin (A) having one or more bonds and / or groups (polar element portions) selected from the group consisting of groups is included. In the case of the curable resin (A) having the polar element portion in such a molecule, the value of n in the formula (1) is not particularly limited in the silicon-containing characteristic group in the curable resin (A). .
The polar element part contained in the curable resin (A) includes a urethane bond represented by the following formula (2), a thiourethane bond represented by the following formula (3) to the following formula (5), and the following formula: A urea bond represented by (6), a thiourea bond represented by the following formula (7), a substituted urea bond represented by the following formula (8), a substituted thiourea bond represented by the following formula (9), Amide bond represented by the following formula (10), hydroxyl group represented by the following formula (11), sulfide bond represented by the following formula (12), secondary amino group represented by the following formula (13) And those represented by the tertiary amino group represented by the following formula (14).

但し、Ｙは分子量５００以下の有機基を示す。

Y represents an organic group having a molecular weight of 500 or less.

Furthermore, the urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group and tertiary amino group in the present invention are as follows: Those produced by the reaction of are included.
The urethane bond in the present invention includes a bond formed by a reaction between a hydroxyl group and an isocyanate group. An example of a reaction scheme in which a urethane bond is generated is shown in the following formula (15).

  The thiourethane bond in the present invention is formed by a reaction between a hydroxyl group and an isothiocyanate group (reaction 1), a reaction between a mercapto group and an isocyanate group (reaction 2), or a reaction between a mercapto group and an isothiocyanate group (reaction 3). Contains the bond to generate. In general, the thiourethane group produced by reaction 1 is sometimes called a thiocarbonyl type thiourethane, and the thiourethane group produced by reaction 2 is sometimes called a thioester type thiourethane. Groups produced by 3 are collectively referred to as thiourethane bonds. An example of a reaction scheme in which a thiourethane bond is generated is shown in the following formula (16) to the following formula (18).

The urea bond in the present invention includes a bond formed by a reaction between a primary amino group and an isocyanate group. An example of a reaction scheme in which a urea bond is generated is shown in the following formula (19).

The thiourea bond in the present invention includes a bond formed by a reaction between a primary amino group and an isothiocyanate group. An example of a reaction scheme in which a thiourea bond is generated is shown in the following formula (20).

The substituted urea bond in the present invention includes a bond formed by a reaction between a secondary amino group and an isocyanate group. An example of a reaction scheme in which a substituted urea bond is generated is shown in the following formula (21).

The substituted thiourea bond in the present invention includes a bond formed by a reaction between a secondary amino group and an isothiocyanate group. An example of a reaction scheme for generating a substituted thiourea bond is shown in the following formula (22).

The sulfide bond in the present invention includes a bond formed by a reaction of a mercapto group with an α, β-unsaturated carbonyl compound and / or an acrylonitrile compound or an alkenyl group. An example of a reaction scheme in which a sulfide bond is generated is shown in the following formula (23) and the following formula (24).

The hydroxyl group in the present invention includes a group generated by a reaction between an epoxy group and a primary amino group, secondary amino group, mercapto group, hydroxyl group and / or carboxyl group. An example of a reaction scheme in which a hydroxyl group is generated is shown in the following formula (29) to the following formula (29).

The secondary amino group in the present invention includes a group formed by a reaction between a primary amino group and an equivalent amount of an α, β-unsaturated carbonyl compound and / or an acrylonitrile compound. An example of a reaction scheme for producing a secondary amino group is shown in the following formula (30).

The tertiary amino group in the present invention includes a primary amino group and a group formed by a reaction with an α, β-unsaturated carbonyl compound and / or an acrylonitrile compound in an amount twice as large as the amino group. It is. An example of a reaction scheme for producing a tertiary amino group is shown in the following formula (31).

  The method for introducing the silicon-containing characteristic group into the curable resin (A) is not particularly limited. Specifically, for example, a method of adding a hydrosilane compound to a polymer having an alkenyl terminal (Japanese Patent Publication Nos. 45-36319, 46-12154, 49-32673, JP-A-50-156599, 51-73561, 54-6096, 55-82123, 55-123620, 55-125121, 55-131022, 55-135135, 55-137129, JP 46-12154, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 2512468, Japanese Patent Application Laid-Open No. 64-22904, Japanese Patent Publication No. 2539445, etc.) A method of radically adding a mercaptosilane compound to a polymer (Japanese Patent Laid-Open No. 55-137129), The silicon-containing characteristic group is introduced simultaneously with the polymerization by the method of starting polymerization with one initiator, the method using the chain transfer agent having the silicon-containing characteristic group, and the method using the copolymerizable monomer having the silicon-containing characteristic group. Methods (for example, JP-A-54-123192, JP-A-57-179210, JP-A-59-78220, JP-A-60-23405) and vinyl polymers having an alkenyl group And then introducing the above silicon-containing characteristic groups by hydrosilylation (for example, JP 54-40893, JP 11-80571), reacting an aminosilane compound or the like with a urethane prepolymer. Methods for introducing the above silicon-containing characteristic groups (for example, JP-A Nos. 11-100197, 2000-143757, 2000- No. 69544, JP-A No. 2002-212415, JP-A No. 2004-123900, JP-A No. 2004-123901, Japanese Patent No. 3030020, Japanese Patent No. 3295663, Japanese Patent No. 3313360, Japanese Patent No. 3317353 In addition to known methods such as Japanese Patent Publication No. 3350011), the synthesis method of the curable resin (A) described in the present invention is included.

Polar element part (urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group and tertiary amino group) The method of introducing is not particularly limited. The linking group generated when linking a plurality of raw materials by a chemical reaction may be the polar element part, or the compound containing the polar element part may be linked by a chemical reaction from the beginning. Further, any number of the polar element portions may be included in the curable resin (A).
Although the specific manufacturing method of the said curable resin (A) containing the said silicon-containing characteristic group and the said polar element part is not limited, As a typical example, for example, manufacture of the following curable resin (A) Methods (1) to (6) are included. Hereinafter, each manufacturing method will be described.

"Description of production methods (1) to (6) of the curable resin (A)"
Curable resin (A) (selected from the group consisting of at least one hydrolyzable silyl group and silanol group represented by the above formula (1) in the molecule without containing the polar element part in the molecule) Method for producing a curable resin having a silicon-containing characteristic group composed of one or more groups (1)
For example, a method in which a hydrosilylation reaction is carried out using a hydrosilane moiety of a hydrosilane compound as a catalyst with a group VII transition metal compound (S-5) as an alkenyl group of a polymer whose terminal is alkenylated, such as the following resin (e), and polymerization Radical polymerization of a reactive vinyl monomer and a (meth) acrylsilane compound having a hydrolyzable silyl group such as KBM-503 or KBM-5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). The hydrosilylation reaction may be performed by the following known reaction method (3), and the radical polymerization may be performed by the following known reaction method (4).

Curable resin (A) ( silicon-containing characteristic group consisting of one or more groups selected from the group consisting of at least one hydrolyzable silyl group and silanol group represented by the above formula (1) in the molecule; Production method (2-1) of curable resin having at least one urethane bond and / or thiourethane bond ):
A method of reacting a hydroxyl group in the following resin (a) with an isocyanate group and / or an isothiocyanate group in the following compound group (C), or a hydroxyl group in the following resin (a) and the following compound (z) The functional group capable of reacting with the isocyanate group and the isothiocyanate group in the following compound group (A) with the isocyanate group in the isocyanate group-containing compound (synthetic product (I-z)) reacted with the isocyanate group of Primary amino group, secondary amino group, hydroxyl group and mercapto group), or the hydroxyl group in the following resin (a) and the isocyanate group and / or isothiocyanate in the following compound group (B) An alkenyl group in the alkenyl group-containing compound (synthetic product (I-B)) obtained by reacting the group with the mercapto in the following compound (f) Or a alkenyl group-containing compound obtained by reacting a hydroxyl group in the following resin (A) with an isocyanate group and / or an isothiocyanate group in the following compound group (B) (composite (I- B)) a alkenyl group and a hydrosilane compound (the following compound (g)) are added by a hydrosilylation reaction, or a carboxyl group in the following resin (f) and an isocyanate group in the following compound group (C) and And / or reacting with an isothiocyanate group. The reaction between the following resin (I) and the following compound group (C) may be carried out by the following known reaction method (1). The reaction between the following resin (I) and the following compound (z) and the reaction between the synthesized product (I-z) and the following compound group (A) may be carried out by the known reaction method (1) below. The reaction between the following resin (A) and the following compound group (B) and the reaction between the compound (I-B) and the following compound (f) may be carried out by the known reaction method (2) below. The reaction between the following resin (I) and the following compound group (B) is carried out by the following known reaction method (1). (3) may be performed. The reaction between the following resin (f) and the following compound group (C) may be carried out by the known reaction method (1) below. Depending on the raw materials used, the polar element part (specifically, urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond) may be present in the molecule. , Hydroxyl group, secondary amino group and tertiary amino group) may be contained. When such a compound is used, the polar element portion is introduced into the curable resin (A) in an overlapping manner. May be.

Curable resin (A) ( silicon-containing characteristic group consisting of one or more groups selected from the group consisting of at least one hydrolyzable silyl group and silanol group represented by the above formula (1) in the molecule; Production method (2-2) of curable resin having at least one thiourethane bond :
A method of reacting a mercapto group in the following resin (b) with an isocyanate group and / or an isothiocyanate group in the following compound group (C), or a mercapto group in the following resin (b) and the following compound (z) The functional group capable of reacting with the isocyanate group and the isothiocyanate group in the following compound group (A) with the isocyanate group in the isocyanate group-containing compound (synthetic product (roz)) reacted with the isocyanate group of A primary amino group, a secondary amino group, a hydroxyl group and a mercapto group), or a mercapto group in the following resin (b) and an isocyanate group and / or iso group in the following compound group (B). An alkenyl group in an alkenyl group-containing compound obtained by reacting with a thiocyanate group (synthetic product (B)) and a mercapto group in the following compound (f) In a compound containing alkenyl group obtained by reacting a mercapto group in the following resin (b) with an isocyanate group and / or an isothiocyanate group in the following compound group (B) (synthetic product (b)) Or a hydrosilane compound (the following compound (g)) is added by a hydrosilylation reaction, or an alkenyl group in the following resin (e) and a primary amino group in the following compound (v) and / or Alternatively, a method of reacting a mercapto group in a mercapto group-containing compound (synthetic product (v-C)) obtained by reacting a secondary amino group with an isocyanate group and / or an isothiocyanate group in the following compound group (C) . The reaction between the following resin (B) and the following compound group (C) may be carried out by the known reaction method (1) below. The reaction between the following resin (b) and the following compound (z) and the reaction between the synthesized product (roz) and the following compound group (A) may be carried out by the known reaction method (1) below. The reaction between the following resin (b) and the following compound group (B) is carried out by the following known reaction method (1), and the reaction between the compound (b) and the following compound (f) is carried out by the following known reaction method (2). ). The reaction between the following resin (B) and the following compound group (B) is carried out by the following known reaction method (1), and the hydrosilylation reaction between the compound (B) and the following compound (g) is carried out by the following known reaction method. (3) may be performed. The reaction between the following compound (v) and the following compound group (C) is carried out by the following known reaction method (1), and the reaction between the following resin (e) and the compound (vC) is carried out by the following known reaction method (2). ). Depending on the raw materials used, the polar element part (specifically, urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond) may be present in the molecule. , Hydroxyl group, secondary amino group and tertiary amino group) may be contained. When such a compound is used, the polar element portion is introduced into the curable resin (A) in an overlapping manner. May be.

Curable resin (A) ( silicon-containing characteristic group consisting of one or more groups selected from the group consisting of at least one hydrolyzable silyl group and silanol group represented by the above formula (1) in the molecule; Curable resin having at least one urea bond, thiourea bond, substituted urea bond or substituted thiourea bond ) (3):
A method of reacting a primary amino group and / or a secondary amino group in the following resin (C) with an isocyanate group and / or an isothiocyanate group in the following compound group (C); An isocyanate group in an isocyanate group-containing compound (composite (haz)) obtained by reacting a primary amino group and / or a secondary amino group in) with an isocyanate group in the following compound (z); A method of reacting a functional group (for example, a primary amino group, a secondary amino group, a hydroxyl group and a mercapto group) capable of reacting with an isocyanate group and an isothiocyanate group in the following compound group (A); Including alkenyl group obtained by reacting primary amino group and / or secondary amino group in resin (c) with isocyanate group and / or isothiocyanate group in compound group (B) below A method of reacting an alkenyl group in the compound (synthesized product (ha-B)) with a mercapto group in the following compound (f), or a primary amino group and / or a second compound in the following resin (ha) The alkenyl group in the alkenyl group-containing compound obtained by reacting the isocyanate group and / or the isothiocyanate group in the following compound group (B) (the synthesized product (HA-B)) and the hydrosilane compound (the following compound ( g)) by a hydrosilylation reaction, or an alkenyl group in the following resin (e), a primary amino group and / or a secondary amino group in the following compound (w) and the following compound group ( A method of reacting a mercapto group of a mercapto group-containing compound (composite (wC)) obtained by reacting the isocyanate group and / or isothiocyanate group in C). The reaction between the following resin (C) and the following compound group (C) may be carried out by the known reaction method (1) below. The reaction between the following resin (C) and the following compound (z) and the reaction between the compound (HA) and the following compound group (A) may be carried out by the known reaction method (1) below. The reaction between the following resin (C) and the following compound group (B) is carried out by the following known reaction method (1), and the reaction between the compound (C) and the following compound (f) is carried out by the following known reaction method (2). ). The reaction between the following resin (C) and the following compound group (B) is performed by the following known reaction method (1), and the hydrosilylation reaction between the compound (C) and the following compound (g) is performed by the following known reaction method (3) may be performed. The reaction between the following compound (w) and the following compound group (C) is carried out by the following known reaction method (1), and the reaction between the following resin (e) and the synthesized product (w-C) is carried out by the following known reaction method (2). ). Depending on the raw materials used, the polar element part (specifically, urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond) may be present in the molecule. , Hydroxyl group, secondary amino group and tertiary amino group) may be contained. When such a compound is used, the polar element portion is introduced into the curable resin (A) in an overlapping manner. May be.

Curable resin (A) ( silicon-containing characteristic group consisting of one or more groups selected from the group consisting of at least one hydrolyzable silyl group and silanol group represented by the above formula (1) in the molecule; Method (4) for producing a curable resin having at least one hydroxyl group :
A method of reacting a mercapto group in the following resin (b) with an epoxy group in the following compound (h), or an alkenyl group in the following resin (e), a mercapto group in the following compound (v) and the following compound A method of reacting a mercapto group in a mercapto group-containing compound (synthetic product (vh)) obtained by reacting with an epoxy group in (h), or a primary amino group in the resin (c) and / or Or a method of reacting a secondary amino group with an epoxy group in the following compound (h), or an epoxy group in the following resin (d) and a primary amino group in the following compound group (E); A method of reacting with a primary amino group and / or a mercapto group, or a hydroxyl group in the following resin (a), a mercapto group in the following resin (b) and a primary amino group in the following resin (c) and / or Or a secondary amino group and the following compound (z) Isocyanate group-containing compounds (synthetic products (I-z), synthetic products (RO-z) and synthetic products (HA-Z)) obtained by reacting with the isocyanate groups of the above, and epoxy in the following compound (u) A hydroxyl group in a hydroxyl group-containing compound (synthetic product (u-E)) obtained by reacting a group with a primary amino group, a secondary amino group and / or a mercapto group in the following compound group (E). Method of reacting, or mercapto group in the following resin (b), epoxy group in the following compound (s), and primary amino group, secondary amino group and / or mercapto in the following compound group (E) A method of reacting an alkenyl group in an alkenyl group-containing compound (synthetic product (s-E)) reacted with a group, or a carboxyl group in the following resin (f) and an epoxy group in the following compound (h) Who react with . What is necessary is just to perform reaction with the following resin (b) and the following compound (h) by the well-known following reaction method (1). The reaction between the following compound (v) and the following compound (h) is carried out by the following known reaction method (1), and the reaction between the following resin (e) and the compound (vh) is carried out by the following known reaction method (2). Can be done. The reaction between the resin (c) and the compound (h) may be carried out by the known reaction method (1) below. The reaction between the following resin (d) and the following compound group (E) may be carried out by the known reaction method (1) below. Reaction of the following resin (a), the following resin (b) and the following resin (c) with the following compound (z), reaction between the following compound (u) and the following compound group (E), and a synthetic product ( The reaction between (i-z), the compound (ro-z), and the compound (ha-z) and the compound (u-E) may be carried out by the following reaction method (1). The reaction between the following compound (s) and the following compound group (E) is carried out by the following known reaction method (1), and the reaction between the following resin (b) and the compound (s-E) is carried out by the following known reaction method (2). ). The reaction between the following resin (f) and the following compound (h) may be carried out by the known reaction method (1) below. Depending on the raw materials used, the polar element part (specifically, urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond) may be present in the molecule. , Hydroxyl group, secondary amino group and tertiary amino group) may be contained. When such a compound is used, the polar element portion is introduced into the curable resin (A) in an overlapping manner. May be.

Curable resin (A) ( silicon-containing characteristic group consisting of one or more groups selected from the group consisting of at least one hydrolyzable silyl group and silanol group represented by the above formula (1) in the molecule; One or more selected from the group consisting of urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group or tertiary amino group Curable resin having a bond or group of (5):
A method of reacting a mercapto group in the following resin (b) with an α, β-unsaturated carbonyl group of a silane compound containing an acryloxy group such as the following compound (i) and / or γ-acryloxypropyltrimethoxysilane, or , A method of reacting a mercapto group in the following resin (b) with an alkenyl group in the following compound (j), or an alkenyl group in the following resin (e) and a mercapto group in the following compound (v) A method of reacting a mercapto group in a mercapto group-containing compound (synthetic product (vi)) obtained by reacting an α, β-unsaturated carbonyl group in compound (i), or in the following resin (e) And a mercapto group in a mercapto group-containing compound (synthesis (vj)) obtained by reacting a mercapto group of the following compound (v) with an alkenyl group in the following compound (j) Or a method of reacting the primary amino group and / or secondary amino group in the following resin (C) with the α, β-unsaturated carbonyl group in the compound (i), or the following resin A method of reacting an α, β-unsaturated carbonyl group in (g) with a primary amino group, secondary amino group and / or mercapto group in the following compound group (E), or the following resin (f) And a primary amino group and / or a secondary amino group in the following compound (c). The reaction between the following resin (b) and the following compound (i) may be carried out by the known reaction method (1) below. The reaction between the following resin (b) and the following compound (j) may be carried out by the known reaction method (2) below. The reaction between the following compound (v) and the following compound (i) is carried out by the following known reaction method (1), and the reaction between the following resin (e) and the synthesized product (vi) is carried out by the following known reaction method (2). It may be performed by. The reaction between the following compound (v) and the following compound (j) and the reaction between the following resin (e) and the synthesized product (vj) may be carried out by the known reaction method (2) below. The reaction between the following resin (C) and compound (i) may be carried out by the known reaction method (1) below. The reaction between the following resin (g) and the following compound group (E) may be carried out by the known reaction method (1) below. The reaction between the resin (f) and the following compound (c) may be carried out by the known reaction method (1) below.

Curable resin (A) ( containing at least one group selected from the group consisting of hydrolyzable silyl group and silanol group represented by the above formula (1) in the molecule, the molecular chain of which is a vinyl polymer) Silicon characteristic group and at least one urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group or tertiary Production method (6) of a curable resin having one or more bonds or groups selected from the group of amino groups :
As a polymerizable monomer, at least one urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group in the molecule or Polymerizable alkenyl compound (P-1) having a tertiary amino group (including the following compound (i) and the following compound (j)) and / or at least one silicon-containing characteristic group in the molecule and at least Polymerization having one urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group or tertiary amino group Using an alkenyl compound (P-2) as a chain transfer agent, at least one silicon-containing characteristic group and at least one urethane in the molecule Thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group or tertiary amino group and at least one mercapto group Compound (T-1) (including compound (f)) and / or at least one urethane bond, thiourethane bond, urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide in the molecule A method of copolymerizing a compound (T-2) having a bond, sulfide bond, hydroxyl group, secondary amino group or tertiary amino group and at least one mercapto group. Furthermore, you may copolymerize with other polymeric alkenyl compounds (For example, the following compound (t), the following compound (i), the following compound (j), etc.). However, when the polymerization component is only the compound (P-1) and / or the compound (T-2), the polymerizable compound having the silicon-containing characteristic group is used as another polymerizable alkenyl compound, or a chain is used. It is necessary to use a chain transfer agent having the above silicon-containing characteristic group as a transfer agent. The polymerization reaction may be performed by the following reaction method (4).

In addition, “resins (a) to (g)” , “compounds (a) to (z)” , “ a ” and “compounds (a) to (z)” used in the above “ explanation of the production methods (1) to (6) of the curable resin (A) ” For the “compound groups (A) to (E)” and “reaction methods (1) to (4)” , the following paragraph numbers [0054] to [0074] , [0075] to [0198] , [0199] to [0201] and [0202] to [0204].
"Description of the above resins (I) to (G)"
The resin (A) represents a resin having at least one hydroxyl group in the molecule.
The resin (b) is a resin having at least one mercapto group in the molecule.
The resin (C) represents a resin having at least one primary amino group and / or secondary amino group in the molecule.
The resin (d) indicates a resin having at least one epoxy group in the molecule.
The resin (e) is a resin having at least one alkenyl group in the molecule.
The resin (f) is a resin having at least one carboxyl group in the molecule.
The resin (g) represents a resin having at least one α, β-unsaturated carbonyl group in the molecule.

The main chain skeletons of the resin (b), the resin (b), the resin (c), the resin (d), the resin (e), the resin (f), and the resin (g) are not particularly limited. , Preferably polyoxyalkylene, saturated hydrocarbon polymer, vinyl polymer (for example, acrylic monomer copolymer), polyester and polycarbonate, more preferably polyoxyalkylene, saturated hydrocarbon polymer and vinyl. Polymers, more preferably polyoxyalkylene and vinyl polymers.
Polyoxyalkylene serving as a main chain skeleton of the resin (b), the resin (b), the resin (c), the resin (d), the resin (e), the resin (f), and the resin (g) As the polymer, those produced by reacting a monoepoxide or the like with an initiator in the presence of a catalyst are preferable. As the initiator, a hydroxy compound having one or more hydroxyl groups can be used.

As the monoepoxide, ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, tetrahydrofuran, or the like can be used in combination.
Examples of the catalyst include, but are not limited to, alkali metal catalysts such as potassium compounds and cesium compounds, complex metal cyanide complex catalysts, and metal porphyrin catalysts. The complex metal cyanide complex catalyst is preferably a complex mainly composed of zinc hexacyanocobaltate, an ether and / or alcohol complex. As the composition of the ether and / or alcohol complex, those essentially described in JP-B-46-27250 can be used. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable from the viewpoint of handling at the time of producing the complex. As the alcohol, for example, those described in JP-A-4-145123 can be used, and tert-butanol is particularly preferable.

  The raw material polyoxyalkylene polymer preferably has 2 or more functional groups, and specific examples include copolymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene. It is done. Preferred raw material polyoxyalkylene polymers are di- to hexavalent polyoxypropylene polyols, particularly polyoxypropylene diol and polyoxypropylene triol. Furthermore, a polyoxyalkylene polymer containing an amino group in the molecule can also be used.

  Hydrocarbons that serve as the main chain skeleton of the resin (b), the resin (b), the resin (c), the resin (d), the resin (e), the resin (f), and the resin (g) Examples of the polymer include polymers having 1 to 6 carbon monoolefins such as ethylene, propylene, 1-butene, isobutene and 1-hexene as main monomers, homopolymers of diolefins such as butadiene and isoprene, and the like. Examples thereof include a hydrogenated product of a copolymer of a diolefin and the above monoolefin. Among these hydrocarbon polymers, polymers with isobutene as the main monomer and hydrogenated products of butadiene polymers are easy to introduce functional groups at the terminals and adjust the molecular weight. Can be increased, which is preferable.

The polymer containing isobutene as the main monomer is a copolymer containing 50% by weight or less, preferably 30% by weight or less, more preferably 10% by weight or less of a monomer copolymerizable with isobutene in addition to a homopolymer of isobutene. Can also be used.
Examples of monomers that can be copolymerized with isobutene include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes. Examples of such monomers include 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and vinyl. Examples include cyclohexene, methyl vinyl ether, ethyl vinyl ether, isobutyl vinyl ether, styrene, α-methyl styrene, divinyl styrene, vinyl trimethoxy silane, vinyl triethoxy silane, allylaminotrimethyl silane, and allyl dimethoxy silane.

Vinyl polymer that is the main chain skeleton of the resin (b), the resin (b), the resin (c), the resin (d), the resin (e), the resin (f), and the resin (g) Examples of the polymer include a polymer of a compound having at least one polymerizable alkenyl group in the molecule. The reaction of polymerizing a compound having at least one polymerizable alkenyl group in the molecule to form the main chain skeleton of the vinyl polymer may be carried out by the following reaction method (4).
Examples of the polyester as the main chain skeleton of the resin (b), the resin (b), the resin (c), the resin (d), the resin (e), the resin (f), and the resin (g) Although what was synthesize | combined by the method of Unexamined-Japanese-Patent No. 2003-193019 can be used, it is not limited to these.

As the resin (b), the resin (b), the resin (c), the resin (d), the resin (e), the resin (f), and the polycarbonate serving as the main chain skeleton of the resin (g) Although synthesized by the method described in JP-A No. 2002-356550, JP-A No. 2002-179787, etc. can be used, it is not limited to these.
The molecular weights of the main chain skeletons of the resin (b), the resin (b), the resin (c), the resin (d), the resin (e), the resin (f), and the resin (g) are particularly limited. However, the number average molecular weight is preferably 500 to 30,000, and particularly preferably 2,000 to 20,000.

The above resins (A) are commercially available and can be used in the present invention. As a commercially available product, for example, as a polyether polyol, Asahi Denka Kogyo Co., Ltd. trade name; P-2000, P-3000, PR3007, PR5007, Asahi Glass Co., Ltd. trade name; PML-3005, PML-3010, PML-3012 , PML-4002, PML-4010, PML-S-4011, PML-S-4012, PML-5005 and other preminol series, Sumika Bayer Urethane, Inc. trade names; Product names manufactured by Chemical Co., Ltd .; P-28, P-21, etc .; product names manufactured by Daicel Chemical Industries; PTMG-1000, PTMG-2000, PTMG-3000, etc., polyolefin polyols, product names manufactured by Nippon Soda Co., Ltd .; GI- 1000, GI-200 Etc., Mitsubishi Chemical Co., Ltd .; Polytail H, Polytail HA, etc. As acrylic polyols, Otake Akira Shin Chemical Co., Ltd., APO series, Toagosei Co., Ltd., UH-2000 etc. UH series, UC As the -3000 series and polyester polyol, trade names manufactured by Degussa Japan; DYNACOLL7000 series, etc .; trade names manufactured by Asahi Denka Kogyo; F18-62, F7-67, Y9-10, Y4-5, Y13-35, F9 -30, Y6-10, Y6-22, Y52-13, NS2400, NS2700, etc., trade names made by Ito Oil; URIC series such as URICH-30, trade names made by Daicel Chemical Industries; As a polycarbonate polyol, a product made by Daicel Chemical Industries, Ltd. Plaxel CD220 and the like, Asahi Kasei Finechem brand name; CX series and the like; Arakawa Chemical Industries brand name; Rosin polyol, Kyowa Hakko Kogyo brand name; TOE-2000H, Kyowapol PA and the like However, it is not limited to these.
In addition, the resin (a) is a method of copolymerizing with a compound having at least one hydroxyl group and at least one polymerizable alkenyl group and / or other polymerizable alkenyl monomer in the molecule, and at least one in the molecule. It can also be synthesized by a method of copolymerizing a compound having one hydroxyl group and at least one mercapto group and a polymerizable alkenyl monomer. The polymerization reaction may be performed by the following reaction method (4).

The above resins (b) are commercially available and can be used in the present invention. Examples of the commercially available products include, but are not limited to, product names manufactured by Toray Rethiol Co .; thiocol LP-32, thiocol LP-3, thiocol LP-33, thiocol LP-2, and the like.
The resin (b) can also be synthesized from the resin (e) having at least one alkenyl group in the molecule. As a synthesis method for converting the resin (e) to the resin (c), the polymer capto compound (the following compound (v)) having at least two mercapto groups in the molecule is added to the resin (e). A method of adding a radical is mentioned. The radical addition reaction may be performed by the following reaction method (2).

The above resins (c) are commercially available and can be used in the present invention. Commercially available products include, for example, trade names manufactured by Sun Techno Japan Co .; Jeffamine D-230, D-400, D-200 and the like as polyoxypropylene having a primary amino group at the terminal, but are not limited thereto. Is not to be done.
The resin (c) is a compound having at least one primary amino group and / or secondary amino group and at least one polymerizable alkenyl group in the molecule, and / or other polymerizable compounds. A method of copolymerizing with an alkenyl monomer, a compound having at least one primary amino group and / or a secondary amino group and at least one mercapto group in the molecule, and a method of copolymerizing a polymerizable alkenyl monomer Can also be synthesized. The polymerization reaction may be performed by the following reaction method (4).

The resin having a secondary amino group in the resin (c) can be synthesized from the resin having a primary amino group in the resin (c). A method for synthesizing a resin having a secondary amino group in the resin (c) includes a resin having a primary amino group in the resin (c) and an α, β-unsaturated carbonyl compound (the following compound). (L)) and the method of making it react with 1 type, or 2 or more types chosen from an acrylonitrile type compound (following compound (l-1)). The reaction may be performed by the following reaction method (1).
The resin (c) can be synthesized from the resin (e) having at least one alkenyl group in the molecule. As a synthesis method for converting the resin (e) to the resin (b), the resin (e) may contain at least one mercapto group and at least one primary amino group and / or second in the molecule. Examples include a method of radically adding a compound having a secondary amino group (the following compound (w)). The radical addition reaction may be performed by the following reaction method (2).

The above resins (d) are commercially available and can be used in the present invention. Commercially available products include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, other epoxy resins, trade names manufactured by Daicel Chemical Industries; Celoxide 2021, Celoxide 2080, Celoxide 3000, Epolide GT300, Epolide GT400, EHPE, etc. Asahi Denka Kogyo Co., Ltd. trade names: Adeka Resin EP4005, Adeka Resin EP4006, Adeka Resin EP4000, Adeka Resin EP4100, Adeka Resin EP4080, etc .; Kyoeisha Chemicals Co., Ltd. trade names; 400P, Epolite 1500NP, Epolite 1600, Epolite 80MF, Epolite 100MF, Eporai 4000, Epolite 3002, Epolite FR-1500, etc., trade names manufactured by Japan Epoxy Resins; Epicoat series such as Epicoat 828, Epicoat 807, etc .; Trade names made by Toagosei Co., Ltd .; UG-4000 series are limited to these. It is not something.
The resin (d) can also be synthesized from the resin (b), the resin (b), and the resin (c). As a synthesis method for converting the resin (b), the resin (b), and the resin (c) to the resin (d), the following synthesis methods (1) and (2), or JP-A-9-132737 The following synthesis methods (3) to (5) described below are included.

Synthesis method (1) of the resin (d):
An isocyanate group-containing compound (synthesis) by reacting the resin (b), the resin (b) and the resin (c) with a polyisocyanate compound having at least two isocyanate groups in the molecule (the following compound (z)). Compound (i-u), compound (ro) and compound (ha)), and compound (u), compound (ro) and compound (ha) And the following compound (u) having at least one hydroxyl group and at least one epoxy group in the molecule. The reaction of the resin (b), the resin (b) and the resin (c) with the following compound (z) may be carried out by the following reaction method (1). Moreover, the reaction of the compound (u), the compound (ro) and the compound (ha) with the following compound (u) may be carried out by the following reaction method (1).

Synthesis method (2) of the above resin (d):
A method of radically adding a polymerizable alkenyl compound having at least one polymerizable alkenyl group and an epoxy group in the molecule (the following compound (s)) to the resin (b). The radical addition reaction may be performed by the following reaction method (2).
Synthesis method (3) of the above resin (d):
A conventional method in which the resin (i) is reacted with epihalohydrin in the presence of a basic compound such as sodium hydroxide.
Synthesis method (4) of the resin (d):
A conventional method of synthesizing a polyhalohydrin ether compound by reacting the resin (i) with epihalohydrin in the presence of an acidic compound such as boron trifluoride, and then reacting a basic compound such as sodium hydroxide.

Synthesis method (5) of the resin (d):
A conventional method in which a polyhalohydrin ether compound is synthesized by reacting the resin (i) with epihalohydrin in the presence of a basic compound such as triethylamine, and then a basic compound such as sodium hydroxide is allowed to act.
Furthermore, the resin (d) can also be synthesized by a method of copolymerizing with a compound having at least one epoxy group and at least one polymerizable alkenyl group in the molecule and / or other polymerizable alkenyl monomer. . The polymerization reaction may be performed by the following reaction method (4).

  The above resins (e) are commercially available, and they can be used in the present invention. As a commercial item, Asahi Denka Kogyo Co., Ltd. brand name; LX-1164, ARA-200, ARA-4000 etc. are mentioned, for example, It is not limited to these. The resin (e) can also be synthesized from the resin (a) having at least one hydroxyl group in the molecule. Synthetic methods for converting the resin (a) to the resin (e) are known. For example, the hydroxyl group of the resin (a) is sodium alkoxided with metal sodium or the like, and then an alkenyl group such as allyl chloride or the like is converted. Examples thereof include a method of reacting a halide or the like, but is not limited thereto.

  The resin (e) includes the resin (b) having at least one mercapto group in the molecule and the resin having at least one primary amino group and / or secondary amino group in the molecule. It can also be synthesized from (c). Examples of the synthesis method for converting the resin (b) and the resin (c) to the resin (e) include, for example, a mercapto group in the resin (b) and a primary amino group in the resin (c) and A method of reacting a secondary amino group with an epoxy group in the following compound (s) is included. The reaction of the resin (b) and the resin (c) with the following compound (s) may be carried out by the following reaction method (1).

The above resins (f) are commercially available, and they can be used in the present invention. As a commercial item, Daicel Chemical Industries Ltd. brand name; Plaxel 200BA etc. are mentioned, for example.
The resin (f) can also be synthesized by a method of copolymerizing a compound having at least one carboxyl group and at least one polymerizable alkenyl group in the molecule and / or other polymerizable alkenyl monomer. . The polymerization reaction may be performed by the following reaction method (4).

  The above resins (g) are commercially available, and they can be used in the present invention. As a commercial item, for example, Toagosei Co., Ltd. trade name; UVA-2000 series, Kyoeisha Chemical Co., Ltd. trade name; light ester EG, light ester 2EG, light ester 3EG, light ester 4EG, light ester 9EG, light ester 14EG, Light ester NP, Light ester 1 / 3BG, Light ester 1 / 4BG, Light ester 1 / 6HX, Light ester 1-9ND, Light ester 1 / 10DC, Light ester TMP, Light ester G-101P, Light ester G-201P, Light ester BP-2EM, Light acrylate 3EG-A, Light acrylate 4EG-A, Light acrylate 9EG-A, Light acrylate 14EG-A, Light acrylate NP-A, Light acrylate 1.6HX-A, Light acrylate 1.9 ND-A, light acrylate DCP-A, light acrylate BP-4EA, light acrylate BP-4PA, light acrylate TMP-A, light acrylate TMP-6EO-3A, light acrylate PE-3A, light acrylate PE- 4A, light acrylate DPE-6A, light acrylate BA-104, light acrylate BA-134, light ester G-201P, light acrylate HPP-A, light acrylate PTMGA-250, light acrylate TMP-3EO-A, epoxy ester 40EM, Epoxy ester 70PA, Epoxy ester 200PA, Epoxy ester 80MFA, Epoxy ester 3002M, Epoxy ester 3002A, Epoxy Este 1600A, epoxy ester 3000M, epoxy ester 3000A, epoxy ester 200EA, epoxy ester 400EA, AH-600, AT-6000, UA-306H, AI-600, UA-101T, UA-101I, UA-306T, UA-306I, etc. However, it is not limited to these.

  The resin (g) includes the resin (b) having at least one hydroxyl group in the molecule, the resin (b) having at least one mercapto group in the molecule, and a primary amino group in the molecule. It can also be synthesized from the above resin (c) having at least one group and / or secondary amino group. As the synthesis method, the hydroxyl group in the resin (a) having at least one hydroxyl group in the molecule, the mercapto group in the resin (b) having at least one mercapto group in the molecule, and the molecule The primary amino group and / or secondary amino group of the above resin (c) having at least one primary amino group and / or secondary amino group in the above, such as acrylic acid chloride or methacrylic acid chloride Although the method of making the acid chloride which has at least 1 or more (alpha), (beta)-unsaturated carbonyl group in a molecule | numerator act is mentioned, it is not limited to these.

“Description of the above compounds (a) to (z)”
The compound (a) represents an isocyanate silane compound having at least one silicon-containing characteristic group and at least one isocyanate group in the molecule.
The compound (b) represents an isothiocyanate silane compound having at least one silicon-containing characteristic group and at least one isothiocyanate group in the molecule.
The compound (c) represents an aminosilane compound having in the molecule at least one silicon-containing characteristic group, at least one primary amino group and / or at least one secondary amino group.
The compound (d) represents a hydroxysilane compound having at least one silicon-containing characteristic group and at least one hydroxyl group in the molecule.
The compound (e) is a compound having at least one silicon-containing characteristic group and at least one mercapto group in the molecule, and has a protonic polar group other than the silicon-containing characteristic group and mercapto group in the molecule. The mercaptosilane compound which does not have is shown.

The compound (f) represents a mercaptosilane compound having at least one silicon-containing characteristic group and at least one mercapto group in the molecule.
The compound (g) represents a hydrosilane compound in which a hydrogen atom is bonded directly to a silicon atom.
The compound (h) represents an epoxysilane compound having at least one silicon-containing characteristic group and at least one epoxy group in the molecule.
The compound (i) represents an α, β-unsaturated carbonylsilane compound having at least one silicon-containing characteristic group and at least one α, β-unsaturated carbonyl group in the molecule.
The compound (j) represents an alkenylsilane compound having at least one silicon-containing characteristic group and at least one alkenyl group in the molecule.

The compound (k-1) represents an aminosilane compound having at least one silicon-containing characteristic group and at least one primary amino group in the molecule.
The compound (k-2) represents an aminosilane compound having at least one silicon-containing characteristic group, at least one primary amino group, and at least one secondary amino group in the molecule.
The compound (l) represents an α, β-unsaturated carbonyl compound having at least one α, β-unsaturated carbonyl group in the molecule.
The compound (l-1) represents an acrylonitrile compound.
The compound (m) represents an isocyanate compound having at least one isocyanate group in the molecule.
The compound (n-1) represents an amine compound having at least one primary amino group in the molecule.
The compound (n-2) represents an amine compound having at least one secondary amino group in the molecule.

The compound (o) represents a thiol compound having at least one mercapto group in the molecule.
The compound (p) represents an epoxy compound having at least one epoxy group in the molecule.
The compound (q) represents a hydroxyl group-containing α, β-unsaturated carbonyl compound having at least one hydroxyl group and at least one α, β-unsaturated carbonyl group in the molecule.
The compound (s) is a polymerizable alkenyl compound having at least one polymerizable alkenyl group and an epoxy group in the molecule.
The compound (t) represents a polymerizable alkenyl compound having at least one polymerizable alkenyl group in the molecule.
The compound (u) represents a glycidol-based compound having at least one hydroxyl group and at least one epoxy group in the molecule.

The compound (v) represents a polymercapto compound having at least two mercapto groups in the molecule.
The compound (w) represents an aminothiol compound having at least one amino group and at least one mercapto group in the molecule.
The compound (x) represents an alkenyl isothiocyanate compound having at least one alkenyl group and at least one isothiocyanate group in the molecule.
The compound (y) represents an alkenyl isocyanate compound having at least one alkenyl group and at least one isocyanate group in the molecule.
The compound (z) represents a polyisocyanate compound having at least two isocyanate groups in the molecule.

但し、Ｒ¹、Ｘ、ｎは上記と同意義であり、Ｒ³は分子量１，０００以下の二価の有機基を示す。 Hereinafter, the compound (a) to the compound (z) will be described in detail.
The compound (a) is a compound having at least one silicon-containing characteristic group and at least one isocyanate group in the molecule, and includes a compound represented by the following formula (32).

However, R ^1, X, n are as defined above, R ³ represents a molecular weight of 1,000 or less divalent organic group.

Specific examples of the compound (a) include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatepropyltrimethoxysilane. Examples include, but are not limited to, silane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatopropyltriethoxysilane.
Moreover, the compound (a) is commercially available and can be used in the present invention. Examples of commercially available products include, but are not limited to, trade names manufactured by Shin-Etsu Chemical Co., Ltd .; KBE-9007, KBE-9207, trade names manufactured by Nippon Unicar Co., Ltd .; Y-5187, A-1310, and the like.

但し、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義である。
上記化合物（ｂ）は公知の方法により合成することができる。例えば、γ−イソシアネートプロピルトリエトキシシランの合成は、Org. Prep. Proced. Int., 24, 346 (1995)等に記載の方法を用いることができる。 The compound (b) is a compound having at least one silicon-containing characteristic group and at least one isothiocyanate group in the molecule, and includes a compound represented by the following formula (33).

However, R ¹ , R ³ , X, and n are as defined above.
The compound (b) can be synthesized by a known method. For example, the method described in Org. Prep. Proced. Int., 24, 346 (1995) can be used for the synthesis of γ-isocyanatopropyltriethoxysilane.

但し、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義であり、Ｒ²は水素原子又は分子量１，０００以下の有機基を、Ｒ⁴は水素原子又は式−ＣＯＯＲ¹⁵で示される基（Ｒ¹⁵は水素原子又は分子量１，０００以下の有機基を示す。）又は分子量１，０００以下の有機基を、Ｒ⁵は水素原子又は分子量１，０００以下の有機基を、Ｒ⁶は水素原子、ＯＲ¹⁶、Ｒ¹⁶又はＮＨ₂ であり、Ｒ¹⁶は水素原子または上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基をそれぞれ示す。
The compound (c) is a compound having at least one silicon-containing characteristic group and at least one amino group in the molecule, and is represented by the following formula (34) to the following formula (40) and the following formula (45). The compounds represented are included.

Wherein R ¹ , R ³ , X and n are as defined above, R ² is a hydrogen atom or an organic group having a molecular weight of 1,000 or less, R ⁴ is a hydrogen atom or a group represented by the formula —COOR ¹⁵ ( R ¹⁵ represents a hydrogen atom or an organic group having a molecular weight of 1,000 or less.) Or an organic group having a molecular weight of 1,000 or less, R ⁵ represents a hydrogen atom or an organic group having a molecular weight of 1,000 or less, and R ⁶ represents a hydrogen atom. OR ¹⁶ , R ¹⁶ or NH ₂ , wherein R ¹⁶ represents a hydrogen atom or an organic group having a molecular weight of 1,000 or less, which may contain the above silicon-containing characteristic group.

但し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｘ、ｎは上記と同意義である。 The compound represented by the above formula (34) can be synthesized by the following method. As the synthesis method, an amino group of an aminosilane compound (k-1) represented by the following formula 121 and an α, β-unsaturated carbonyl compound (compound (l)) represented by the following formula (123): Examples include a method of reacting with a β-unsaturated carbonyl group. The reaction may be performed by the following reaction method (1).

However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , X, n are as defined above.

但し、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義であり、Ｒ⁷はフェニル基、シクロヘキシル基又は炭素数１〜２０の有機基を示す。 The compound represented by the above formula (35) can be synthesized by the following method. As the synthesis method, an amino group in an aminosilane compound (k-1) represented by the following formula 121 and α, β in an acrylonitrile-based compound (compound (l-1)) represented by the following formula (125) -The method of making it react with an unsaturated carbonyl group is mentioned. The reaction may be performed by the following reaction method (1).

^{However, R 1, R 3, X} , n are as defined above, R ⁷ represents a phenyl group, a cyclohexyl group or an organic group having 1 to 20 carbon atoms.

但し、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義であり、Ｒ⁸は上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基を示す。 The compound represented by the above formula (36) can be synthesized by the following method. As a synthesis method thereof, the amino group of the aminosilane compound (k-1) represented by the following formula (121) and the following formula (124) contained in the α, β-unsaturated carbonyl compound (compound (l)) And a method of reacting the α, β-unsaturated carbonyl group of the maleimide compound represented by the formula: The reaction may be performed by the following reaction method (1).

However, R ¹ , R ³ , X, and n are as defined above, and R ⁸ represents an organic group having a molecular weight of 1,000 or less that may contain the silicon-containing characteristic group.

但し、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義であり、Ｒ⁹は水素原子、フェニル基、炭素数１〜２０個の有機基又は上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基を示す。 The compound represented by the above formula (37) can be synthesized by the following method. As the synthesis method, the amino group of the aminosilane compound (k-1) represented by the following formula (121) is reacted with the isocyanate group of the monoisocyanate compound (compound (m)) represented by the following formula (126). The method of letting it be mentioned. The reaction may be performed by the following reaction method (1).

However, R ¹ , R ³ , X, and n are as defined above, and R ⁹ is a molecular weight that may contain a hydrogen atom, a phenyl group, an organic group having 1 to 20 carbon atoms, or the above silicon-containing characteristic group. 1,000 or less organic groups are shown.

但し、Ｒ²、Ｒ⁴、Ｒ⁵及びＲ⁶は、上記と同意義である。 R ¹ , R ³ , X and n are as defined above, R ¹⁰ is an organic group having a molecular weight of 1,000 or less, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen atoms or the following formulae Groups represented by (41), formula (42), formula (43) or formula (44) are shown respectively. Furthermore, when R ¹³ is the following formula (41), R ¹⁴ is the following formula (41), the following formula (42), the following formula (43) or the following formula (44), and when R ¹³ is the following formula (42). When the following formula (42), the following formula (43) or the following formula (44), R ¹³ is the following formula (43), when the following formula (43) or the following formula (44), R ¹³ is the following formula (44) Each represents a hydrogen atom.

However, R ² , R ⁴ , R ⁵ and R ⁶ are as defined above.

但し、Ｒ²、Ｒ⁴及びＲ⁵は、上記と同意義である。

但し、Ｒ⁷は上記と同意義である。

However, R ² , R ⁴ and R ⁵ are as defined above.

However, R ⁷ has the same meaning as above.

但し、Ｒ⁸は上記と同意義である。
上記式（３８）〜上記式（４０）で表される化合物は、以下の方法で合成することができる。その合成方法としては、下記式（１２２）で表されるアミノシラン化合物（ｋ−２）と下記式（１２３）及び下記式（１２４）で表されるα，β−不飽和カルボニル化合物（化合物（ｌ））、下記式（１２５）で表されるアクリロニトリル系化合物（化合物（ｌ−１））及び下記式（１２６）で表されるモノイソシアネート化合物（化合物（ｍ））から選ばれる１種又は２種以上とを反応させる方法が挙げられる。反応は、下記反応方法（１）により行えばよい。

However, R ⁸ has the same meaning as above.
The compounds represented by the above formula (38) to the above formula (40) can be synthesized by the following method. As the synthesis method, an aminosilane compound (k-2) represented by the following formula (122), an α, β-unsaturated carbonyl compound represented by the following formula (123) and the following formula (124) (compound (l )), An acrylonitrile-based compound (compound (l-1)) represented by the following formula (125) and a monoisocyanate compound (compound (m)) represented by the following formula (126) The method of making the above react is mentioned. The reaction may be performed by the following reaction method (1).

但し、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁸、Ｘ、ｎは上記と同意義である。
上記式（４５）で表される化合物は、以下の方法で合成することができる。その合成方法としては、分子内に少なくとも１個の上記含珪素特性基と少なくとも１個のα，β−不飽和カルボニル基を有する化合物（ｉ）のα，β−不飽和カルボニル基と下記式（１２７）で表されるアミン化合物（化合物（ｎ−１））の第１級アミノ基とを反応させる方法が挙げられる。反応は、下記反応方法（１）により行えばよい。

However, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁸ , X, and n are as defined above.
The compound represented by the above formula (45) can be synthesized by the following method. As the synthesis method, the α, β-unsaturated carbonyl group of the compound (i) having at least one silicon-containing characteristic group and at least one α, β-unsaturated carbonyl group in the molecule and the following formula ( 127), and a method of reacting with a primary amino group of an amine compound (compound (n-1)). The reaction may be performed by the following reaction method (1).

Further, as the compound (c), (1) a primary amino group in an aminosilane compound (k-1) represented by the following formula (121) or an aminosilane compound (k-) represented by the following formula (122) 2) at least one silicon-containing characteristic group and at least one in the molecule synthesized by the reaction of a primary amino group in (2) and an equivalent amount of a cyclic carbonate compound with respect to the primary amino group. Also included are compounds having an amino group of Specific examples of the cyclic carbonate compound include, but are not limited to, ethylene carbonate and propylene carbonate. These reactions may be performed by the following reaction method (1).
Further, as the compound (c), (1) a mercapto group in an aminothiol compound (the following compound (w)) having at least one amino group and at least one mercapto group in the molecule; In the molecule synthesized by radical addition reaction of at least one silicon-containing characteristic group and an alkenyl group in the alkenylsilane compound having at least one alkenyl group (the following compound (j)), at least one Also included are compounds having silicon characteristic groups and at least one amino group. The radical addition reaction may be performed by the following reaction method (2).

  Specific examples of the compound (c) include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, aminophenyltrimethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, 4-amino-3-dimethylbutylmethyldiethoxysilane, N -Phenyl-γ-aminopropyltrimethoxysilane, N-naphthyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-naphthyl-γ-aminopropylmethyldimethoxysilane, N- ( n-butyl)- γ-aminopropyltrimethoxysilane, N- (n-butyl) -γ-aminopropylmethyldimethoxysilane, N-ethyl-γ-aminopropyltrimethoxysilane, N-ethyl-γ-aminopropylmethyldimethoxysilane, N- Ethyl-aminoisobutyltrimethoxysilane, N-methyl-γ-aminopropyltrimethoxysilane, N-methyl-γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N- β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-3 -[Amino (dipropyleneoxy)] aminopropyltrimethoxy Sisilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, bis (trimethoxysilyl) Propyl) amine and the like, but is not limited thereto.

  Moreover, the said compound (c) is marketed, and they can be used in this invention. As commercial products, trade names manufactured by Shin-Etsu Chemical Co., Ltd .; KBM-602, KBM-603, KBE-603, KBM-903, KBE-903, KBM-902, KBE-902, KBM-573, etc., manufactured by Nihon Unicar Product name; A-1100, A-1102, A-1110, A-1120, A-1122, A-1170, A-9669, A-link15, Y-11637, etc. Product name manufactured by Degussa-HulsAG; DYNASYLAN1189, etc. Trade names manufactured by Chisso Corp .; S360, S320, S310, etc .; trade names manufactured by GE Toshiba Silicone Corp .; TSL8331, TSL8340, TSL8345, etc., but are not limited thereto.

但し、上記式（４６）及び上記式（４７）における、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義であり、Ｒ¹⁷及びＲ¹⁸は水素原子または上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基をそれぞれ示す。 The compound (d) is a compound having at least one silicon-containing characteristic group and at least one hydroxyl group in the molecule, and includes compounds represented by the following formulas (46) to (57). It is.

However, in the above formula (46) and the above formula (47), R ¹ , R ³ , X and n are as defined above, and R ¹⁷ and R ¹⁸ contain a hydrogen atom or the above silicon-containing characteristic group. Each of the organic groups having a molecular weight of 1,000 or less is shown.

但し、上記式（４８）及び上記式（４９）における、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義であり、Ｒ¹⁹は水素原子または上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基を示す。 The compounds represented by the above formula (46) and the above formula (47) can be synthesized by the following method. As the synthesis method, an epoxy group of the epoxysilane compound (h) represented by the following formula (62) and an amine compound (compound) represented by the following formula (127), the following formula (128) and the following formula (129) The method of making the amino group of (n-1) and a compound (n-2)) react is mentioned. The reaction may be performed by the following reaction method (1).

However, in the above formula (48) and the above formula (49), R ¹ , R ³ , X, and n are as defined above, and R ¹⁹ is a molecular weight that may contain a hydrogen atom or the above silicon-containing characteristic group. 1,000 or less organic groups are shown.

但し、上記式（５０）及び上記式（５１）における、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義であり、Ｒ²⁰及びＲ²¹は水素原子または上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基をそれぞれ示す。 The compounds represented by the above formula (48) and the above formula (49) can be synthesized by the following method. As the synthesis method, the epoxy group of the epoxysilane compound (h) represented by the following formula (62) is reacted with the mercapto group of the thiol compound (compound (o)) represented by the following formula (130). Is mentioned. The reaction may be performed by the following reaction method (1).

However, in the above formula (50) and the above formula (51), R ¹ , R ³ , X and n are as defined above, and R ²⁰ and R ²¹ contain a hydrogen atom or the above silicon-containing characteristic group. Each of the organic groups having a molecular weight of 1,000 or less is shown.

但し、上記式（５２）及び上記式（５３）における、Ｒ¹、Ｒ³、Ｒ²¹、Ｘ、ｎは上記と同意義である。 The compounds represented by the above formula (50) and the above formula (51) can be synthesized by the following method. As a synthesis method thereof, an amino group of a compound having a primary amino group and / or a secondary amino group in the compound (c) and a monoepoxy compound represented by the following formula (131) (compound (p )) And a method of reacting with an epoxy group. The reaction may be performed by the following reaction method (1).

However, R ¹ , R ³ , R ²¹ , X, and n in the above formula (52) and the above formula (53) have the same meaning as above.

但し、上記式（５４）及び上記式（５５）における、Ｒ¹、Ｒ³、Ｒ²⁰、Ｘ、ｎは上記と同意義であり、Ｒ²²は分子量１，０００以下の有機基を示す。 The compounds represented by the above formula (52) and the above formula (53) can be synthesized by the following method. As the synthesis method, a mercapto group of the mercaptosilane compound (compound (e)) represented by the following formula (58) and an epoxy group of the monoepoxy compound (compound (p)) represented by the following formula (131) Can be mentioned. The reaction may be performed by the following reaction method (1).

However, in the above formula (54) and the above formula (55), R ¹ , R ³ , R ²⁰ , X and n are as defined above, and R ²² represents an organic group having a molecular weight of 1,000 or less.

但し、上記式（５６）及び上記式（５７）における、Ｒ¹、Ｒ³、Ｒ²²、Ｘ、ｎは上記と同意義である。 The compound represented by the above formula (54) or the above formula (55) can be synthesized by the following method. As a synthesis method thereof, at least one amino group in the aminosilane compound (compound (k-1)) represented by the following formula (121) and a molecule represented by the following formula (132) or the following formula (133) are used. And the α, β-unsaturated carbonyl group of a compound having at least one α, β-unsaturated carbonyl group (compound (q)). The reaction may be performed by the following reaction method (1).

However, R ¹ , R ³ , R ²² , X, and n in the above formula (56) and the above formula (57) are the same as above.

The compound represented by the above formula (56) or the above formula (57) can be synthesized by the following method. As the synthesis method, at least one mercapto group of the mercaptosilane compound (compound (e)) represented by the following formula (58) and at least one molecule in the molecule represented by the following formula (132) or the following formula (133) are used. Examples include a method of reacting a hydroxyl group with an α, β-unsaturated carbonyl group of a compound having at least one α, β-unsaturated carbonyl group (compound (q)). The reaction may be performed by the following reaction method (1).
The compound (d) includes an alkenyl group in the compound having at least one hydroxyl group and at least one alkenyl group in the molecule, the following compound (e) and / or the following compound (f): A compound having at least one hydroxyl group in a molecule obtained by radical addition reaction of a mercapto group is also included. The radical addition reaction may be performed by the following reaction method (2).

但し、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義である。 The compound (e) is a compound having at least one silicon-containing characteristic group and at least one mercapto group in the molecule, and has a protonic polar group other than the silicon-containing characteristic group and mercapto group in the molecule. It is a compound which does not have, and the compound represented by the following formula (58) is included.

However, R ¹ , R ³ , X, and n are as defined above.

Specific examples of the compound (e) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, and the like. It is not limited to.
Moreover, the said compound (e) is marketed, and they can be used in this invention. Commercially available products include: Shin-Etsu Chemical Co., Ltd. trade names; KBM-803, KBM-802, etc .; Nippon Unicar Corporation trade names; A-189, AZ-6129, etc .; Chisso Corporation trade names; S810, etc., GE Toshiba Silicone Product name; TSL8380 etc. are mentioned, but it is not limited to these.

但し、上記式（５９）及び上記式（６０）における、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義であり、Ｒ²³は分子量１００００以下の二価の有機基を示す。
また、上記式（５９）及び上記式（６０）は合成することができる。上記式（５９）及び上記式（６０）の製造方法としては、下記式（６２）で表される上記エポキシシラン化合物（ｈ）中のエポキシ基と下記式（１３７）で表される上記ポリメルカプト化合物（ｖ）中のメルカプト基とを反応させる方法が挙げられる。反応は、下記反応方法（１）により行えばよい。 The compound (f) is a compound having at least one silicon-containing characteristic group and at least one mercapto group in the molecule, and includes compounds represented by the following formula (59) and the following formula (60). It is.

However, in the above formula (59) and the above formula (60), R ¹ , R ³ , X, and n are as defined above, and R ²³ represents a divalent organic group having a molecular weight of 10,000 or less.
Moreover, the said Formula (59) and the said Formula (60) are compoundable. The production method of the above formula (59) and the above formula (60) includes the epoxy group in the above epoxy silane compound (h) represented by the following formula (62) and the above polymercapto represented by the following formula (137). The method of making it react with the mercapto group in a compound (v) is mentioned. The reaction may be performed by the following reaction method (1).

但し、Ｒ¹、Ｘ、ｎは上記と同意義であり、ｍは０又は１、ａは０又は１〜１９の整数を示す。さらに、ａ個の繰り返しの中のｍは同じであってもよく異なっていてもよい。 The compound (g) is a hydrosilane compound in which a hydrogen atom is directly bonded to a silicon atom, and includes a compound represented by the following formula (61).

However, R ^1, X, n are as defined above, m is 0 or 1, a is an integer of 0 or 1 to 19. Furthermore, m in a repetitions may be the same or different.

  Specific examples of the compound (g) include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane, methyldimethoxysilane, phenyldimethoxysilane. Alkoxysilanes such as 1,3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane; acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane; bis (dimethyl Ketoximate) methylsilane, bis (cyclohexylketoxymate) methylsilane, bis (diethylketoxymate) trimethylsiloxysilane and other ketoximatesilanes; dimethylsilane, trimethylsiloxymethylsilane, 1 1 - dimethyl-3,3 - hydrosilane such as dimethyl siloxane; tri the like alkenyloxy silanes such as (isopropenyloxy) silane and the like, but is not limited thereto.

但し、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義である。 The compound (h) is a compound having at least one silicon-containing characteristic group and at least one epoxy group in the molecule, and includes a compound represented by the following formula (62).

However, R ¹ , R ³ , X, and n are as defined above.

Specific examples of the compound (h) include β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ-glycidoxy. Examples thereof include, but are not limited to, propyltriethoxysilane and γ-glycidoxypropylmethyldiethoxysilane.
Moreover, the said compound (h) is marketed, and they can be used in this invention. As a commercial item, Shin-Etsu Chemical Co., Ltd. trade name; KBM-403, KBM-402, KBM-303, GE Toshiba Silicone trade name; TSL8350, TSL8355, Nihon Unicar trade name; A-186, A- 187 etc., Chisso brand name; S510, S520 etc. are mentioned, but it is not limited to these.

  Furthermore, the compound (h) can be synthesized. As a synthesis method of the compound (h), a method of reacting an isocyanate group and / or isothiocyanate group in the compound group (C) with a hydroxyl group in the compound (u), or represented by the following formula (85): A method in which a mercapto group in the compound (e) and / or the compound (f) is subjected to a radical addition reaction with an alkenyl group in a compound having at least one alkenyl group and at least one epoxy group in the molecule. It is done. The reaction between the compound group (C) and the compound (u) has at least one alkenyl group and at least one epoxy group in the molecule represented by the following formula (85) by the following reaction method (1). The reaction of the compound with the compound (e) and / or the compound (f) may be carried out by the following reaction method (2).

The compound (i) is a compound having at least one silicon-containing characteristic group and at least one α, β-unsaturated carbonyl group in the molecule, and (1) represented by the following formula (63) An α, β-unsaturated carbonyl group in the polyvalent (meth) acrylate compound and (2) an amino group in one compound selected from the compound (c), the compound (e) and the compound (f), or A reaction product (i-1) obtained by Michael addition reaction with a mercapto group, and (1) an epoxy group in an epoxy compound represented by the following formula (65) and (2) the compound (c), the above A reaction product (i-2) obtained by reacting an amino group or a mercapto group in one compound selected from the compound (e) and the compound (f), and (1) represented by the following formula (66) Isocyanate-based isocyanate And (2) a reaction product (i-3) obtained by reacting an amino group, a hydroxyl group or a mercapto group in one compound selected from the compound group (A) and the compound (f), and ( 1) a reaction product (i-4) obtained by reacting a hydroxyl group in a hydroxy compound represented by the following formula (67) with an isocyanate group of one compound selected from (2) the above compound group (C) ) And (1) as represented by the following formula (68) generated by reacting the hydroxyl group in the hydroxy compound represented by the following formula (67) with the isocyanate group of the following compound (z). A reaction product (io-z) having at least one isocyanate group and at least one α, β-unsaturated carbonyl group in the molecule, and (2) from the compound group (A) and the compound (f) 1 chosen Amino group in compounds of include reaction products obtained by reacting a hydroxyl group or a mercapto group (i-5) is. The compound (i) is an acid chloride having at least one α, β-unsaturated carbonyl group in the molecule such as acrylic acid chloride or methacrylic acid chloride, the compound (c), and the compound (d). It can also be synthesized by reacting with the compound (e) and the compound (f). Further, specific examples of the compound (i) include γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, γ- in addition to the above synthesis examples. Acrylic silane compounds such as acryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, etc. However, it is not limited to these.

但し、Ｒ⁵は上記と同意義であり、Ａは分子内に下記式（６４）（ａ）で示される基と他の分子内に下記式（６４）（ｂ）で示される基を有する（メタ）アクリル系化合物の残基を、ｍ及びｎは１〜３の整数をそれぞれ示す。また、一分子中に含まれる複数のＲ⁵は、同じであってもよいし異なっていてもよい。

However, R ⁵ is as defined above, and A has a group represented by the following formula (64) (a) in the molecule and a group represented by the following formula (64) (b) in the other molecule ( As for the residue of a (meth) acrylic-type compound, m and n show the integer of 1-3, respectively. A plurality of R ⁵ contained in one molecule may be the same or different.

但し、上記式（６４）におけるＲ⁵、ｍ及びｎは上記と同意義である。

However, R ^5, m and n in the formula (64) are the same as defined above.

但し、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁵¹は分子量１，０００以下の有機基を示す。

^{However, R 2, R 4, R} 5, R 51 represents a molecular weight of 1,000 or less of the organic groups.

但し、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁵¹は上記と同意義である。

However, R ² , R ⁴ , R ⁵ and R ⁵¹ are as defined above.

但し、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁵¹は上記と同意義である。

However, R ² , R ⁴ , R ⁵ and R ⁵¹ are as defined above.

但し、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁵¹は上記と同意義であり、Ｒ⁵²は上記ポリイソシアネート化合物（ｚ）のイソシアネート基以外の残基を示す。

However, R ² , R ⁴ , R ⁵ and R ⁵¹ are as defined above, and R ⁵² represents a residue other than the isocyanate group of the polyisocyanate compound (z).

Next, reaction products (i-1) to (i-5) contained in the compound (i) will be described in detail using specific examples.
Specific examples of the polyvalent (meth) acrylate compound represented by the above formula (63) (methacrylacrylic) include butanediol, hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tripropylene glycol, glycerin, Polyacrylate or polymethacrylate of polyol compounds such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, polyethylene glycol, polypropylene glycol, etc., for example, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentae Thritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and the like, which are commercially available as (meth) acrylic acid adducts of polyglycidyl ethers of the above polyol compounds. Kyoei Chemical Co., Ltd. product names: Epoxy esters 40EM, 70PA, 200PA, 80MF, 3002M, 30002A and the like can be used, but are not limited thereto.

Method for synthesizing reaction product (i-1):
(1) Amino in one compound selected from the polyvalent (meth) acrylate compound represented by the above formula (63) and (2) the above compound (c), the above compound (e) and the above compound (f) A method of synthesizing the reaction product (i-1) by a Michael addition reaction with a group or a mercapto group may be performed by the following reaction method (1). Specifically, the following formula (69) (reaction between the polyvalent (meth) acrylate compound represented by the above formula (63) and the above compound (c)), the following formula (70) (in the above formula (63) Reaction of the polyvalent (meth) acrylate compound represented by the above compound (e)) and the following formula (71) (the polyvalent (meth) acrylate compound represented by the above formula (63) and the above compound (f)) Reaction).

上記式（６５）で表されるエポキシ系化合物の具体例としては、グリシジル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、共栄社化学社製商品名；ライトエステルＧ、ダイセル化学工業社製商品名；ＣＹＣＬＯＭＥＲＭ１００、ＣＹＣＬＯＭＥＲＡ２００、Ｍ−ＧＭＡ等が挙げられるが、これらに限定されるものではない。

Specific examples of the epoxy compound represented by the above formula (65) include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, trade name manufactured by Kyoeisha Chemical Co .; light ester G, trade name manufactured by Daicel Chemical Industries, Ltd. CYCLOMERM100, CYCLOMERA200, M-GMA etc. are mentioned, However, It is not limited to these.

Method for synthesizing reaction product (i-2):
(1) An epoxy group in the epoxy compound represented by the above formula (65) and (2) amino in one compound selected from the above compound (c), the above compound (e) and the above compound (f) A method of synthesizing the reaction product (i-2) by reaction with a group or a mercapto group may be performed by the following reaction method (1). Specifically, the following formula (72) (reaction between the epoxy compound represented by the above formula (65) and the above compound (c)), the following formula (73) (the epoxy represented by the above formula (65)). Reaction of the compound based on the compound (e) and the following formula (74) (reaction between the epoxy compound represented by the formula (65) and the compound (f)).
Hereinafter, R in the reaction formula represents a residue of each compound.

上記式（６６）で表されるイソシアネート系化合物の具体例としては、２−メタクリロイロキシエチルイソシアネート、昭和電工社製商品名；カレンズＭＯＩ等が挙げられるが、これらに限定されるものではない。

Specific examples of the isocyanate compound represented by the formula (66) include 2-methacryloyloxyethyl isocyanate, trade name of Showa Denko KK; Karenz MOI, but are not limited thereto.

Method for synthesizing reaction product (i-3):
(1) an isocyanate group in the isocyanate-based compound represented by the formula (66) and (2) an amino group, a hydroxyl group or a hydroxyl group in one compound selected from the compound group (A) and the compound (f) A method of synthesizing the reaction product (i-3) by reaction with a mercapto group may be performed by the following reaction method (1). Specifically, the following formula (75) (reaction between the isocyanate compound represented by the above formula (66) and the above compound (c)), the following formula (76) (the isocyanate represented by the above formula (66)). Reaction of a compound based on the above compound (d)) and the following formula (77) (reaction between an isocyanate compound represented by the above formula (66) and the above compound (e)). In addition, when one compound selected from the compound group (A) and the compound (f) has a plurality of reactive functional groups with respect to the isocyanate group, each reactive functional group is represented by the formula (66). It becomes the mixture of the compound which reacted with the isocyanate group in the isocyanate compound represented by. For example, when a compound in which a hydroxyl group and a mercapto group coexist is used as in the case of the compound (f), a reaction mixture of the following formula (76) and the following formula (77) is obtained.

上記式（６７）で表されるヒドロキシ系化合物の具体例としては、４−ヒドロキシブチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、Ｎ−メチロールアクリルアミド等のヒドロキシ基含有（メタ）アクリレート等が挙げられるが、これらに限定されるものではない。

Specific examples of the hydroxy compound represented by the above formula (67) include 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, N-methylolacrylamide and the like. However, it is not limited to these.

Method for synthesizing reaction product (i-4):
(1) Reaction generated by reaction of a hydroxyl group in the hydroxy compound represented by the formula (67) with an isocyanate group or isothiocyanate group in one compound selected from (2) the compound group (C). The method for synthesizing the product (i-4) may be carried out by the following reaction method (1). Specifically, a reaction such as the following formula (78) (reaction between the hydroxy compound represented by the formula (67) and the compound group (C)) is shown.

By reacting the hydroxyl group in the hydroxy compound represented by the above formula (67) with the isocyanate group in the following compound (z), at least one in the molecule as represented by the above formula (68) The method of synthesizing the reaction product (io-z) having an isocyanate group and at least one α, β-unsaturated carbonyl group may be carried out by the following reaction method (1). Specifically, a reaction like the following formula (79) is shown.

Method for synthesizing reaction product (i-5):
(1) Intramolecular as represented by the above formula (68) produced by reacting a hydroxyl group in the hydroxy compound represented by the above formula (67) with an isocyanate group in the following compound (z) A reaction product (io-z) having at least one isocyanate group and at least one α, β-unsaturated carbonyl group, and (2) 1 selected from the following compound group (A) and the compound (f): The method of synthesizing the reaction product (i-5) by reaction with an amino group, a hydroxyl group or a mercapto group in the seed compound may be performed by the following reaction method (1). Specifically, the following formula (80) (reaction between the reaction product (io-z) and the compound (c)), the following formula (81) (the reaction product (io-z) and the compound ( reaction with d) and the following formula (82) (reaction between the above reaction product (io-z) and the above compound (e)). In addition, when one kind of compound selected from the compound group (A) has a plurality of reactive functional groups with respect to the isocyanate group, each reactive functional group is contained in the reaction product (io-z). It becomes a mixture of compounds reacted with isocyanate groups. For example, when a compound in which a hydroxyl group and a mercapto group coexist is used as in the case of the compound (f), a reaction mixture of the following formula (81) and the following formula (82) is obtained.

The compound (j) is a compound having at least one silicon-containing characteristic group and at least one alkenyl group in the molecule, and (1) in a polyvalent allylic compound represented by the following formula (83) A reaction product (2) obtained by reacting an α, β-unsaturated carbonyl group of (2) with an amino group or a mercapto group in one compound selected from the compound (c), the compound (e) and the compound (f) ( j-1) and (1) an epoxy group in the epoxy compound represented by the following formula (85) and (2) one kind selected from the compound (c), the compound (e) and the compound (f) A reaction product (j-2) obtained by reacting an amino group, a hydroxyl group or a mercapto group in the compound, and (1) an isocyanate group in the isocyanate compound represented by the following formula (86) and (2) From compound group (A) and compound (f) A reaction product (j-3) obtained by reacting an amino group, a hydroxyl group or a mercapto group in one selected compound, and (1) a hydroxyl in a hydroxy compound represented by the following formula (87): Reaction product (j-4) obtained by reacting an isocyanate group and / or an isothiocyanate group in one compound selected from the group (2) compound group (C), and (1) the following formula (87 And at least one isocyanate group and at least one in the molecule represented by the following formula (90) synthesized by the reaction of the hydroxyl group in the hydroxy compound represented by An isocyanate group in the reaction product (jo-z) having one alkenyl group and (2) an amino group in one compound selected from the compound group (A) and the compound (f), A reaction product (j-5) obtained by reacting a droxyl group or a mercapto group, (1) a mercapto group in a thiol compound represented by the following formula (88) and (2) a compound group (C) A reaction product (j-6) obtained by reacting an isocyanate group and / or an isothiocyanate group in one compound, and (1) a mercapto group in a thiol compound represented by the following formula (88): A reaction product (js- having at least one isocyanate group and at least one alkenyl group in the molecule represented by the following formula (91) synthesized by reaction with an isocyanate group in the compound (z): reaction in which an isocyanate group in z) and (2) an amino group, a hydroxyl group or a mercapto group in one compound selected from the compound group (A) and the compound (f) are reacted Α, β in one compound selected from the compound (j-7) and (1) a mercapto group in the thiol-based compound represented by the following formula (88) and (2) the above compound (i) A reaction product (j-8) obtained by reacting with an unsaturated carbonyl group, and (1) a mercapto group in a thiol compound represented by the following formula (88) and (2) in the compound (h) The reaction product (j-9) obtained by reacting with the epoxy group of (1), and (1) the amino group in the amine compound represented by the following formula (89) and (2) the compound group (C) A reaction product (j-10) obtained by reacting an isocyanate group and / or an isothiocyanate group in one compound, and (1) an amino group in an amine compound represented by the following formula (89): The following formula (3) synthesized by reaction with an isocyanate group in the compound (z) 2) the isocyanate group in the reaction product (jn-z) having at least one isocyanate group and at least one alkenyl group in the molecule as represented by 2), (2) the compound group (A) and the above compound A reaction product (j-11) obtained by reacting an amino group, a hydroxyl group or a mercapto group in one compound selected from (f), and (1) an amine system represented by the following formula (89) A reaction product (j-12) obtained by reacting an amino group in the compound with (2) an α, β-unsaturated carbonyl group in one compound selected from the compounds (i), and (1) A reaction product (j-13) obtained by reacting an amino group in the amine compound represented by the following formula (89) with an epoxy group in the compound (h) (2) is included.

但し、Ｒ⁵は上記と同意義であり、Ａは分子内に下記式（８４）（ａ）で示される基と他の分子内に下記式（８４）（ｂ）で示される基を有する（メタ）アクリル系化合物の残基を、ｍ及びｎは１〜３の整数をそれぞれ示す。また、一分子中に含まれる複数のＲ⁵は、同じであってもよいし異なっていてもよい。

However, R ⁵ is as defined above, and A has a group represented by the following formula (84) (a) in the molecule and a group represented by the following formula (84) (b) in the other molecule ( As for the residue of a (meth) acrylic-type compound, m and n show the integer of 1-3, respectively. A plurality of R ⁵ contained in one molecule may be the same or different.

但し、上記式（８４）におけるＲ⁵、ｍ及びｎは上記と同意義である。

但し、Ｒ⁵¹は上記と同意義である。

However, R ⁵ , m and n in the above formula (84) are as defined above.

However, R ⁵¹ is as defined above.

但し、Ｒ⁵¹は上記と同意義である。

但し、Ｒ⁵¹は上記と同意義である。

However, R ⁵¹ is as defined above.

However, R ⁵¹ is as defined above.

但し、Ｒ⁵¹は上記と同意義である。

但し、Ｒ⁵¹は上記と同意義であり、Ｒ⁵³は水素原子または上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基を示す。

However, R ⁵¹ is as defined above.

However, R ⁵¹ is as defined above, and R ⁵³ represents a hydrogen atom or an organic group having a molecular weight of 1,000 or less which may contain the above-mentioned silicon-containing characteristic group.

但し、Ｒ⁵¹、Ｒ⁵²は上記と同意義である。

但し、Ｒ⁵¹、Ｒ⁵²は上記と同意義である。

However, R ⁵¹ and R ⁵² are as defined above.

However, R ⁵¹ and R ⁵² are as defined above.

但し、Ｒ⁵¹、Ｒ⁵²、Ｒ⁵³は上記と同意義である。
上記式（８３）で表され多価アリル系化合物は、上記多価（メタ）アクリレート系化合物がその両末端等の少なくとも二つの末端が（メタ）アクリロイル基になっているのに対して、一末端が（メタ）アクリロイル基であり、少なくともその他末端がアリル基になっている化合物である。それらの化合物の具体例としては、多価（メタ）アクリレート系化合物の上記具体例の一末端の（メタ）アクリロイル基がアリル基になっている化合物が挙げられる。

However, R ⁵¹ , R ⁵² and R ⁵³ are as defined above.
The polyvalent allyl compound represented by the above formula (83) is different from the polyvalent (meth) acrylate compound in that at least two ends such as both ends thereof are (meth) acryloyl groups. It is a compound in which the terminal is a (meth) acryloyl group and at least the other terminal is an allyl group. Specific examples of these compounds include compounds in which the (meth) acryloyl group at one end of the above specific example of the polyvalent (meth) acrylate compound is an allyl group.

Method for synthesizing reaction product (j-1):
(1) A polyvalent allyl compound represented by the above formula (83) and (2) an amino group in one compound selected from the above compound (c), the above compound (e) and the above compound (f) or A method of synthesizing the reaction product (j-1) by a Michael addition reaction with a mercapto group may be performed by the following reaction method (1). Specifically, the following formula (93) (reaction between the polyvalent allyl compound represented by the above formula (83) and the above compound (c)), the following formula (94) (represented by the above formula (83)). Reaction of the polyvalent allylic compound with the compound (e)) and the following formula (95) (reaction of the polyvalent allylic compound represented by the formula (83) with the compound (f)) A reaction is indicated.

上記式（８５）で表されるエポキシ系化合物の具体例としては、アリルグリシジルエーテル、３−ビニルシクロヘキセンオキシド、ダイソー社製商品名；ネオアリルＧ、ダイセル化学工業社製商品名；セロキサイド２０００等が挙げられるが、これらに限定されるものではない。

Specific examples of the epoxy compound represented by the above formula (85) include allyl glycidyl ether, 3-vinylcyclohexene oxide, a trade name of Daiso Corporation; Neoallyl G, a trade name of Daicel Chemical Industries; Celoxide 2000, and the like. However, it is not limited to these.

Method for synthesizing reaction product (j-2):
(1) An epoxy group in the epoxy compound represented by the above formula (85) and (2) amino in one compound selected from the above compound (c), the above compound (e) and the above compound (f) A method of synthesizing the reaction product (j-2) by reaction with a group or a mercapto group may be performed by the following reaction method (1). Specifically, the following formula (96) (reaction between the epoxy compound represented by the above formula (85) and the above compound (c)), the following formula (97) (the epoxy represented by the above formula (85)) Reaction of the system compound and the compound (e)) and the following formula (98) (reaction of the epoxy compound represented by the formula (85) and the compound (f)).

上記式（８６）で表されるイソシアネート系化合物の具体例としては、アリルイソシアネート、ｍ−イソプロペニル−α，α−ジメチルベンジルイソシアネート、日本サイテックインダストリー社製商品名；ｍ−ＴＭＩ等が挙げられるが、これらに限定されるものではない。

Specific examples of the isocyanate compound represented by the above formula (86) include allyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, a trade name manufactured by Nippon Cytec Industries, Inc .; m-TMI, and the like. However, it is not limited to these.

Method for synthesizing reaction product (j-3):
(1) an isocyanate group in the isocyanate compound represented by the above formula (86) and (2) an amino group, a hydroxyl group in one compound selected from the compound group (A) and the compound (f), or The method of synthesizing the reaction product (j-3) by reaction with a mercapto group may be performed by the following reaction method (1). Specifically, the following formula (99) (reaction between the isocyanate compound represented by the above formula (86) and the above compound (c)), the following formula (100) (the isocyanate represented by the above formula (86)). Reaction of a compound based on the above compound (d)) and the following formula (101) (reaction between an isocyanate compound represented by the above formula (86) and the above compound (e)). In addition, when one compound selected from the compound group (A) and the compound (f) has a plurality of reactive functional groups with respect to the isocyanate group, each reactive functional group is represented by the formula (86). It becomes the mixture of the compound which reacted with the isocyanate group in the isocyanate type compound represented by these. For example, when a compound in which a hydroxyl group and a mercapto group coexist is used as in the case of the compound (f), a reaction mixture of the following formula (100) and the following formula (101) is obtained.

上記式（８７）で表されるヒドロキシ系化合物の具体例としては、アリルアルコール、ダイセル化学工業社製商品名；プラクセルＣＦ−２００等が挙げられるが、これらに限定されるものではない。

Specific examples of the hydroxy compound represented by the above formula (87) include, but are not limited to, allyl alcohol, trade name of Daicel Chemical Industries; Plaxel CF-200, and the like.

Method for synthesizing reaction product (j-4):
(1) A reaction product is produced by a reaction between a hydroxyl group in the hydroxy compound represented by the above formula (87) and an isocyanate group or an isothiocyanate group in one compound selected from (2) compound group (C). The method of synthesizing the product (j-4) may be performed by the following reaction method (1). Specifically, a reaction like the following formula (102) is shown.

Method for synthesizing reaction product (jo-z):
By reacting the hydroxyl group in the hydroxy compound represented by the formula (87) with the isocyanate group in the compound (z), at least one molecule in the molecule as represented by the formula (90) is reacted. A method of synthesizing a reaction product (jo-z) having an isocyanate group and at least one alkenyl group may be performed by the following reaction method (1). Specifically, a reaction like the following formula (103) is shown.

Method for synthesizing reaction product (j-5):
(1) At least in the molecule represented by the above formula (90) synthesized by the reaction of the hydroxyl group in the hydroxy compound represented by the above formula (87) and the isocyanate group in the above compound (z) An isocyanate group in the reaction product (jo-z) having one isocyanate group and at least one alkenyl group, and (2) an amino group, a hydroxyl group or a hydroxyl group in one compound selected from the compound group (A) The method of synthesizing the reaction product (j-5) by reaction with a mercapto group may be performed by the following reaction method (1). Specifically, the following formula (104) (reaction between the reaction product (jo-z) represented by the above formula (90) and the above compound (c)), the following formula (105) (the above formula (90) Reaction of the reaction product represented by (jo-z) and the above compound (d)) and the following formula (106) (the reaction product represented by the above formula (90) (jo-z) and the above compound ( Reaction with e) is shown. In addition, when one compound selected from the compound group (A) has a plurality of reactive functional groups with respect to the isocyanate group, each reactive functional group is an isocyanate in the reaction product (jo-z). A mixture of compounds reacted with the group. For example, when a compound in which a hydroxyl group and a mercapto group coexist is used as in the case of the compound (f), a reaction mixture of the following formula (105) and the following formula (106) is obtained.

上記式（８８）で表されるチオール系化合物の具体例としては、アリルメルカプタン、フルフリルメルカプタン等が挙げられるが、これらに限定されるものではない。

Specific examples of the thiol-based compound represented by the above formula (88) include, but are not limited to, allyl mercaptan and furfuryl mercaptan.

Method for synthesizing reaction product (j-6):
(1) A reaction product obtained by a reaction between a mercapto group in the thiol-based compound represented by the formula (88) and an isocyanate group or an isothiocyanate group in one compound selected from (2) the compound group (C). The method of synthesizing (j-6) may be performed by the following reaction method (1). Specifically, a reaction represented by the following formula (107) is shown.

Method for synthesizing reaction product (js-z):
At least one in the molecule represented by the above formula (91) synthesized by the reaction of the mercapto group in the thiol compound represented by the above formula (88) and the isothiocyanate group in the above compound (z). The method of synthesizing the reaction product (js-z) having an isocyanate group and at least one alkenyl group may be carried out by the following reaction method (1). Specifically, a reaction like the following formula (108) is shown.

Method for synthesizing reaction product (j-7):
(1) At least in the molecule represented by the above formula (91) synthesized by the reaction of the mercapto group in the thiol compound represented by the above formula (88) and the isocyanate group in the above compound (z). An isocyanate group in a reaction product (js-z) having one isocyanate group and at least one alkenyl group; and (2) in one compound selected from the compound group (A) and the compound (f). The method of synthesizing the reaction product (j-7) by reaction with an amino group, hydroxyl group or mercapto group may be carried out by the following reaction method (1). Specifically, the following formula (109) (reaction of the reaction product (js-z) represented by the above formula (91) with the above compound (c)), the following formula (110) (the above formula (91) Reaction of the reaction product (js-z) represented by the following compound (d)) and the above formula (111) (reaction product (js-z) represented by the above formula (91)) and the above compound ( Reaction with e) is shown. In addition, when one kind of compound selected from the compound group (A) has a plurality of reactive functional groups with respect to the isocyanate group, each reactive functional group is an isocyanate in the reaction product (js-z). It becomes a mixture of compounds that have reacted with the group. For example, when a compound in which a hydroxyl group and a mercapto group coexist is used as in the case of the compound (f), a reaction mixture of the following formula (110) and the following formula (111) is obtained.

Method for synthesizing reaction product (j-8):
(1) Reaction by reaction of a mercapto group in the thiol-based compound represented by the above formula (88) with an α, β-unsaturated carbonyl group in one compound selected from (2) the above compound (i) The method for synthesizing the product (j-8) may be performed by the following reaction method (1). Specifically, a reaction like the following formula (112) is shown.

Method for synthesizing reaction product (j-9):
(1) A method of synthesizing a reaction product (j-9) by reaction of a mercapto group in the thiol-based compound represented by the formula (88) and (2) an epoxy group in the compound (h), What is necessary is just to perform by the following reaction method (1). In general, in the reaction involving the ring opening of the epoxy group, two kinds of products can be produced depending on the direction of the ring opening. Specifically, a reaction like the following formula (113) is shown.

Method for synthesizing reaction product (j-10):
(1) Reaction product by reaction of an amino group in the amine compound represented by the above formula (89) with an isocyanate group or an isothiocyanate group in one compound selected from (2) compound group (C) The method of synthesizing (j-10) may be performed by the following reaction method (1). Specifically, a reaction like the following formula (114) is shown.

Method for synthesizing reaction product (jn-z):
By reacting an amino group in the amine compound represented by the formula (89) with an isocyanate group in the compound (z), at least one molecule in the molecule represented by the formula (92) is reacted. The method of synthesizing the reaction product (jn-z) having an isocyanate group and at least one alkenyl group may be performed by the following reaction method (1). Specifically, a reaction like the following formula (115) is shown.

Method for synthesizing reaction product (j-11):
(1) At least in a molecule represented by the above formula (92) synthesized by a reaction between an amino group in the amine compound represented by the above formula (89) and an isocyanate group in the above compound (z). An isocyanate group in a reaction product (jn-z) having one isocyanate group and at least one alkenyl group, and (2) in one compound selected from the compound group (A) and the compound (f) A method of synthesizing the reaction product (j-11) by reaction with an amino group, a hydroxyl group or a mercapto group may be performed by the following reaction method (1). Specifically, the following formula (116) (reaction between the reaction product (jn-z) represented by the above formula (92) and the above compound (c)), the following formula (117) (the above formula (92) Of the reaction product (jn-z) represented by the above formula (d)) and the following formula (118) (the reaction product (jn-z) represented by the above formula (92) and the above compound ( Reaction with e) is shown. In addition, when one compound selected from the compound group (A) has a plurality of reactive functional groups with respect to the isocyanate group, each reactive functional group is an isocyanate in the reaction product (jn-z). A mixture of compounds reacted with the group. For example, when a compound in which a hydroxyl group and a mercapto group coexist is used as in the case of the compound (f), a reaction mixture of the following formula (117) and the following formula (118) is obtained.

Method for synthesizing reaction product (j-12):
(1) Reaction by reaction of an amino group in the amine compound represented by the above formula (89) and (2) an α, β-unsaturated carbonyl group in one compound selected from the above compound (i) The method for synthesizing the product (j-12) may be performed by the following reaction method (1). Specifically, a reaction like the following formula (119) is shown.

また、上記化合物（ｊ）には、分子内に少なくとも１個の上記含珪素特性基と少なくとも１個の極性要素部分と少なくとも１個のアルケニル基を有する化合物も含まれる。そのような化合物は市販されており、本発明ではそれらを用いることができる。市販品としては、信越化学工業社製商品名；ＫＢＭ−５７６、Ｘ−１２−５７５、Ｘ−１２−５７７、Ｘ−１２−５６３Ｂ、Ｘ−１２−５６５等が挙げられるが、これらに限定されるものではない。 Method for synthesizing reaction product (j-13):
(1) The method of synthesizing the reaction product (j-13) by reacting the amino group in the amine compound represented by the above formula (89) with (2) the epoxy group in the compound (h), What is necessary is just to perform by the following reaction method (1). In general, a reaction involving the ring opening of an epoxy group can produce at least two kinds of products depending on the direction of ring opening. Specifically, a reaction like the following formula (120) is shown.

The compound (j) also includes a compound having at least one silicon-containing characteristic group, at least one polar element portion, and at least one alkenyl group in the molecule. Such compounds are commercially available and can be used in the present invention. Examples of commercially available products include Shin-Etsu Chemical Co., Ltd. trade names; KBM-576, X-12-575, X-12-577, X-12-563B, X-12-565, etc., but are not limited thereto. It is not something.

但し、Ｒ¹、Ｒ³、Ｘ、ｎは上記と同意義である。
上記化合物（ｋ−１）の具体例としては、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルメチルジエトキシシラン、アミノフェニルトリメトキシシラン、４−アミノ−３−ジメチルブチルトリメトキシシラン、４−アミノ−３−ジメチルブチルメチルジメトキシシラン、４−アミノ−３−ジメチルブチルトリエトキシシラン、４−アミノ−３−ジメチルブチルメチルジエトキシシラン等が挙げられるが、これらに限定されるものではない。 The compound (k-1) is a compound having at least one silicon-containing characteristic group and one primary amino group or secondary amino group in the molecule, and is represented by the following formula (121). Are included.

However, R ¹ , R ³ , X, and n are as defined above.
Specific examples of the compound (k-1) include γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, aminophenyltrimethoxy. Silane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, 4-amino-3-dimethylbutylmethyldiethoxysilane However, it is not limited to these.

Moreover, the said compound (k-1) is marketed, and they can be used in this invention. As a commercial item, Shin-Etsu Chemical Co., Ltd. trade names; KBM-903, KBM-902, KBE-903, etc., Nihon Unicar Corporation trade names; A-1100, A-1102, A-1110, Y-11637, The product name manufactured by Chisso Corporation; S360 and the like; the product name manufactured by GE Toshiba Silicone; TSL8331 and the like are exemplified, but not limited thereto.
Among the above compounds (k-1), γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxy are preferred because they are easy to react and are easily commercially available. Silane, 4-amino-3-dimethylbutyltrimethoxysilane is preferred.

但し、Ｒ¹、Ｒ³、Ｒ¹⁰、Ｘ、ｎは上記と同意義である。 The compound (k-2) is a compound having at least one silicon-containing characteristic group and at least one primary amino group and / or secondary amino group in the molecule. The compound represented by these is included.

However, R ¹ , R ³ , R ¹⁰ , X, and n are as defined above.

Specific examples of the compound (k-2) include N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (amino Ethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N-3- [amino (dipropyleneoxy)] aminopropyltrimethoxysilane, (aminoethylamino) Examples include, but are not limited to, methyl) phenethyltrimethoxysilane, N- (6-aminohexyl) aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, and the like. is not.
Moreover, the said compound (k-2) is marketed, and they can be used in this invention. As commercial products, trade names manufactured by Shin-Etsu Chemical Co., Ltd .; KBM-603, KBM-602, KBE-603, KBM-6063, X-12-896, etc. However, it is not limited to these.
Among the above compounds (k-2), N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) are easy to react and are widely commercially available. ) -Γ-aminopropyltriethoxysilane and N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane are preferred.

但し、Ｒ²、Ｒ⁴、Ｒ⁵、Ｒ⁶は上記と同意義である。

但し、Ｒ⁷は上記と同意義である。
上記化合物（ｌ）としては、（メタ）アクリル酸系化合物、ビニルカルボニル系化合物、マレイン酸系化合物、マレイミド系化合物が含まれる。
上記化合物（ｌ）の具体例としては、それぞれ以下のものが挙げられるが、これらに限定されるものではない。 The compound (l) is an α, β-unsaturated carbonyl compound having at least one α, β-unsaturated carbonyl group in the molecule, and is represented by the following formula (123) or the following formula (124). Compounds are included.

^{However, R 2, R 4, R} 5, R 6 are as defined above.

However, R ⁷ has the same meaning as above.
Examples of the compound (l) include (meth) acrylic acid compounds, vinylcarbonyl compounds, maleic acid compounds, and maleimide compounds.
Specific examples of the compound (l) include the following, but are not limited thereto.

(Meth) acrylic acid compounds:
(Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) ) Acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) ) Acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, dicyclopentadienyl (meth) Acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acryl , Tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, diacetone (meth) acrylate, isobutoxymethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) ) Acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Nt-octyl (meth) acrylamide, N -Isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, diacetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- [3- ( Dimethylamino) propyl] methacrylamide, (meth) acryloylmorpholine, 2- (meth) acryloyloxyethyl succinate, maleic acid, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyldiethoxysilane, γ- Acryloxypropyltrimethoxysilane, γ-acryloxymethyldimethoxysilane, manufactured by Kyoeisha Chemical Co., Ltd .: Light ester M, light ester E, light ester NB, light ester IB, light ester EH, light Steal ID, light ester L, light ester L-5, light ester L-7, light ester TD, light ester L-8, light ester S, light ester MC, light ester 130MA, light ester 041MA, light ester CH, light Ester THF, light ester BZ, light ester PO, light ester IB-X, light ester HO, light ester HOP, light ester HOA, light ester HOP-A, light ester HOB, light ester DM, light ester DE, light ester A , Light ester HO-MS, Light ester HO-HH, Light ester HO-MPP, Light ester G, Light ester TB, Light ester IS, Light ester MTG, Light ester BO, La Toester CL, light ester M-3F, light ester M-4F, light ester M-6F, light ester FM-108, light acrylate IAA, light acrylate LA, light acrylate SA, light acrylate BO-A, light Acrylate EC-A, Light acrylate MTG-A, Light acrylate 130A, Light acrylate DPM-A, Light acrylate PO-A, Light acrylate P-200A, Light acrylate NP-4EA, Light acrylate NP-8EA, Light acrylate THF-A , Light acrylate IB-XA, light acrylate HO-A, light acrylate HOP-A, epoxy ester M-600A, HOA-MPL, HOA-MPE, light acrylate IO- , Light acrylate IM-A, light acrylate IS-A, light acrylate EHDG-A, light acrylate HOB-A, HOA-HH, light acrylate FA-108, light acrylate P2H-A, manufactured by Kyowa Hakko Kogyo Co., Ltd. Acetone acrylic amide, Showa Denko Co., Ltd. trade name: Karenz MOI-BM, Mitsubishi Chemical Co., Ltd. trade name: 4-hydroxybutyl acrylate, Shin-Nakamura Chemical Co., Ltd. trade name: NK ester M-20G, NK ester M-40G, NK Ester M-90G, NK ester M-230G, NK ester CB-1, NK ester SA, topolene M, NK ester S, NK ester AMP-10G, NK ester AMP-20G, NK ester AMP-20GY, NK ester AMP- 60G, NK ester AM- 30G, NK ester AM-90G, NK ester A-SA, NK ester LA, NK ester CMP-1E, NK ester NPA-10G, NK ester NPA-5E, NK ester NPA-5P, NK ester LMA, NK ester ACB- 21, NK ester CB-23, NK ester CB-26, NK ester CBX-1, NK ester A-IB, NK ester IB, NK ester A-MO, NK ester 702A, NK ester A-OC-18E, NK ester S-1800A, NK ester S-1800M, NK ester A-L4, NK ester # 401P, NK ester A-NP-1E, NK oligo EA-5120, NK oligo EA-5122, NK oligo EA-5123, Toagosei Co., Ltd. Product name: Aronix M-101, A Knicks M-102, Aronix M-110, Aronix M-111, Aronix M-113, Aronix M-114, Aronix M-117, Aronix M-120, Aronix M-150, Aronix M-156, Aronix M-5300, Aronix M-5400, Aronix M-5600, Aronix M-5700, manufactured by Nagase Kasei Kogyo Co., Ltd .: Denacol Acrylate DA-141, manufactured by Nippon Oil & Fats Co., Ltd .: Blemmer BMA, Blemmer IBMA, Blemmer CHMA, Blemmer EHMA-25 , Blemmer TBCHMA, Blemmer DSMA, Blemmer LMA, Blemmer SLMA, Blemmer PMA, Blemmer CMA, Blemmer SMA, Blemmer VMA, Blemmer B-12, Blemma CHA, Blemmer LA, Blemmer SLA, Blemmer CA, Blemmer SA, Blemmer B-18A, Blemmer G, Blemmer GH, Blemmer GH-LC, Blemmer GS, Blemmer GLM, Blemmer GLM-R, Blemmer G-FA, Blemmer G-O Blemmer G-SB, Blemmer E, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400, Blemmer P, Blemmer PP-1000, Blemmer PP- 500, Blemmer PP-800, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer AP-800, Blemmer 50 PEP-300, Blemmer 70 PEP-350B, Blemmer 55PET-800, Blemmer 30PPT-800, Blemmer 55PET-800, Blemmer AET series, Blemmer 30PPT-800, Blemmer 50PPT-800, Blemmer 70PPT-800, Blemmer APT series, Blemmer 10PPB-500B, Blemmer 10APB- 500B, Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer PME-4000, Blemmer AME-400, Blemmer 50POEP-800B, Blemmer 50AOEP-800B, Blemmer PLE-200, Blemmer ALE- 200, Blemmer ALE-800, Blemmer PSE-200, Blemmer PSE 400, Blemmer PSE-1300, Blemmer ASEP series, Blemmer PKEP series, Blemmer ANE-300, Blemmer ANE-1300, Blemmer PNEP series, Blemmer PNPE series, Blemmer 43ANEP-500, Blemmer 70ANEP-550, Mitsubishi Gas Chemical Co., Ltd. : GE-110, MMA, EMA, GE-310, GE-320, EHMA, GE-410, GE-420, DPMA, SMA, GE-510, GE-610, GE-650, GE-710, GE-720 AMA, CHMA, DAA, manufactured by Mitsubishi Rayon Co., Ltd. Trade names: Acryester M, Acryester E, Acryester IB, Acryester TB, Acryester EH, Acryester L, Acryester SL, Acry Ester TD, acrylate S, acrylate CH, acrylate BZ, acrylate IBX, acrylate G, acrylate GU, acrylate THF, acrylate A, acrylate HO, acrylate HISS, acrylate HP, acrylate MT Acrylate ester ET, acrylate ester PA, acrylate ester HH, acrylate ester DM, acrylate ester DE, acrylate ester 3FE, acrylate ester 17FE, Shin-Etsu Chemical Co., Ltd. trade names: KBM-503, KBM-5103 and the like.

Vinylcarbonyl compounds:
Vinyl acetone, vinyl ethyl ketone, vinyl butyl ketone, mesityl oxide, acrolein, methacrolein, cinnamyl compounds, crotonaldehyde, etc.
Maleic acid compounds:
Maleic acid, itaconic acid, crotonic acid, dimethyl maleate, diethyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, dioctyl maleate and the like.
Maleimide compounds:
N-phenylmaleimide, N-cyclohexylmaleimide, hydroxyphenylmonomaleimide, N-laurelmaleimide, diethylphenylmonomaleimide, p-hydroxyphenylmaleimide, N- (2-chlorophenyl) maleimide and the like.

  Furthermore, specific examples of the compound (l) other than the (meth) acrylic acid compound, the vinylcarbonyl compound, the maleic acid compound, and the maleimide compound include a fluorine atom, a sulfur atom, A compound containing a phosphorus atom and a polymerizable alkenyl compound containing the polar element moiety are also included. Examples of the compound containing a fluorine atom include perfluorooctylethyl (meth) acrylate and trifluoroethyl (meth) acrylate, and examples of the compound containing a phosphorus atom include (meth) acryloxyethyl phenyl acid phosphate.

  Among the compounds (l), methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, t-butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, from the viewpoint of easy reaction, wide commercial availability, and availability. Lauryl acrylate, dimethyl maleate, diethyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, N-phenylmaleimide, N-cyclohexylmaleimide and the like are preferable. Of these, methyl acrylate and ethyl acrylate are particularly preferable for imparting fast curability, and 2-ethylhexyl acrylate and lauryl acrylate are particularly desirable for imparting flexibility. Moreover, the said compound (l) can be used 1 type, or 2 or more types.

但し、Ｒ²、Ｒ⁴、Ｒ⁵は上記と同意義である。
上記化合物（ｌ−１）の具体例としては、アクリロニトリル、α−メチルアクリロニトリル、２，４−ジシアノブテン等が挙げられるが、これらに限定されるものではない。 The compound (l-1) is an acrylonitrile compound, and includes a compound represented by the following formula (125).

However, R ² , R ⁴ and R ⁵ are as defined above.
Specific examples of the compound (1-1) include, but are not limited to, acrylonitrile, α-methylacrylonitrile, 2,4-dicyanobutene, and the like.

但し、Ｒ²⁴は上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基を示す。
上記化合物（ｍ）の具体例としては、エチルイソシアネート、ｎ−ヘキシルイソシアネート、ｎ−ドデシルイソシアネート、ｐ−トルエンスルホニルイソシアネート、ｎ−オクタデシルイソシアネート、フェニルイソシアネート、ベンジルイソシアネート、２−メトキシフェニルイソシアネート等の他、信越化学工業社製商品名；ＫＢＭ−９００７（γ−イソシアネートプロピルトリメトキシシラン）等のイソシアネートシラン、住化バイエルウレタン社製商品名；アディティブＴＩ等が挙げられるが、これらに限定されるものではない。 The compound (m) is an isocyanate compound having at least one isocyanate group in the molecule, and includes a compound represented by the following formula (126).

However, R ²⁴ represents an organic group having a molecular weight of 1,000 or less that may contain the silicon-containing characteristic group.
Specific examples of the compound (m) include ethyl isocyanate, n-hexyl isocyanate, n-dodecyl isocyanate, p-toluenesulfonyl isocyanate, n-octadecyl isocyanate, phenyl isocyanate, benzyl isocyanate, 2-methoxyphenyl isocyanate, and the like. Trade names manufactured by Shin-Etsu Chemical Co., Ltd .; isocyanate silanes such as KBM-9007 (γ-isocyanatopropyltrimethoxysilane), trade names manufactured by Sumika Bayer Urethane Co .; additive TI, etc. .

但し、Ｒ²⁴は上記と同意義である。 The compound (n-1) is an amine compound having at least one primary amino group in the molecule, and includes a compound represented by the following formula (127).

However, R ²⁴ is as defined above.

  Specific examples of the compound (n-1) include aniline, o-toluidine, m-toluidine, p-toluidine, 2,3-xylidine, 2,4-xylidine, mesitylamine, methylamine, ethylamine, propylamine, isopropyl. Amine, n-butylamine, s-butylamine, t-butylamine, pentylamine, n-hexylamine, cyclohexylamine, benzylamine, 2-ethylhexylamine, octylamine, phenethylamine, dodecylamine, stearylamine, γ-aminopropyltrimethoxy Silane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, aminophenyltrimethoxysilane, 4-amino-3-dimethylbutyltrimethyl Xisilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, 4-amino-3-dimethylbutylmethyldiethoxysilane, trade name of Shin-Etsu Chemical Co., Ltd .; KBM-903 , KBM-902, KBE-903, KBE-902, etc., trade names manufactured by Nippon Unicar Co., Ltd .; A-1100, A-1110, Y-11637, etc., but are not limited thereto.

但し、Ｒ²⁴は上記と同意義であり、Ｒ²⁵は上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基又は上記式（４１）〜式（４４）を示す。Ｒ²⁴とＲ²⁵は同じ基であってもよい。

但し、Ｒ³は上記と同意義である。 The compound (n-2) is an amine compound having at least one secondary amino group in the molecule, and includes compounds represented by the following formula (128) and the following formula (129).

However, R ²⁴ has the same meaning as described above, and R ²⁵ represents an organic group having a molecular weight of 1,000 or less which may contain the silicon-containing characteristic group, or the above formulas (41) to (44). R ²⁴ and R ²⁵ may be the same group.

However, R ³ has the same meaning as above.

  Specific examples of the compound (n-2) include piperidine, pyrrolidine, pyrrole, 3-pyrroline, N-methylaniline, N-ethylaniline, N-propylaniline, N-butylaniline, N-pentylaniline, benzylmethyl. Amine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, di-n-butylamine, di-s-butylamine, di-t-butylamine, dipentylamine, di-n-hexylamine, dicyclohexylamine, dibenzylamine, di-2-ethylhexylamine , Dioctylamine, diphenethylamine, didodecylamine, distearylamine, N-phenyl-aminopropyltrimethoxysilane, N-ethyl-aminoisobutyltrimethoxysilane, N- (n-butyl) -3-aminopropylto Methoxysilane, trade name manufactured by Shin-Etsu Chemical Co., Ltd .; KBM-573, etc .; trade name manufactured by Nihon Unicar; Y-9669, A-link15, etc., trade name manufactured by Degussa-HulsAG; DYNASYLAN 1189, etc. Is not to be done.

但し、Ｒ²⁴は上記と同意義である。
上記化合物（ｏ）の具体例としては、メタンチオール、エタンチオール、プロパンチオール、イソプロパンチオール、ｎ−ブタンチオール、ｓ−ブタンチオール、ｔ−ブタンチオール、ペンタンチオール、ヘキサンチオール、２−エチルヘキサンチオール、オクタンチオール、デカンチオール、ドデカンチオール、チオフェノール、γ−メルカプトプロピルトリメトキシシラン、γ−メルカプトプロピルメチルジメトキシシラン、γ−メルカプトプロピルトリエトキシシラン、γ−メルカプトプロピルメチルジエトキシシラン等が挙げられるが、これらに限定されるものではない。 The compound (o) is a thiol compound having one mercapto group in the molecule, and includes a compound represented by the following formula (130).

However, R ²⁴ is as defined above.
Specific examples of the compound (o) include methanethiol, ethanethiol, propanethiol, isopropanethiol, n-butanethiol, s-butanethiol, t-butanethiol, pentanethiol, hexanethiol, 2-ethylhexanethiol. , Octanethiol, decanethiol, dodecanethiol, thiophenol, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldiethoxysilane, etc. However, it is not limited to these.

但し、Ｒ²⁶は水素原子または上記含珪素特性基を含んでいてもよい分子量１，０００以下の有機基を示す。 The compound (p) is an epoxy compound having at least one epoxy group in the molecule, and includes a compound represented by the following formula (131).

However, R ²⁶ represents a hydrogen atom or an organic group having a molecular weight of 1,000 or less which may contain the silicon-containing characteristic group.

  Specific examples of the compound (p) include ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, cyclohexene oxide, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, allyl glycidyl ether, and pt-butylphenol mono. Glycidyl ether, neopentyl alcohol monoglycidyl ether, monoglycidyl ether of alkyl alcohol having an alkyl moiety having 1 to 12 carbon atoms, 3-vinylcyclohexene oxide, 1,6-hexanediol diglycidyl ether, epi Chlorohydrin, β-methylepichlorohydrin, glycidol, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, Daicel Chemical Industries trade name; GD, AOE, MECH, CHXO, PNO, STO, allyl glycidyl ether, Daiso trade name; Neoallyl G, Daicel The above-mentioned compound (h), such as Chemical Industry's product name; Celoxide 2000, is mentioned, but it is not limited to these.

但し、上記式（１３２）及び下記式（１３３）における、Ｒ²、Ｒ⁴、Ｒ⁵及びＲ²²は上記と同意義である。 The compound (q) is a hydroxyl group-containing α, β-unsaturated carbonyl compound having at least one hydroxyl group and at least one α, β-unsaturated carbonyl group in the molecule, and has the following formula (132) And a compound represented by the following formula (133).

However, R ² , R ⁴ , R ⁵ and R ²² in the above formula (132) and the following formula (133) have the same meanings as described above.

Specific examples of the compound (q) include 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxy group-containing (meta ) Acrylate and the like, but not limited thereto.
The compound (s) is a polymerizable alkenyl compound having at least one polymerizable alkenyl group and an epoxy group in the molecule, and includes a compound represented by the formula (85).

但し、Ｒ²、Ｒ⁴、Ｒ⁵は上記と同意義であり、Ｒ²⁷は分子量１，０００以下の有機基を示す。
さらに、上記式（１３４）におけるＲ²⁷が下記式（１３５）で表される場合、一般的に重合反応に用いられるアクリル酸系化合物となり、本発明には好適である。

但し、Ｒ²、Ｒ³、Ｒ⁴は上記と同意義であり、Ｒ²⁸は分子量１，０００以下の有機基を示す。 The compound (t) is a polymerizable alkenyl compound having at least one polymerizable alkenyl group in the molecule, and includes a compound represented by the following formula (134).

However, R ² , R ⁴ and R ⁵ are as defined above, and R ²⁷ represents an organic group having a molecular weight of 1,000 or less.
Furthermore, when R ²⁷ in the above formula (134) is represented by the following formula (135), it is an acrylic acid compound generally used in a polymerization reaction, and is suitable for the present invention.

However, R ² , R ³ and R ⁴ are as defined above, and R ²⁸ represents an organic group having a molecular weight of 1,000 or less.

Specific examples of the compound (t) include acrylic acid, methacrylic acid (hereinafter referred to as (meth) acrylic acid together with acrylic acid compound and methacrylic acid compound), methyl (meth) acrylate, and ethyl (meth) acrylate. , Propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate , Hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (Meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, Benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, methoxy Polyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylic , Dicyclopentadienyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate , Diacetone (meth) acrylate, isobutoxymethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, glycidyl (meth) acrylate , (Meth) acrylamide, N, N-dimethyl (meth) acrylamide, Nt-octyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-methylol (meth) acrylamide, dye Acetone (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, (meth) acryloylmorpholine, acrylonitrile, α- Methylacrylonitrile, 2,4-dicyanobutene, 2- (meth) acryloyloxyethyl succinate, maleic acid, dimethyl maleate, diethyl maleate, dibutyl maleate, di-2-ethylhexyl maleate, dioctyl maleate, 2-maleic acid 2- (Meth) acryloyloxyethyl, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl Ethoxysilane, γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxymethyldimethoxysilane, vinyl glycidyl ether, allyl glycidyl ether, vinyl pyrrolidone, vinyl carbazole , Alkyl vinyl ethers such as styrene, α-methyl styrene, m-methyl styrene, p-methyl styrene, p-ethyl styrene, p-methoxy styrene, divinyl benzene, methyl vinyl ether, methyl cinnamate, ethyl cinnamate, cinnamic acid Cinnamic compounds such as cinnamic aldehyde, cinnamyl alcohol, cinnamic acid amide, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (medium ) Hydroxyl group-containing (meth) acrylates such as acrylate, 2-acryloyloxypropyl (meth) acrylate, N-methyl roll acrylamide, allyl alcohol, allylphenol, eugenol, hydroxystyrene, 3-methyl-1-butyne-3- All, 3-methyl-1-pentyn-3-ol, 3,5-dimethyl-1-hexyn-3-ol, propargyl alcohol, 2-methyl-3-butyn-2-ol, undecylenic acid, 2-butenoic acid , Furfuryl alcohol, 9-decenol-1,5-hexen-1-ol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monobutyl ether, mesityl oxide, vinyl chloride, Vinyl acetate, vinyl propionate, pig Ene, isoprene, chloroprene, ethylene, other olefins, unsaturated esters, halogenated olefins, Kyoeisha Chemical Co., Ltd. trade names: Light Ester M, Light Ester E, Light Ester NB, Light Ester IB, Light Ester EH , Light ester ID, light ester L, light ester L-5, light ester L-7, light ester TD, light ester L-8, light ester S, light ester MC, light ester 130MA, light ester 041MA, light ester CH , Light ester THF, light ester BZ, light ester PO, light ester IB-X, light ester HO, light ester HOP, light ester HOA, light ester HOP-A, light ester HOB, light Ester DM, light ester DE, light ester A, light ester HO-MS, light ester HO-HH, light ester HO-MPP, light ester G, light ester TB, light ester IS, light ester MTG, light ester BO, light Ester CL, light ester M-3F, light ester M-4F, light ester M-6F, light ester FM-108, light acrylate IAA, light acrylate LA, light acrylate SA, light acrylate BO-A, light Acrylate EC-A, Light acrylate MTG-A, Light acrylate 130A, Light acrylate DPM-A, Light acrylate PO-A, Light acrylate P-200A, Light acrylate NP-4EA, LA Acrylate NP-8EA, light acrylate THF-A, light acrylate IB-XA, light acrylate HO-A, light acrylate HOP-A, epoxy ester M-600A, HOA-MPL, HOA-MPE, light acrylate IO-A, Light Acrylate IM-A, Light Acrylate IS-A, Light Acrylate EHDG-A, Light Acrylate HOB-A, HOA-HH, Light Acrylate FA-108, Light Acrylate P2H-A, Product Name: Kyowa Hakko Kogyo Co., Ltd. Acrylic amide, etc., Showa Denko Co., Ltd., trade name: Karenz MOI-BM, etc., Mitsubishi Chemical Co., Ltd., trade name: 4-hydroxybutyl acrylate, Shell Chemical Co., Ltd., trade names: Veova 9, Veova 10, etc., Shin Nakamura Chemical Co., Ltd. Name: NK Ester -20G, NK ester M-40G, NK ester M-90G, NK ester M-230G, NK ester CB-1, NK ester SA, topolene M, NK ester S, NK ester AMP-10G, NK ester AMP-20G, NK ester AMP-20GY, NK ester AMP-60G, NK ester AM-30G, NK ester AM-90G, NK ester A-SA, NK ester LA, NK ester CMP-1E, NK ester NPA-10G, NK ester NPA- 5E, NK ester NPA-5P, NK ester LMA, NK ester ACB-21, NK ester CB-23, NK ester CB-26, NK ester CBX-1, NK ester A-IB, NK ester IB, NK ester A- MO, NK ester 702A NK ester A-OC-18E, NK ester S-1800A, NK ester S-1800M, NK ester A-L4, NK ester # 401P, NK ester A-NP-1E, NK oligo EA-5120, NK oligo EA-5122 NK Oligo EA-5123, etc., trade names manufactured by Daiichi Kogyo Seiyaku Co., Ltd .: New Frontier PHE, New Frontier PHE-2, New Frontier NP-2, New Frontier NP-4, New Frontier ME-3, New Frontier EH-2 , New Frontier IBA, New Frontier DPGA, New Frontier MPEM-400, New Frontier NPEM-1000, New Frontier BR-30, New Frontier BR30M, New Frontier BR-31, etc., Daicel Chemical Product name: Celoxide 2000, MVE, Plaxel FM1, Plaxel FM1D, Plaxel FM2D, Plaxel FM3, Plaxel FM3X, Plaxel FM4, Plaxel FM4X, Plaxel FM4DX, Plaxel FM5, Plaxel FM5L, D6 Plaxel FA3, Plaxel FA4DT, Plaxel FA5, Plaxel FA10L, Plaxel FD101, Plaxel FD102, Plaxel FD201, Plaxel FM1A, Plaxel FM4A, Plaxel FM10A, CYCLOMERM100, GY G, Toagosei Co., Ltd. Product name: Aroni Cox M-101, Aronix M-102, Aronix M-110, Aronix M-111, Aronix M-113, Aronix M-114, Aronix M-117, Aronix M-120, Aronix M-150, Aronix M-156, Aronix M-5300, Aronix M-5400, Aronix M-5600, Aronix M-5700, Nagase Kasei Kogyo brand name: Denacol Acrylate DA-141, Nippon Oil & Fats brand name: Blemmer BMA, Blemmer IBMA, Blemmer CHMA Blemmer EHMA-25, Blemmer TBCHMA, Blemmer DSMA, Blemmer LMA, Blemmer SLMA, Blemmer PMA, Blemmer CMA, Blemmer SMA, Blemmer VMA, Blemma B-12, Blemmer CHA, Blemmer LA, Blemmer SLA, Blemmer CA, Blemmer SA, Blemmer B-18A, Blemmer G, Blemmer GH, Blemmer GH-LC, Blemmer GS, Blemmer GLM, Blemmer GLM-R, Blemmer G-FA , Blemmer G-O, Blemmer G-SB, Blemmer E, Blemmer PE-90, Blemmer PE-200, Blemmer PE-350, Blemmer AE-90, Blemmer AE-200, Blemmer AE-400, Blemmer P, Blemmer PP- 1000, Blemmer PP-500, Blemmer PP-800, Blemmer AP-150, Blemmer AP-400, Blemmer AP-550, Blemmer AP-800, Blemmer 50PEP-300, Blemmer 70P EP-350B, Blemmer AEP series, Blemmer 55PET-400, Blemmer 30PET-800, Blemmer 55PET-800, Blemmer AET series, Blemmer 30PPT-800, Blemmer 50PPT-800, Blemmer 70PPT-800, Blemmer APT series, Blemmer 10PPB-500B , Blemmer 10APB-500B, Blemmer PME-100, Blemmer PME-200, Blemmer PME-400, Blemmer PME-1000, Blemmer PME-4000, Blemmer AME-400, Blemmer 50POEP-800B, Blemmer 50AOEP-800B, Blemmer PLE-200 , Blemmer ALE-200, Blemmer ALE-800, Blemmer PSE-20 , Blemmer PSE-400, Blemmer PSE-1300, Blemmer ASEP series, Blemmer PKEP series, Blemmer ANE-300, Blemmer ANE-1300, Blemmer PNEP series, Blemmer PNPE series, Blemmer 43ANEP-500, Blemmer 70ANEP-550, Mitsubishi Gas Chemical Company product number: GE-110, MMA, EMA, GE-310, GE-320, EHMA, GE-410, GE-420, DPMA, SMA, GE-510, GE-610, GE-650, GE-710 , GE-720, AMA, CHMA, DAA, manufactured by Mitsubishi Rayon Co., Ltd. Trade name: Acryester M, Acryester E, Acryester IB, Acryester TB, Acryester EH, Acryester L, Aque Ester SL, Acryester TD, Acryester S, Acryester CH, Acryester BZ, Acryester IBX, Acryester G, Acryester GU, Acrylate THF, Acryester A, Acryester HO, Acryester HISS, Acryester HP Acryester MT, Acryester ET, Acryester PA, Acryester HH, Acryester DM, Acryester DE, Acryester 3FE, Acryester 17FE, etc., trade names manufactured by Nippon Kayaku Co., Ltd. Product name: Biscoat 3700, manufactured by Osaka Organic Chemical Co., Ltd. Product name: KBM-503, KBM-5103, KBM-1403, KBM-1003, etc. manufactured by Shin-Etsu Chemical Co., Ltd., allylamine compounds Product, allyl mercaptan compound, furfuryl mercaptan compound, compound (i), compound (j), compound (l), compound (l-1), compound (q) and the like. It is not limited.

但し、Ｒ²³は上記と同意義である。
上記化合物（ｕ）の具体例としては、グリシドール、ジグリセロールジグリシジルエーテル、４−ヒドロキシ−３−メトキシシクロヘキシルエチレンオキサイド等が挙げられるが、これらに限定されるものではない。 The compound (u) is a glycidol-based compound having at least one hydroxyl group and at least one epoxy group in the molecule, and includes a compound represented by the following formula (136).

However, R ²³ is as defined above.
Specific examples of the compound (u) include, but are not limited to, glycidol, diglycerol diglycidyl ether, 4-hydroxy-3-methoxycyclohexylethylene oxide, and the like.

但し、Ｒ²³は上記と同意義である。 The compound (v) is a polymercapto compound having at least two or more mercapto groups in the molecule, and includes a compound represented by the following formula (137).

However, R ²³ is as defined above.

  Specific examples of the compound (v) include 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,2-butanedithiol, 1,3-butanedithiol, 2,3- Butanedithiol, 1,4-butanedithiol, 2,5-dimercapto-1,3,4-thiadiazole, dimercaptobenzene, dimercaptotoluene, dimercaptoxylene, 1,5-dimercapto-3-thiapentane, 1,8- Dimercapto-3,6-dioxaoctane, dimercaptonaphthalene, (±) -dithiothreitol, dithioerythritol, bis (3-mercaptopropionic acid) 1,4-butanediol, bis (3-mercaptopropionic acid) ethylene glycol Bis (3-mercaptopropionic acid) tetraethylene glycol, tris (3-mercapto Propionic acid) trimethylolpropane, tetrakis (3-mercaptopropionic acid) pentaerythritol, hexakis (3-mercaptopropionic acid) dipentaerythritol, and the like. Can also be selected, but is not limited thereto.

  Moreover, the said compound (v) is marketed, and they can be used in this invention. Commercially available products include Toray Fine Chemical Co., Ltd. trade names; Thiocol LP-32, Thiocol LP-3, Thiocol LP-33, Thiocol LP-2, etc., PTI trade names; Capcure 3-800, Capcure 40 sec, etc. Product name: QE340, QE340M, etc., Japan Epoxy Resins Co., Ltd .; QX-11, QX-40, etc., Asahi Denka Kogyo Co., Ltd .; EH-310, EH-317, etc., Maruzen Chemical Co., Ltd. DMDS, DMDO, etc., trade names manufactured by Sanyo Chemical Industries, Ltd .; Neoquick LP2840, and the like, but are not limited thereto.

但し、Ｒ²³及びＲ²⁵は上記と同意義である。
上記化合物（ｗ）の具体例としては、アミノメチルチオール、２−アミノエチルチオール、３−アミノプロピルチオール、４−アミノブチルチオール、ｏ−アミノチオフェノール、ｐ−アミノチオフェノール等が挙げられるが、これらに限定されるものではない。 The compound (w) is an aminothiol compound having at least one amino group and at least one mercapto group in the molecule, and includes a compound represented by the following formula (138).

However, R ²³ and R ²⁵ are as defined above.
Specific examples of the compound (w) include aminomethylthiol, 2-aminoethylthiol, 3-aminopropylthiol, 4-aminobutylthiol, o-aminothiophenol, p-aminothiophenol, It is not limited to these.

但し、Ｒ¹、Ｒ³上記と同意義である。
上記化合物（ｘ）の具体例としては、アリルイソチオシアネート等が挙げられるが、これらに限定されるものではない。 The compound (x) is an alkenyl isothiocyanate compound having at least one alkenyl group and at least one isothiocyanate group in the molecule, and includes a compound represented by the following formula (139).

However, R ¹ and R ³ are as defined above.
Specific examples of the compound (x) include, but are not limited to, allyl isothiocyanate.

但し、Ｒ¹、Ｒ³、Ｙは上記と同意義である。
上記化合物（ｙ）の具体例としては、アリルイソシアネート、ｍ−イソプロペニル−α，α−ジメチルベンジルイソシアネート、２−メタクリロイロキシエチルイソシアネート、三井武田ケミカル社製商品名；ｍ−ＴＭＩ、昭和電工社製商品名；カレンズＭＯＩ等が挙げられるが、これらに限定されるものではない。 The compound (y) is an alkenyl isocyanate compound having at least one alkenyl group and at least one isocyanate group in the molecule, and includes a compound represented by the following formula (140).

However, R ¹ , R ³ and Y are as defined above.
Specific examples of the compound (y) include allyl isocyanate, m-isopropenyl-α, α-dimethylbenzyl isocyanate, 2-methacryloyloxyethyl isocyanate, trade names manufactured by Mitsui Takeda Chemical Company; m-TMI, Showa Denko Product name; Karenz MOI and the like, but not limited thereto.

The compound (z) is a polyisocyanate compound having at least two or more isocyanate groups in the molecule, and examples thereof include diisocyanate compounds, polyisocyanate compounds excluding diisocyanate compounds, and the like. Examples of the diisocyanate compound include aliphatic, alicyclic, araliphatic, and aromatic diisocyanate compounds. Specific examples thereof will be given below.
Aliphatic diisocyanate compounds: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2, 4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, and the like.

Alicyclic diisocyanate compound: 1,3-cyclopentene diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl) Isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like.
Aroaliphatic diisocyanate compounds: 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, ω, ω'-diisocyanate-1,4-diethylbenzene, 1,3- or 1,4-bis (1-isocyanate) -1-methylethyl) benzene or a mixture thereof. Aromatic diisocyanate compounds: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, and the like.

Examples of the polyisocyanate compound excluding the diisocyanate compound include, but are not limited to, aliphatic, alicyclic, araliphatic, and aromatic polyisocyanate compounds.
Specific examples thereof will be given below.
Aliphatic polyisocyanate compounds: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-tri Isocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane, and the like.

  Alicyclic polyisocyanate compound: 1,3,5-triisocyanatecyclohexane, 1,3,5-trimethylisocyanatecyclohexane, 3-isocyanate-3,3,5-trimethylcyclohexylisocyanate, 2- (3-isocyanatepropyl)- 2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2- (3-isocyanatopropyl) -2,6-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 5 -(2-isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2-isocyanatomethyl-3- (3 -Isocyanatopropyl) -bicyclo [2,2,1] heptane, -(2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2- (3-isocyanatopropyl)- Bicyclo [2,2,1] heptane and the like.

Aro-aliphatic polyisocyanate compound: 1,3,5-triisocyanate methylbenzene and the like.
Aromatic polyisocyanate compounds: triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatebenzene, 2,4,6-triisocyanatetoluene, 4,4′-diphenylmethane-2, 2 ', 5,5'-tetraisocyanate and the like.
Other polyisocyanate compounds: diisocyanates containing sulfur atoms such as phenyl diisothiocyanate.

"Description of the above compound groups (A) to (E)"
The compound group (A) represents a compound group having at least one silicon-containing characteristic group in the molecule and a functional group capable of reacting with at least one isocyanate group and / or isothiocyanate group in the molecule. The compound group (A) includes the compound (c), the compound (d), and the compound (e).
The compound group (B) represents a compound group having at least one alkenyl group and at least one isocyanate group and / or isothiocyanate group in the molecule. The compound group (B) includes the compound (y) and the compound (x).

The compound group (C) represents a compound group having at least one silicon-containing characteristic group and at least one isocyanate group and / or isothiocyanate group in the molecule. The compound group (C) includes the compound (a), the compound (b), an isocyanate group-containing compound obtained by reacting the compound (z) and the compound group (A), and the compound group (B). And an isocyanate group-containing or isothiocyanate group-containing compound obtained by reacting the compound (f) with an isocyanate group-containing or isothiocyanate group-containing compound obtained by reacting the compound group (B) and the compound (g). included. The reaction between the compound (z) and the compound group (A) and the reaction between the compound group (B) and the compound (f) may be carried out by the following reaction method (2). Further, the reaction between the compound group (B) and the compound (g) may be carried out by the following reaction method (3) which is publicly known.

The compound group (D) represents a compound group having at least one silicon-containing characteristic group, at least one epoxy group and / or an α, β-unsaturated carbonyl group in the molecule. The compound group (D) includes the compound (h) and the compound (i).
The compound group (E) represents a compound group having at least one silicon-containing characteristic group and at least one primary amino group, secondary amino group and / or mercapto group in the molecule. The compound group (E) includes the compound (c) and the compound (f).

“Description of the above reaction methods (1) to (4)”
The reaction method (1) is a known conventional method for carrying out a nucleophilic addition reaction. The nucleophilic addition reaction involves reacting with an isocyanate group and / or an isothiocyanate group and an isocyanate group and / or an isothiocyanate group. Reaction with functional groups (specifically, primary amino group, secondary amino group, hydroxyl group and mercapto group), epoxy group and primary amino group, secondary amino group or mercapto group Reaction, reaction of α, β-unsaturated carbonyl compound or acrylonitrile compound with primary amino group, secondary amino group or mercapto group (generally called Michael addition type reaction or Michael addition reaction) It is. Specifically, the reaction may be performed at −20 ° C. to + 150 ° C. for about 1 hour to 1000 hours. In this reaction method (1), a known reaction catalyst such as a metal compound (S-1) such as a tin compound and / or an amine compound (S-2) can be used. Furthermore, in this reaction method (1), a known reaction solvent (S-3) can be used. The metal compound and amine compound used as a catalyst and the reaction solvent are not particularly limited as long as they are suitable for each raw material or reaction, but specifically, the following can be used.
The reaction method (2) is a known ordinary method for performing a radical addition reaction between an alkenyl group and a mercapto group. Specifically, the reaction may be performed in the temperature range of 40 to 150 ° C. for about 1 to 500 hours. This radical addition reaction is performed in the presence of a radical initiator (S-4). Furthermore, this radical addition reaction is also possible by ultraviolet irradiation. Furthermore, this radical addition reaction can also be performed in the presence of a reaction catalyst (S-3).

In the reaction method (3) , a metal compound (S-5) such as a group VII transition metal compound is used as a catalyst to cause an addition reaction between the hydrosilane moiety of the hydrosilane compound represented by the above formula (61) and an alkenyl group. It is a known ordinary method. For example, the method of adding the above hydrosilane compound to an alkenyl-terminated polyether compound is described in JP-B Nos. 45-36319, 46-12154, 49-32673, JP-A-50-156599, and 51-73561. 54-6096, 55-82123, 55-123620, 55-125121, 55-133122, 55-135135, 55-137129, JP-B 46-12154, Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 2512468, Japanese Patent Application Laid-Open No. 64-22904, Japanese Patent Publication No. 2539445, and the like.

The reaction method (4) is a known ordinary method in which a polymerization reaction is performed using a compound having a polymerizable alkenyl group. Specifically, a radical initiator (S-4) and / or a chain transfer agent (S-6) is added to the compound having a polymerizable alkenyl group as necessary, and the temperature is 50 to 150 ° C. for 1 to 12 hours. React to a certain extent. Moreover, a reaction solvent (S-3) can be used. Furthermore, you may carry out in presence of curable resin (A) and / or another curable compound (M) as described in this invention. The polymerization method is not particularly limited, and a known radical polymerization reaction, cation polymerization reaction, or anion polymerization reaction can be used, but a radical polymerization reaction is preferable because of the ease of the reaction. The polymerization reaction may be a living polymerization reaction or not a living polymerization reaction.

Examples of the metal compound (S-1) include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dimaleate, dioctyltin dimaleate, dibutyltin phthalate, dioctyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin dimethoxide, dioctyl Tin dimethoxide, dibutyltin diacetylacetate, dioctyltin diacetylacetate, dibutyltin diversate, dioctyltin diversate, reaction product of dibutyltin oxide and phthalic diester, tin compounds such as tin stearate, bismuth compounds, Nitto Kasei Co., Ltd. Product name: T-100, U-100, U-130, U-15, U-20, U-200, U-220, U-230, U-28, U-300, U-303, U- 317, U-340U-40 , U-50, U-500, U-550, U-600, U-660, U-700, U-700ES, U-8, U-800, U-810, U-830, U-ES, U -280, U-350, U-360, U-840, U-850, U-860, U-870, trade names manufactured by Sansha Co., Ltd .; SCAT-1, SCAT-1W, SCAT-4A, SCAT- 7, SCAT-8, SCAT-8B, SCAT-24, SCAT-25, SCAT-27, SCAT-31A, SCAT-32A, SCAT-46A, SCAT-51, SCAT-52A, No. 7 918, STANNBL, STANNSNT-1F, trade name of Sumika Bayer Urethane Co., Ltd .; Desmorapide PA, Desmorrapid SO, acetylacetone metal salts such as aluminum or chromium, and the like are included, but are not limited thereto It is not a thing.

Examples of the amine compound (S-2) include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, trimethylamine, triethylamine, and tributylamine. Aliphatic amines such as oleylamine; mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, 1,2-diaminocyclohexane, bis (4-amino-3- Methylcyclohexyl) methane, bis (4-amino-methylcyclohexyl) methane, polycyclohexylpolyamine, 1,8-diazabicyclo [5,4 0] Cycloaliphatic amines such as undecene-7 (DBU); aromatic amines such as metaphenylenediamine and 4,4′-diaminodiphenylsulfone; m-xylylenediamine, benzyldimethylamine, 2- (dimethylamino) Fatty aromatic amines such as methyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol; 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5 , 5] Undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylene diamine, polyoxypropylene triamine, polyoxyethylene diamine and other amine-containing amines; diethanolamine, triethanolamine and other hydroxyl group-containing amines; Dimer triamine or diethyl to dimer acid Polyamides obtained by reacting polyamines such as tetramine, polyamide polyamides using polycarboxylic acids other than dimer acid; imidazoles such as 2-ethyl-4-methylimidazole; dicyandiamide, polyoxypropylene diamine, poly Polyoxypropylene-based amines such as oxypropylene-based triamines; epoxy-modified amines obtained by reacting the above amines with epoxy compounds, Mannich-modified amines obtained by reacting the above amines with formalin and phenols, Michael addition modification Modified amines such as amine and ketimine; compounds such as amine salts such as 2-ethylhexanoate of 2,4,6-tris (dimethylaminomethyl) phenol, tetramethylammonium chloride, benzalkonium chloride, etc. Quaternary ammonium salts, DABCO (registered trademark) series, DABCO BL series, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3 manufactured by Sankyo Aero Products, Ltd. .0] -5-nonene, 1,4-diazabicyclo [2.2.2] linear or cyclic tertiary amine salt containing a plurality of nitrogen atoms such as octane, γ-aminopropyltrimethoxysilane, γ -Aminosilanes such as aminopropyltriethoxysilane, trade names manufactured by Sumika Bayer Urethane Co., Ltd .; Desmorapid DB, Desmorapid PP, Desmorapid PV, Desmorapide 10/9, Desmorapid LA, etc. are limited thereto. Is not to be done.

Examples of the reaction solvent (S-3) include aliphatic hydrocarbons such as hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene, alicyclic hydrocarbons such as cyclohexane and cycloheptane, ethyl acetate, and butyl acetate. Ester compounds such as acetone, methyl ethyl ketone, ether compounds such as diethyl ether and tetrahydrofuran, alcohol compounds such as methanol, ethanol, propanol and butanol, amide compounds such as dimethylformamide and diethylformamide, dimethyl sulfoxide, diethyl sulfoxide, etc. However, it is not limited to these.

Examples of the radical initiator (S-4) include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4- Dimethylvaleronitrile), 2,2'-azobis (2-methyl-4-trimethoxysilylpentonitrile), 2,2'-azobis (2-methyl-4-methyldimethoxysilylpentonitrile), Wako Pure Chemical Industries, Ltd. Product names: VA-066B, VA-057, VA-061, VA-085, VA-086, VA-096, V-601, V-65, VAm-110 and other azo compounds, benzoyl peroxide, t- Peroxides such as alkyl peroxyesters, acetyl peroxide and diisopropyl peroxycarbonate are used.
Examples of the metal compound (S-5) include platinum compounds such as platinum black, chloroplatinic acid, platinum alcohol compounds, platinum olefin complexes, platinum aldehyde complexes, and platinum ketone complexes, but are not limited thereto. is not.

Examples of the chain transfer agent (S-6) include n-butyl mercaptan, ethylthioglycolate, isopropyl mercaptan, t-butyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, thiophenol, thio- β-naphthol, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-trimethoxysilylpropyl disulfide, compound (e), compound (f), compound (o) and other mercapto compounds, benzene, toluene Aromatic hydrocarbon compounds such as disulfide compounds, disulfide bond-containing silane coupling agents, and the like, but are not limited thereto.

The curable compound (M) is not particularly limited as long as it is a curable compound other than the curable resin (A) in the present invention. Specifically, organopolysiloxane, modified silicone (for example, trade name manufactured by Kaneka Chemical Co., Ltd .; S203, S303, S810, SAT010, SAT030, SAT070, SAT200, SAT350, SAT400, S203, S810, MA903, MA904, MAX923) , S911, S943, EST200, EST250, ESX280, SAT070, SAX720, SAX725, SAX770, MA430, MA440, MA440A, MA447, MAX610, etc., trade names made by Asahi Glass; ES-S2410, ES-S2420, ES-S3430, ES- S3630, etc.), Japanese Patent Publication No. 4-69659, Japanese Patent Publication No. 7-108928, Japanese Patent Publication No. 2512468, Japanese Patent Application Laid-Open No. 64-22904, Japanese Patent Publication No. 2539445, etc. Reactive silyl group-containing saturated hydrocarbon polymer, trade name manufactured by Kaneka Chemical Co., Ltd .; Epion series, reactive silyl group-containing vinyl polymer (for example, trade name manufactured by Kaneka Chemical Co., Ltd .; SA100S, OR100S, SA300S, SA110S, etc.), silicone alkoxy oligomers (for example, trade names manufactured by Shin-Etsu Chemical Co., Ltd .; KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-217, KR-9218, KR-213, KR-510, X-40-9227, X-40-9247, X-41-1053, X-41-1056, X-40-1805, X-40-1810, X- 40-2651, X-40-2308, X-40-9238, etc.), silane compounds (for example, vinyltrimethoxysilane, vinylmethyl) Vinylsilane compounds such as methoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltrichlorosilane, bis (3-trimethoxysilylpropyl) tetrasulfane, bis (3-methyldimethoxysilylpropyl) tetrasulfane, bis ( 3-triethoxysilylpropyl) tetrasulfane, bis (3-methyldiethoxysilylpropyl) tetrasulfane, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) disulfide, bis (3 -Triethoxysilylpropyl) disulfide, silane compounds having sulfide bonds such as bis (3-methyldiethoxysilylpropyl) disulfide, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanate Anurate silane, 1,3,5-N-tris (3-methyldimethoxysilylpropyl) isocyanurate silane, 1,3,5-N-tris (3-triethoxysilylpropyl) isocyanurate silane, 1,3, Isocyanurate silane compounds such as 5-N-tris (3-methyldiethoxysilylpropyl) isocyanurate silane, the compound (a), the compound (b), the compound (c), the compound (d), and the compound (E), compound (f), compound (h), compound (i), compound (j), etc.), epoxy resin having at least one epoxy group in the molecule, at least one in the molecule Urethane prepolymer having an isocyanate group, titanium coupling agent, silicate compound (for example, methyl silicate, ethyl silicate) Over DOO, produced by Mitsubishi Chemical Corporation, trade name; MS51) or the like including without being limited thereto.

  In addition, the curable resin (A) used in the present invention includes JP-A Nos. 11-100197, 2000-143757, 2000-169544, 2002-212415, No. 2004-123900, JP-A-2004-123901, Japanese Patent No. 3030020, Japanese Patent No. 3295663, Japanese Patent No. 3313360, Japanese Patent No. 3317353, Japanese Patent No. 3350011, etc. Silylated urethane resins, and curable resins carbonated by the action of carbon dioxide on an epoxy resin and then silylated with an aminosilane compound, JP-A 63-83131, JP-A 63-83160, JP Terminal epoxy group polymer as proposed in 2-238045 etc. Aromatic dithiol compound and / or an aromatic diimino compounds curable resin obtained by adding epoxy silane compound was terminated thiolated by the action of the like are also included.

Of the curable resins suitably used in the present invention, oxyalkylene polymers having a main chain skeleton include those described in JP-B Nos. 45-36319, 46-12154, 49-32673, and JP-A-50-156599. No. 51-73561 No. 54-6096 No. 55-82123 No. 55-123620 No. 55-125121 No. 55-13122 No. 55-135135 No. 55-137129 No. Resins generally referred to as modified silicones proposed in each publication are included.
As a method for producing the oxyalkylene polymer, a method in which an alkenyl group of a polyoxyalkylene having an alkenyl group is subjected to an addition reaction of a silicon hydride compound having the silicon-containing characteristic group in the molecule, or an alkenyl group is included. A method of radically adding a mercapto group of a mercaptosilane compound having a mercapto group and a silicon-containing characteristic group in the molecule to an alkenyl group of polyoxyalkylene is well known.

  Furthermore, examples of the curable resin suitably used in the present invention include reactive silyl group-containing vinyl polymers (for example, JP-A-9-272715, JP-A-9-272714, JP-A-11-080249, etc. -080250, etc., JP-A-11-005815, etc., JP-A-11-116617, etc., JP-A-11-116606, etc., JP-A-11-080571, etc., JP-A-11-080570, etc., JP-A-11-130931, etc. JP 1003133, JP 11-116763, JP 2003-82192, etc., JP 2003-119339, JP 2003-171416, JP 2003-246861, JP 2003-327852, JP 2003-327620. Reactive silyl group-containing vinyl polymerization described in JP-A-2004-002835 Product name manufactured by Toagosei Co., Ltd .; Reactive plasticizer XPR series such as XPR-15 and XPR-22; Product name manufactured by Soken Chemical Co., Ltd .; Actflow AS-300, Actflow AS-301, Actflow ASM-4001, etc.) Trade names manufactured by Kaneka Chemical Co., Ltd .; SA100S, OR100S, SA300S, SA110S, and the like.

  The said curable resin (A) is marketed and can be used in this invention. Examples of commercially available products include polyoxyalkylenes containing hydrolyzable silyl groups (for example, trade names manufactured by Asahi Glass Co., Ltd .; ES-GX3440ST, etc.), polyolefins containing hydrolyzable silyl groups (for example, trade names made by Degussa Japan); VESTOPLAST 206, etc.), a vinyl polymer containing a hydrolyzable silyl group (for example, product name manufactured by Toagosei Co., Ltd .; reactive plasticizer XPR series such as XPR-15, XPR-22, product name manufactured by Soken Chemical Co., Ltd .; Actflow) AS-300, Actflow AS-301, Actflow ASM-4001, trade names manufactured by Kaneka Chemical Industry Co., Ltd .; SA100S, OR100S, SA300S, SA110S, etc.), hydrolyzable polyoxyalkylenes containing hydrolyzable silyl groups Mixed resin with vinyl polymer containing silyl group (eg Kaneka Chemical Company trade name; MA430, MA440, MA440A, MA447, MAX610, etc.) and the like.

II. About the Lewis acid and / or its complex (B) The Lewis acid and / or its complex (B) has a hydrolyzable silyl group and a silanol group in the molecule, and a specific compound such as a urethane bond in the molecule. It is useful as a curing catalyst for the curable resin (A) containing a bond and / or a group, and cures the curable resin (A) in a very short time.
Examples of the Lewis acid that can be suitably used in the present invention include titanium chloride, tin chloride, zirconium chloride, aluminum chloride, iron chloride, zinc chloride, zinc bromide, copper chloride, antimony chloride and other metal halides, and trifluoride. And boron halide compounds such as boron halide and boron trichloride. The effect on the curability of the curable resin (A) is considered to be influenced by the acid strength of the Lewis acid. Examples of the Lewis acid complex include, but are not limited to, amine complexes, alcohol complexes, and ether complexes. Examples of the amine compound used for the amine complex include ammonia, monoethylamine, triethylamine, pyridine, piperidine, aniline, morpholine, cyclohexylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, and the above compound (c). However, it is not limited to these. Examples of alcohols used in the alcohol complex include primary alcohols such as methanol, ethanol, propanol and n-butanol, and secondary alcohols such as isopropanol and 2-butanol, but are not limited thereto. Examples of ethers used in the ether complex include, but are not limited to, dimethyl ether, diethyl ether, and n-dibutyl ether.
Among the Lewis acids, titanium chloride (IV), tin chloride (IV), zirconium chloride (IV), aluminum chloride (III), and boron trifluoride are preferable. From the viewpoint of stability, zirconium chloride (IV), three Boron fluoride is more preferable, and boron trifluoride is particularly preferable from the viewpoint of catalytic activity.

As the Lewis acid complex, a boron trifluoride complex is particularly preferable because it is easy to handle. Of the boron trifluoride complexes, amine complexes having both stability and catalytic activity are particularly preferred. Such boron trifluoride amine complexes are commercially available and can be used in the present invention. Commercially available products of boron trifluoride amine complexes include trade names manufactured by Air Products Japan, Inc .: Anchor 1040, Anchor 1115, Anchor 1170, Anchor 1222, BAK 1171, and the like.
The said Lewis acid and / or its complex (B) may be used independently, and may be used together 2 or more types. The blending ratio of the Lewis acid and / or its complex (B) is preferably 0.001 to 10 parts by weight, more preferably 0.01 to 5 parts by weight per 100 parts by weight of the curable resin (A). Part.

III. About the aminosilane compound (C) The aminosilane compound (C) is a silicon-containing compound comprising at least one group selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the formula (1) in the molecule. It is an aminosilane compound containing a characteristic group and an amino group in the molecule. Specific examples of the aminosilane compound (C) include compounds contained in the compound (c), but are not limited thereto.
Although the compounding quantity of the said aminosilane compound (C) is not specifically limited, Preferably it is 0.1-20 weight part per 100 weight part of curable resin (A), Most preferably, it is 1-10 weight part.

IV. About the mercaptosilane compound (D) The mercaptosilane compound (D) comprises one or more groups selected from the group consisting of hydrolyzable silyl groups and silanol groups represented by the formula (1) in the molecule. It is a mercaptosilane compound containing a silicon-containing characteristic group and a mercapto group in the molecule. Specific examples of the mercaptosilane compound (D) include compounds contained in the compound (e) and the compound (f), but are not limited thereto.
Although the compounding quantity of the said mercaptosilane compound (D) is not specifically limited, Preferably it is 0.1-20 weight part per 100 weight part of curable resin (A), Most preferably, it is 1-10 weight part.

V. About the said curing catalyst (E) The said curing catalyst (E) is a curing catalyst which can be used together with the said Lewis' acid and / or its complex (B). Specifically, the curing catalyst (E) includes organic tin compounds, organic metal compounds other than organic tin compounds, bases such as amines, and acids such as carboxylic acids and organic phosphoric acid compounds.
Examples of the organotin compound contained in the curing catalyst (E) include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dimaleate, dioctyltin dimaleate, dibutyltin phthalate, dioctyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyl Examples include tin dimethoxide, dioctyl tin dimethoxide, dibutyl tin diacetyl acetate, dioctyl tin diacetyl acetate, dibutyl tin diversate, dioctyl tin diversate, reaction products of dibutyl tin oxide and phthalic acid diester, and tin compounds such as tin stearate. However, it is not limited to these.

上記式（１４１）において、Ｒ２９及びＲ３０は、炭素数１〜１２個の置換若しくは非置換の炭化水素基を、ｕは１以上の整数をそれぞれ示し、Ｒ²⁹及びＲ³⁰は同じでも異なっても良い。
Ｒ²⁹及びＲ³⁰で表される炭素数１〜１２個の置換若しくは非置換の炭化水素基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ−ブチル、ｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、２−エチルヘキシル、デシル、ラウリル等の直鎖状若しくは分枝直鎖状アルキル基、置換若しくは非置換のフェニル基等が挙げられる。ｕは１以上の整数であれば良いが、好ましくは１〜３の整数である。 Moreover, the said organotin compound contained in a curing catalyst (E) can also use the poly (dialkyl stannoxane) dicarboxylate represented by following formula (141) other than said compound.

In the above formula (141), the R29 and R30, the hydrocarbon group substituted or unsubstituted 1 to 12 carbon atoms, u represents an integer of 1 or more, respectively, R ²⁹ and R ³⁰ are be the same or different good.
Examples of the substituted or unsubstituted hydrocarbon group having 1 to 12 carbon atoms represented by R ²⁹ and R ³⁰ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl. , Heptyl, octyl, 2-ethylhexyl, decyl, lauryl and the like linear or branched linear alkyl groups, substituted or unsubstituted phenyl groups, and the like. u may be an integer of 1 or more, preferably an integer of 1 to 3.

  Specific examples of the poly (dialkylstannoxane) dicarboxylate represented by the above formula (141) include 1,1,3,3-tetramethyl-1,3-bis (acetoxy) distanoxane, 1,1,3, 3,3-tetramethyl-1,3-bis (butyryloxy) distanoxane, 1,1,3,3-tetramethyl-1,3-bis (octanoyloxy) distanoxane, 1,1,3,3-tetramethyl -1,3-bis (2-ethylhexanoyloxy) distanoxane, 1,1,3,3-tetramethyl-1,3-bis (lauroyloxy) distanoxane, 1,1,3,3-tetrabutyl-1, 3-bis (acetoxy) distanoxane, 1,1,3,3-tetrabutyl-1,3-bis (butyryloxy) distanoxane, 1,1,3,3-tetrabutyl- , 3-bis (octanoyloxy) distanoxane, 1,1,3,3-tetrabutyl-1,3-bis (2-ethylhexanoyloxy) distanoxane, 1,1,3,3-tetrabutyl-1,3- Bis (lauroyloxy) distanoxane, 1,1,3,3-tetraoctyl-1,3-bis (acetoxy) distanoxane, 1,1,3,3-tetraoctyl-1,3-bis (butyryloxy) distanoxane, 1 1,1,3,3-tetraoctyl-1,3-bis (octanoyloxy) distanoxane, 1,1,3,3-tetraoctyl-1,3-bis (2-ethylhexanoyloxy) distanoxane, 1, 1,3,3-tetraoctyl-1,3-bis (lauroyloxy) distanoxane, 1,1,3,3-tetralauryl-1,3-bi (Acetoxy) distanoxane, 1,1,3,3-tetralauryl-1,3-bis (butyryloxy) distanoxane, 1,1,3,3-tetralauryl-1,3-bis (octanoyloxy) distanoxane, , 1,3,3-tetralauryl-1,3-bis (2-ethylhexanoyloxy) distanoxane, 1,1,3,3-tetralauryl-1,3-bis (lauroyloxy) distanoxane Distanoxane dicarboxylate, 1,1,3,3,5,5-hexamethyl-1,5-bis (acetoxy) tristanoxane, 1,1,3,3,5,5-hexamethyl-1,5- Bis (butyryloxy) tristanoxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (octanoyloxy) tristanoxa 1,1,3,3,5,5-hexamethyl-1,5-bis (2-ethylhexanoyloxy) tristanoxane, 1,1,3,3,5,5-hexamethyl-1,5 -Bis (lauroyloxy) tristanoxane, 1,1,3,3,5,5-hexabutyl-1,5-bis (acetoxy) tristanoxane, 1,1,3,3,5,5-hexabutyl- 1,5-bis (butyryloxy) tristanoxane, 1,1,3,3,5,5-hexabutyl-1,5-bis (octanoyloxy) tristanoxane, 1,1,3,3,5, 5-hexabutyl-1,5-bis (2-ethylhexanoyloxy) tristanoxane, 1,1,3,3,5,5-hexabutyl-1,5-bis (lauroyloxy) tristanoxane, 1, 1,3,3,5,5-hex Lauryl-1,5-bis (acetoxy) tristanoxane, 1,1,3,3,5,5-hexalauryl-1,5-bis (butyryloxy) tristanoxane, 1,1,3,3,5 , 5-Hexalauryl-1,5-bis (octanoyloxy) tristanoxane, 1,1,3,3,5,5-hexalauryl-1,5-bis (2-ethylhexanoyloxy) tristano And hexaalkyltristanoxane dicarboxylates such as xanthane, 1,1,3,3,5,5-hexalauryl-1,5-bis (lauroyloxy) tristanoxane.

上記式（１４２）において、Ｒ³¹及びＲ³²は炭素数１〜４個のアルキル基を、ｖは０〜３個の整数をそれぞれ示し、Ｒ³¹及びＲ³²は同じでも異なっても良く、Ｒ³¹及びＲ³²は複数の場合はそれらは同じでも異なっても良い。Ｒ³¹及びＲ³²で表される炭素数１〜４個のアルキル基は、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｓ−ブチル、ｔ−ブチルである。 Furthermore, the poly (dialkylstannoxane) dicarboxylate represented by the above formula (141) can be a reaction product with a silicate compound represented by the following formula (142).

In the above formula (142), R ³¹ and R ³² represent an alkyl group having 1 to 4 carbon atoms, v represents an integer of 0 to 3, and R ³¹ and R ³² may be the same or different. ^In the case where a plurality of ³¹ and R ³² are present, they may be the same or different. The alkyl group having 1 to 4 carbon atoms represented by R ³¹ and R ³² is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl.

  Specific examples of the silicate compound represented by the above formula (142) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane, triethoxymethylsilane, and triethoxy. Trialkoxymonoalkylsilanes such as ethylsilane, triethoxypropylsilane, triethoxyisopropylsilane, triethoxybutylsilane, diethoxydimethylsilane, diethoxydiethylsilane, diethoxydipropylsilane, diethoxydiisopropylsilane, diethoxydibutylsilane Dialkoxydialkylsilane, ethoxytrimethylsilane, ethoxytriethylsilane, ethoxytripropylsilane, ethoxytriisopropylsilane, ethoxy Monoalkoxysilane trialkylsilane such as tributyl silane. The hydrolyzate of these alkoxysilanes can also be used similarly to these alkoxysilanes.

上記式（１４３）において、Ｒ³⁰及びＲ³²及びｕは前記と同意義である。また、上記式（１４１）及び上記式（１４３）におけるＲ³⁰がオクチル基であるとき、本発明に好適に用いられるジオクチル錫系触媒となる。 Poly (dialkylstannoxane) which is a reaction product of poly (dialkylstannoxane) dicarboxylate represented by the above formula (141) and a silicate compound represented by the above formula (142) and / or a hydrolyzate thereof. ) The disilicate compound is obtained by reacting both at 100 to 130 ° C. for about 1 to 3 hours and removing the resulting carboxylic acid ester under reduced pressure. As for the reaction ratio of both, it is preferable to react 1 equivalent or more of an alkoxy group with respect to 1 equivalent of a carboxyl group to completely eliminate the carboxyl group. If the carboxyl group remains, the catalytic activity decreases. Although this reaction can be carried out in the presence or absence of a solvent, it is usually preferably carried out in the absence of a solvent. Poly (dialkylstanol) which is a reaction product of the poly (dialkylstannoxane) dicarboxylate represented by the above formula (141) and the silicate compound represented by the above formula (142) and / or a hydrolyzate thereof. A specific example of the reaction product with the xanthine disilicate compound is a compound represented by the following formula (143).

In the above formula (143), R ^30, R ³² and u are as defined above. Further, when R ³⁰ in the above formula (141) and the above formula (143) is an octyl group, it becomes a dioctyl tin-based catalyst suitably used in the present invention.

  The organotin compounds contained in the curing catalyst (E) are commercially available, and they can be used in the present invention. As a commercial item, Nitto Kasei Co., Ltd. brand name; T-100, U-100, U-130, U-15, U-20, U-200, U-220, U-230, U-28, U- 300, U-303, U-317, U-340U-400, U-50, U-500, U-550, U-700, U-700ES, U-8, U-800, U-810, U- 830, U-ES, U-280, U-350, U-360, U-840, U-850, U-860, U-870, etc., trade names manufactured by Sansha Co., Ltd .; SCAT-1, SCAT- 1W, SCAT-4A, SCAT-7, SCAT-8, SCAT-8B, SCAT-24, SCAT-25, SCAT-27, SCAT-31A, SCAT-32A, SCAT-46A, SCAT-51, SCAT-52A, No. 918, STANNBL, STANNSNT-1F, etc., trade names made by Sumika Bayer Urethane Co., Ltd .; Desmolapide PA, Desmolrapid SO and the like can be mentioned, but are not limited thereto.

  Examples of organometallic compounds other than the organotin compounds contained in the curing catalyst (E) include titanate compounds such as bismuth compounds, tetrabutyl titanate, tetraisopropyl titanate, and triethanolamine titanate in which tin of the organotin compound is replaced with bismuth. Carboxylic acid metal salts such as lead octylate, lead naphthenate, nickel naphthenate, lithium naphthenate, cobalt naphthenate, etc., metal acetylacetonate complexes such as aluminum acetylacetonate complex, vanadium acetylacetonate complex, Nitto Kasei Co., Ltd. Product names; U-600, U-660, and the like are listed, but the product names are not limited to these.

  Examples of the amines contained in the curing catalyst (E) include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, methylpentamethylenediamine, trimethylhexamethylenediamine, guanidine, trimethylamine, and triethylamine. Aliphatic amines such as tributylamine and oleylamine; mensendiamine, isophoronediamine, norbornanediamine, piperidine, N, N′-dimethylpiperazine, N-aminoethylpiperazine, 1,2-diaminocyclohexane, bis (4-amino) -3-methylcyclohexyl) methane, bis (4-amino-methylcyclohexyl) methane, polycyclohexylpolyamine, 1,8-diazabicycle Alicyclic amines such as [5,4,0] undecene-7 (DBU); aromatic amines such as metaphenylenediamine and 4,4′-diaminodiphenylsulfone; m-xylylenediamine, benzyldimethylamine, Aliphatic aromatic amines such as 2- (dimethylaminomethyl) phenol and 2,4,6-tris (dimethylaminomethyl) phenol; 3,9-bis (3-aminopropyl) -2,4,8,10- Amines having an ether bond such as tetraoxaspiro [5,5] undecane (ATU), morpholine, N-methylmorpholine, polyoxypropylenediamine, polyoxypropylenetriamine, polyoxyethylenediamine; hydroxyls such as diethanolamine and triethanolamine Group-containing amines; dimer triamine to dimer acid Polyamides obtained by reacting polyamines such as benzene and diethylenetetramine, polyamide polyamides using polycarboxylic acids other than dimer acid; imidazoles such as 2-ethyl-4-methylimidazole; dicyandiamide, polyoxypropylene diamine Polyoxypropylene-based amines such as polyoxypropylene-based triamines; epoxy-modified amines obtained by reacting the above amines with epoxy compounds, Mannich-modified amines obtained by reacting the above amines with formalin and phenols, Michael Modified amines such as addition-modified amines and ketimines; 2,4,6-tris (dimethylaminomethyl) phenol compounds such as 2-ethylhexanoate, tetramethylammonium chloride, benzalkonium chloride Quaternary ammonium salts such as rholide, DABCO (registered trademark) series, DABCO BL series, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4] manufactured by Sankyo Aero Products .3.0] -5-nonene, 1,4-diazabicyclo [2.2.2] linear or cyclic tertiary amine salt containing a plurality of nitrogen atoms such as octane, the above compound (c), Product names manufactured by Kabayer Urethane Co., Ltd .; Desmolapide DB, Desmolapid PP, Desmolapid PV, Desmolapid 10/9, Desmorapid LA, and the like are exemplified, but are not limited thereto.

Examples of the organic phosphoric acid compound contained in the curing catalyst (E) include monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, monoethyl phosphate, diethyl phosphate, triethyl phosphate, di-n-butyl phosphate, mono-n-butyl phosphate, tri-phosphate phosphate. Examples thereof include, but are not limited to, n-butyl and triphenyl phosphate.
The said curing catalyst (E) may be used independently and may be used together 2 or more types. The blending ratio of the curing catalyst (E) is preferably 0.01 to 10 parts by weight, particularly preferably 0.02 to 5 parts by weight, per 100 parts by weight of the curable resin (A).
The curable resin composition according to the present invention includes, for example, an adhesive, a sealant, a paint, a coating agent, a sealant (for example, a sealant for covering a crack so that an injection agent does not leak in repairing a concrete crack), Although used suitably for uses, such as a casting material and a coating | covering material, when using for these uses, it is preferable to mix | blend a silane coupling agent, a filler, various additives, etc. further according to the performance requested | required. In particular, it is preferable to blend a silane coupling agent and a filler.

  Examples of the silane coupling agent that can be blended in the curable resin composition according to the present invention include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltrichlorosilane, and other vinylsilane compounds, bis (3-trimethoxysilylpropyl) tetrasulfane, bis (3-methyldimethoxysilylpropyl) tetrasulfane, bis (3-triethoxysilylpropyl) tetrasulfane, bis (3-methyldiethoxysilylpropyl) tetrasulfane Fan, bis (3-trimethoxysilylpropyl) disulfide, bis (3-methyldimethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) disulfide, bis (3-methyldiethoxysilylpropyl) Silane compound having sulfide bond such as sulfide, 1,3,5-N-tris (3-trimethoxysilylpropyl) isocyanurate silane, 1,3,5-N-tris (3-methyldimethoxysilylpropyl) isocyanurate Isocyanurate silane compounds such as silane, 1,3,5-N-tris (3-triethoxysilylpropyl) isocyanurate silane, 1,3,5-N-tris (3-methyldiethoxysilylpropyl) isocyanurate silane The compound (a), the compound (b), the compound (c), the compound (d), the compound (e), the compound (f), the compound (h), the compound (i), the above Compound (j), etc., trade names manufactured by Nippon Unicar Company; Y-5187, A-1310, A-1100, A-1102, A-111 , A-1120, A-1122, A-1170, A-9669, A-link15, Y-11637, A-189, AZ-6129, A-186, A-187, A-1160, A-151, A -171, A-172, A-2171, A-174, Y-9936, Z-6134, AZ-6167, A-162, A-163, AZ-6171, AZ-6177, A-137, A-153 , A-1230, MAC-2101, FZ-3704, A-1289, Y-11597, and the like, but are not limited thereto.

Although the said silane coupling agent may be used independently and may be used together 2 or more types, it is preferable to use the silane coupling agent which has an amino group at least. The blending ratio of the silane coupling agent is preferably 0.1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, per 100 parts by weight of the curable resin (A).
Examples of the filler that can be blended in the curable resin composition according to the present invention include calcium carbonate, various treated calcium carbonates, magnesium carbonate, organic polymer, clay, talc, silica, and fumed silica. , Various balloon systems such as glass balloons and plastic balloons, metal hydroxide systems such as aluminum hydroxide and magnesium hydroxide, acicular crystalline fillers, fibrillated fiber systems, etc., but are not limited thereto. Absent.

Examples of the silica filler include, but are not limited to, hydrophilic silica powder, hydrophobic silica powder, fused silica glass powder, and the like. Among these, hydrophobic silica-based powder is particularly preferable.
Examples of the hydrophobic silica-based powder include silica-based powders such as fumed silica (fumed silica) and silica airgel, which are often used as thixotropic agents in adhesives and the like, and organic silicon compounds such as dimethyldioxide. Hydrophobic treated with chlorosilane, hexamethyldisilazane, dimethylsiloxane, trimethoxyoctylsilane, etc. can be used. Those treated with hexamethyldisilazane are preferred.
The hydrophobizing treatment is performed by stirring the silica-based powder and the organosilicon compound at a high speed at a temperature of about 100 to 400 ° C. In order to make both contact uniformly, it is desirable to carry out in a medium such as an organic solvent. The mixing ratio of the silica-based powder and the organosilicon compound is usually 3 to 40 parts by weight per 100 parts by weight of the silica-based powder.

As the fused silica glass-based powder, those having a SiO ₂ content of 99.8% or more and extremely low impurities such as alkali metals are preferable. The fused silica glass powder may be used as it is, or may be used after surface treatment with a surface treatment agent. Examples of the surface treatment agent include organic titanate compounds, organic aluminum compounds, organic zirconium compounds, and alkoxysilanes. Examples of organic titanate compounds include tetrapropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxy titanium, dipropoxy bis (acetylacetonato) titanium, titanium propoxyoctylene glycolate, titanium stearate, isopropyl Triisostearoyl titanate, isopropyltridodecylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridodecylphosphite) titanate, tetra (2,2-diallyloxy) Methyl-1-butyl) bis (ditridodecyl) phosphite titanate, bis (dioctylpyro) Sufeto) oxyacetate titanate, tris (dioctyl pyrophosphate) ethylene titanate, and the like. Examples of the organic aluminum compound include acetoalkoxyaluminum diisopropylate, and examples of the organic zirconium compound include zirconium butyrate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium lactate, and zirconium stearate butyrate. Alkoxysilanes include vinyltrimethoxysilane, vinyltriethoxysilane, bistris (β-methoxyethoxy) silane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl). ) -Γ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (γ , Δ-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, hexamethyldisilazaza Include hexamethyldisiloxane or the like.

Examples of the organic polymer filler include polyester powder, polycarbonate powder, urethane resin powder, polymethylsilsesquioxane powder, acrylic resin powder, styrene resin powder, and vinyl chloride. Vinyl resin powder such as resin powder, SBR powder, chloroprene powder, NBR powder, rubber powder such as acrylic rubber powder, polyolefin powder such as polyethylene and polypropylene, silicone Examples thereof include, but are not limited to, system powders.
Examples of the fibrillated fiber filler include fibrillated aromatic polyamide fiber, polyester fiber, polyolefin fiber, polyacrylonitrile fiber and the like, and those having an average fiber length of about 0.1 to 5 mm are preferable. In addition, a low fibrillated fiber having a lower fibrillation than the fibrillated fiber can be used in combination with the fibrillated fiber. Low fibrillation means that there are few whisker-like branches per unit length of the trunk fiber. Examples of the low fibrillated fibers include fibrillated or non-fibrillated polyester fibers, polyolefin fibers, polyacrylonitrile fibers, sepiolite, glass fibers, carbon fibers, and the like.

The said filler may be used independently and may be used together 2 or more types. The filler preferably has a particle size of 10 nm to 200 μm, preferably 100 nm to 100 μm, particularly preferably 1.0 to 30 μm. Furthermore, the blending ratio of the filler is preferably 1 to 500 parts by weight per 100 parts by weight of the curable resin (A), preferably 1 to 300 parts by weight, particularly preferably 1 to 1 part by weight. 200 parts by weight.
The various additives that can be blended in the curable resin composition according to the present invention include tackifiers (tackifiers), thixotropic agents, dehydrating agents, diluents, plasticizers, flame retardants, oligomers, anti-aging agents, Examples include, but are not limited to, ultraviolet absorbers, pigments, titanate coupling agents, aluminum coupling agents, drying oils such as tung oil, and curable compounds other than the curable resin (A).

There is no limitation in particular as said tackifier, What can be normally used irrespective of solid and liquid at normal temperature can be used. Specific examples include phenolic resins, modified phenolic resins (eg, cashew oil-modified phenolic resin, tall oil-modified phenolic resin, etc.), terpene phenolic resin, xylene-phenolic resin, cyclopentadiene-phenolic resin, coumarone indene resin, rosin type resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, low molecular weight polystyrene resins, styrene copolymer resins, petroleum resins (e.g., C ₅ hydrocarbon resins, C ₉ hydrocarbon resins, C ₅ · C ₉ hydrocarbons Hydrogenated resin, etc.), hydrogenated petroleum resin, terpene resin, DCPD resin and the like. These may be used alone or in combination of two or more. Among the tackifying resins, terpene phenol resins, rosin ester resins, hydrogenated rosin ester resins, xylene resins, styrene copolymer resins, C ₉ hydrocarbon resins, hydrogenated petroleum resins, terpene resins, particularly phase It is preferable because it has good solubility and good adhesive properties. The blending ratio of the tackifying resin is preferably 2 to 70 parts by weight per 100 parts by weight of the curable resin (A), particularly preferably 5 to 20 parts by weight per 100 parts by weight of the curable resin (A). It is.

Examples of the thixotropic agent include, but are not limited to, anhydrous silica, amide wax, fatty acid bisamide, hydrogenated castor oil, and the like.
Examples of the dehydrating agent include silane coupling agents such as calcium oxide, magnesium oxide, zinc oxide, calcium chloride, orthosilicate ester and vinyltrimethoxysilane, silicate compounds such as methyl silicate and ethyl silicate, activated carbon and zeolite. However, it is not limited to these.
The diluent can be suitably used without limitation as long as it is a solvent having a dilution effect, but preferably has good compatibility with the curable resin (A), and particularly preferably has a water content. 500 ppm or less. The blending ratio of the diluent is not particularly limited.
As the diluent, a reactive diluent containing a crosslinkable functional group such as a hydrolyzable silyl group, an epoxy group, or an isocyanate group in the molecule can be used. Their main chain skeletons are not particularly limited.

  Furthermore, the said diluent which has a hydrolyzable silyl group in a molecule | numerator is marketed, and they can be used in this invention. As such a commercial item, Shin-Etsu Chemical Co., Ltd. brand name: KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-217, KR-9218, KR-213, KR-510, X-40-9227, X-40-9247, X-41-1053, X-41-1056, X-40-1805, X-40-1810, X-40-2651, Examples thereof include, but are not limited to, X-40-2308 and X-40-9238.

  Furthermore, as the diluent, a compound whose main chain is an acrylic polymer can be used. Such compounds are commercially available and can be used in the present invention. As a commercially available compound whose main chain is an acrylic polymer, trade names: XPR-15, 22, 39, 40, UP1000, 1010, 1020, 1021, 1061, 1070, 1080, 1110, UG-4010, manufactured by Toa Gosei Co., Ltd. Product names manufactured by Soken Chemical Co., Ltd .: UMB-1001, 2005, 2005B, 2005P, UME-1001, UMM-1001, 4005, UT-1001, 2001, 2001P, 3001, AS-300, 301, ASM-4001, CB-3060 , BGV-11, 12 and the like, but are not limited thereto.

Examples of the plasticizer include aromatic carboxylic acid esters such as dioctyl phthalate and dibutyl phthalate, aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate, or polyalkylene glycol and polyalkylene glycol-modified products (meta ) Examples include, but are not limited to, acrylic monomer polymers, liquid tackifiers such as terpenes or terpene phenol copolymers having a low degree of polymerization, oils such as naphthenes, aromatics, paraffins, and silicones. is not.
Examples of the flame retardant include, but are not limited to, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, halogen flame retardants and phosphorus flame retardants.

Examples of the oligomer include polyethylene oligomer, liquid polypropylene, oligostyrene, liquid polychloroprene, liquid polyisoprene, liquid SBR, liquid NBR, liquid butyl rubber, liquid polyisobutylene, liquid polybutadiene, polyhydroxypolyolefin oligomer, α-methylstyrene oligomer, Examples thereof include, but are not limited to, phosphorus-containing styrene-α-methylstyrene oligomers and oligoester acrylates.
Examples of the anti-aging agent and the ultraviolet absorber include compounds having a primary amino group, a secondary amino group, a tertiary amino group, a hydroxyl group, a carboxyl group and / or a mercapto group in the molecule. And those widely used as deterioration inhibitors for various resins.

  Specific examples of the anti-aging agent and the ultraviolet absorber include triacetonediamine, poly [(6-morpholino-s-triazine-2,4-diyl) {2,2,6,6-tetramethyl-4- Piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2 , 2,6,6-pentamethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, poly (2,2,4-trimethyl-1,2-dihydroquinoline) 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, N, N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenyl Nylenediamine, N-1,3-dimethylbutyl-N′-phenyl-p-phenylenediamine, mixed N, N′-diallyl-p-phenylenediamine, alkylated diphenylamine, 8-acetyl-3-dodecyl-7,7, 9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3 , 5-triazine-2,4-diyl} {2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {2,2,6,6-tetramethyl-4-piperidyl) imino}] N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro − , 3,5-triazine condensate, diphenylguanidine, di-o-tolylguanidine, N-cyclohexylbenzothiazyl-sulfenamide, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxy Benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone trihydrate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfate trihydrate, 4- Dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy -4-Octoki Cibenzophenone, 2-hydroxy-4-octoxybenzophenone, 2- (2'-hydroxy-5'-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-t-butyl) Phenyl) benzotriazole, 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methyl) Phenyl) -2H-benzotriazole, 5-chloro-2- (3,5-di-tert-butyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3-tert-butyl-2-hydroxy-5) -Methylphenyl) -5-chloro-2H-benzotriazole, 2- (3,5-di-t-pentyl-2-hydroxyphenyl) -2H-benzotriazole, 2- (3,5-di-t-butyl -2-hydroxyphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-t-octylphenyl) -2H-benzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimido-methyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylphenyl) Benzotriazole, 2- (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, n-hexadecyl-3,5-di-t-butyl-4-hydroxybenzoate, 2 ', 4'-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, tris (3,5- Di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanate Nuric acid, ethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], tetrakis [methylene-3 (3 ′, 5′-di-tert-butyl-4′-hydroxy) Phenyl) propionate] methane, n-octadecyl-3 (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, triethylene glycol bis [3- (3-t-butyl-4-hydroxy) -5-methylphenyl) propionate], isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydride) Loxyphenyl) propionate], 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 2,2 ' -Butylidene-bis (4-ethyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6-tert-butylphenol), 2,2'-methylene-bis [4-methyl-6 -T-butylphenol], 2,2'-methylene-bis (4-methyl-t-butylphenol), 2,2'-methylene-bis (4-ethyl-t-butylphenol), 6- (2-benzotriazolyl) ) -4-t-octyl-6'-t-butyl-4'-methyl-2,2'-methylenebisphenol, styrenated phenol, 2,6-di-t-butyl-4-methylphenol 2,4-dimethyl-6- (1-methylcyclohexyl) phenol, 2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5 -(Octyloxy) phenol, 2,6-di-t-butyl-4-ethylphenol, 2- (2H-benzotriazol-2-yl) -4-menthyl-6- (3,4,5,6- Tetrahydrophthalimidylmethyl) phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,5-di-t-butylhydroquinone , Poly (2,2,4-trimethyl-1,2-dihydroquinone), 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinone, 2,5-di-t-amylhydroquinone, 4 , 4 ' Butylidene-bis (6-t-butyl-m-cresol), 2,2'-methylene-bis [6- (1-methylcyclohexyl) -p-cresol], 1- [2- {3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy} -2,2,6,6 -Tetramethylpiperidine, S- (3,5-di-t-butyl-4-hydroxybenzyl) -2-ethyl-n-hexyl-thioglycolate, 4,4'-thiobis (6-t-butyl-m -Cresol), p-benzoquinonedioxime, 1,6-bis (4-benzoyl-3-hydroxyphenoxy) -hexane, 1,4-bis (4-benzoyl-3-hydroxyphenoxy) -butane, sa Phenyllithylate, 4-t-butylphenyl salicylate, 1,1,3-tris (2-methyl-t-butyl-4-hydroxy-5-t-butylphenyl) butane, 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 2-t-butyl-6- (3'-t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, dimethyl succinate -(2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, methyl-3- [3-t-butyl-5- (2H-benzotriazo) (Lu-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol, 3,4-dihydro-2,5,7,8-tetramethyl-2- (4,8,12-trimethyltridecyl) ) -2H-benzopyran-6-ol (Irganox E201), Irganox E201, a mixture of glycerin and low density polyethylene, Irganox E201, a mixture of stearic acid, bis (3,5-di-t-butyl- Ethyl 4-hydroxybenzylsulfonate) mixture of calcium and polyethylene wax, 2,4-bis [(octylthio) methyl] -o-cresol, N, N'-hexamethylenebis (3,5-di-t-butyl -4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzyl Sulfonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2- (3,5-di-tert-butyl) -4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,3-bis [{3- (3,5-di-t -Butyl-4-hydroxyphenyl) propionyl}] propionohydrazide, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5- Triazine, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, mercaptobenzothiazole, 2-mercaptobenzimidazole, trade name: Sanol LS-765, Sankyo Lifetech Co., Ltd. Nol LS-292, Sanol LS-944, Sanol LS-440, Sanol LS-770, Sanol LS-744, Ciba Specialty Chemicals product names: Tinuvin 123, Tinuvin 292, Tinuvin 144, etc. It is not limited to these.

In addition, the anti-aging agent and the ultraviolet absorber that can be used in the present invention include functional groups having reactivity with at least one isocyanate group in the molecule of the anti-aging agent and the ultraviolet absorber (for example, , A compound having a primary amino group, a secondary amino group, a hydroxyl group, a carboxyl group and a mercapto group) and a compound synthesized by the reaction of the compound group (C) can also be used. When such a compound is used, the effects of aging prevention and ultraviolet absorption can be further improved.
The anti-aging agent and the ultraviolet absorber can be used alone or in combination of two or more. The blending ratio of the anti-aging agent and the ultraviolet absorber is preferably 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight per 100 parts by weight of the curable resin (A). Particularly preferred is 0.1 to 2 parts by weight.

Examples of the curable compound other than the curable resin (A) include the curable compound (M), a urethane prepolymer having at least one isocyanate group in the molecule, an epoxy resin, and a maleic anhydride grafted polybutadiene oil (for example, Degussa Japan brand name; POLYVESTOC800S etc.), etc. are mentioned, but it is not limited to these. Moreover, 1 type (s) or 2 or more types can be selected and used for curable compounds other than the said curable resin (A).
The urethane prepolymer is not particularly limited as long as it is a urethane prepolymer having at least one isocyanate group in the molecule. Such a urethane prepolymer can be synthesized by reacting a compound having at least one hydroxyl group, amino group, mercapto group and carboxyl group in the molecule with a compound having at least two isocyanate groups in the molecule. it can. Moreover, in this urethane prepolymer, the compound which has at least 2 isocyanate group may remain | survive in the molecule | numerator used as the raw material.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, epoxy resin obtained by glycidylation of amine, epoxy resin having a heterocyclic ring, alicyclic epoxy resin, hydrogenated bisphenol A type epoxy. Examples thereof include resins, urethane-modified epoxy resins, hydantoin-type epoxy resins, terminal-epoxidized polyoxyalkylenes, and the like, and these can be selected and used.
Moreover, when using the said epoxy resin, it is suitable to use ketimine compounds or oxazolidine compounds, such as ketimine and aldimine. The ketimine compound is a compound having a group represented by the general formula —N═C (X) (Y) (where X is a hydrogen atom or an organic group, and Y is an organic group). In the present invention, for example, The following compounds (1) and (2) are effectively used.

但し、Ｒ３３、Ｒ３４、Ｒ３５及びＲ３６は、各々水素、炭素数１〜６のアルキル基、フェニル基及び炭素数１〜６のアルキル基を有するフェニル基から選択される同一又は異なる基であり、Ｄ１、Ｄ２及びＤＤ３は、各々炭素数２〜６の同一又は異なるアルキレン基であり、ｘは０又は１である。 (1) A compound represented by the following formula (144) and a derivative of the compound. For example, a compound obtained by reacting a compound having an epoxy group with a secondary amino group of the compound.

However, R33, R34, R35 and R36 are the same or different groups each selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, a phenyl group and a phenyl group having an alkyl group having 1 to 6 carbon atoms, and D1 , D2 and DD3 are the same or different alkylene groups each having 2 to 6 carbon atoms, and x is 0 or 1.

  Examples of the compound represented by the above formula (144) include 2,5,8-triaza-1,8-nonadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,10 -Diphenyl-3,5,9-triaza-2,9-undecadiene, 3,11-dimethyl-4,7,10-triaza-3,10-tridecadiene, 3,11-diethyl-4,7,10-triaza -3,10-tridecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadecadiene, 2,4,20,22-tetramethyl-5,12,19 -Triaza-4,19-trieicosadiene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadien, and the like. Things No.

  Examples of the compound having an epoxy group to be reacted with the imino group of the compound represented by the above formula (144) include styrene oxide, butyl glycidyl ether, allyl glycidyl ether, p-ter-butylphenyl glycidyl ether, and p-sec-butylphenyl. Glycidyl ether, m, p-cresyl glycidyl ether, p-cresyl glycidyl ether, vinylcyclohexanedioxide, versatic acid glycidyl ester, cardanol-modified glycidyl ether, dimer acid glycidyl ester, 1,6-hexanediol diglycidyl ether , Resorcinoglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, etc. It is. In particular, a derivative using styrene oxide is preferable. The ketimine derivative may be one in which only one of the two imino groups of the compound represented by the above structural formula has reacted with a compound having an epoxy group.

As a compound represented by the following formula (144) and a derivative of the compound, a compound represented by the following formula (145) and the following formula (146) can also be used. In addition, in following formula (145), n shows the number of 1-6. In the following formula (146), x, y, and z may be the same or different. x + y + z is about 5.3.

(2) A compound obtained by reacting an amine compound having at least one primary amino group in the molecule with a carbonyl compound.
As an amine compound having at least one primary amino group in the molecule, it is generally advantageous to have a primary amino group equivalent of about 2,000 or less, preferably in the range of about 30 to 1,000. It is also preferred to have a number average molecular weight generally less than about 5,000, preferably in the range of about 60-3,000.

  Specific examples of the amine compound include ethylene diamine, propylene diamine, butylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, pentaethylene hexamine, hexamethylene diamine, trimethyl hexamylene diamine, N-aminoethylpiperazine, 1,2 -Polyamines having a polyoxylene skeleton such as diaminopropane, iminobispropylamine, methyliminobispropylamine, poly (oxypropylene) diamine, trade names manufactured by Sun Techno Chemical Co., Ltd .: Polyether skeleton diamine represented by Jeffamine EDR148 , Isophoronediamine, 1,3-bisaminomethylcyclohexane, 1-cyclohexylamino-3-aminopropane, 3-aminomethyl-3,3,5-tri Til-cyclohexylamine, trade name manufactured by Mitsui Chemicals, Inc .: product name manufactured by Mitsubishi Gas Chemical Company, which is a diamine having a norbornane skeleton represented by NBDA, and a diamine having a xylylene skeleton represented by metaxylylenediamine, MXDA, diaminodiphenylmethane , Phenylenediamine, and aliphatic polyamines such as polyamideamine having a primary amino group at the molecular end of the polyamide, aromatic polyamines, and alicyclic polyamines.

Other than these, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane Although silicon atom-containing amine compounds such as silane can be mentioned, among the above amine compounds, polyamine compounds having two or more primary amino groups in the molecule are particularly preferred.
Examples of the carbonyl compound include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, methyl t-butyl ketone, diethyl ketone, dipropyl ketone, diisobutyl ketone, ethyl propyl ketone, ethyl butyl ketone, cyclohexanone, propiophenone, benzophenone, and the like. And aldehydes such as acetaldehyde and benzaldehyde.

  Ketimineization can be achieved by blocking the amine compound with the ketones, and aldimination can be achieved by blocking with the aldehydes. The compound (2) includes both ketiminated and aldiminated compounds. The reaction between the amine compound and the carbonyl compound can be carried out by a method known per se, such that substantially all primary amino groups present in the amine compound react with the carbonyl compound. The reaction is carried out in a quantitative ratio and conditions. Both reactions are accomplished by azeotropic removal of water produced by heating under reflux in the absence of a solvent or in the presence of a non-polar solvent such as hexane, cyclohexane, toluene, or benzene. Further, in order to facilitate the reaction (dehydration reaction), ketones having poor water solubility and small steric hindrance such as methyl isobutyl ketone and methyl ethyl ketone can be used as the carbonyl compound. The epoxy resin and the ketimine compound are preferably used in an amount of 1 to 200 parts by weight of the epoxy resin and 1 to 200 parts by weight of the ketimine compound per 100 parts by weight of the curable resin (A). It is more preferable to use 100 parts by weight and 1-100 parts by weight of the ketimine compound.

  The present invention also comprises a composition (I) comprising the curable resin (A) and a curing agent for the epoxy resin, and a mixture (II) comprising the epoxy resin and a curing catalyst for the curable resin. It can also be. In particular, the blending ratio of each component in the composition is 15 to 80% by weight of the mixture (I) consisting of 100 parts by weight of the curable resin (A) and 0.01 to 80 parts by weight of the curing agent of the epoxy resin, and It is preferable to use 85 to 15% by weight of a mixture (II) comprising 100 parts by weight of an epoxy resin and 0.1 to 20 parts by weight of a curing catalyst for the curable resin.

  Examples of the epoxy resin curing agent include ethylenediamine, 1,3-propanediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, 2,2,4-trimethyl-1,6-hexanediamine, m-xylylenediamine, and bis. (4-aminocyclohexyl) propane, isophoronediamine, tetraethylenepentamine, dipropylenetriamine, bishexamethylenetriamine, 1,3,6-trisaminomethylhexane, trimethylhexamethylenediamine, polyether diamine, diethylaminopropylamine, men Sendiamine, bis (4-amino-3-methylcyclohexyl) methane, N-aminoethylpiperazine, m-phenylenediamine, diaminodiphenylsulfone, diaminodiphenylmethane, etc. Alone and and modified products thereof, but not limited thereto. Examples of the modification method include epoxy compound addition, ethylene oxide addition, propylene oxide addition, acrylonitrile addition, Mannich addition with phenol and its derivatives and formalin, thiourea addition, and ketone blockage.

  Others, phenol novolac, polymercaptan compounds, polysulfides, ketimines, tertiary amines, organic acid hydrazides, dicyandiamide and derivatives thereof, amine imides, carboxylic acid esters, boron trifluoride-amine complexes, imidazoles, Lewis acids, acids Anhydrides, halogenated anhydrides, aromatic diazonium salts, diallyl iodonium salts, triallyl sulfonium salts, triallyl selenium salts, polyamidoamines, polyphenols, alcohols, acetylacetonato metal salts, phosphines, etc. However, it is not limited to these. These may be used alone or in combination of two or more.

The invention is explained in more detail by means of examples. The present invention is not limited to the following examples.
<The synthesis example regarding the manufacturing method (2) of curable resin (A)>
(Synthesis Example 1)
SDX-1690 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., a polyether having an allyl group at both ends, number average molecular weight) in a synthesis reaction vessel of a curable resin having a trimethoxysilyl group in the molecule and having a sulfide bond (3,000) (100 g) and DMDS (trade name, 1,5-dimercapto-3-thiapentane) manufactured by Maruzen Chemical Co., Ltd. were added, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 0.5 g of AIBN (2,2′-azobisisobutyronitrile) and 5 g of toluene is added dropwise over 1 hour, and further reacted at the same temperature for 2 hours to have a mercapto group in the molecule. A compound (reactant PB-1) was synthesized. After the reaction product containing the reaction product PB-1 is cooled to 85 ° C., 15.6 g of KBM5103 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., γ-acryloxypropyltrimethoxysilane) is added, and the reaction is performed at the same temperature for 3 hours. Thus, a liquid curable resin B-1 having a trimethoxysilyl group in the molecule at room temperature was synthesized.

(Synthesis Example 2)
After the reaction product PB-1 was cooled to 85 ° C. in a synthesis reaction vessel of a curable resin having a methyldimethoxysilyl group in the molecule and having a sulfide bond , KBM5102 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., γ- acrylate the filtrate propyl methyl dimethoxy silane) was added 14.6 g, was reacted at the same temperature for 3 hours, to synthesize a curable resin B-2 liquid at room temperature having a methyldimethoxysilyl group in the molecule.

(Synthesis Example 3)
179 g of KBM903 (trade name: γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to a synthetic reaction vessel of a curable resin having a trimethoxysilyl group in the molecule and having a urethane bond and a substituted urea bond. And 184 g of 2-ethylhexyl acrylate was added and reacted at 80 ° C. for 10 hours while stirring and mixing in a nitrogen atmosphere to obtain a reaction product SE-3.
In another reaction vessel, 700 g of PML4010 (trade name; manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000), PR5007 (trade name; manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene-containing polyoxypropylene polyol) ) And 88.8 g of Desmodur I (trade name; manufactured by Sumika Bayer Urethane Co., Ltd., isophorone diisocyanate) are allowed to react at 90 ° C. for 8 hours while stirring and mixing in a nitrogen atmosphere. Polyoxyalkylene resin PB-3 having an isocyanate group was obtained. Thereafter, 119 g of the reaction product SE-3 was added, and the mixture was allowed to react at 90 ° C. for 2 hours while stirring and mixing in a nitrogen atmosphere, so that the curability having a urethane bond, a substituted urea bond, and a silicon-containing characteristic group in the molecule. A liquid curable resin B-3 was obtained at room temperature, which is a polyoxyalkylene resin.

(Synthesis Example 4)
In a reaction vessel for synthesis of a curable resin having a trimethoxysilyl group and a methyldimethoxysilyl group in the molecule and having a urethane bond and a substituted urea bond , KBM903 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltri 35.9 g of methoxysilane), 130.6 g of KBM902 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropylmethyldimethoxysilane) and 114 g of n-butyl acrylate, and while stirring and mixing in a nitrogen atmosphere, The reaction product SE-4 was obtained by reacting at 80 ° C. for 10 hours.
In another reaction vessel, 700 g of PML4010 (trade name; manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000), PR5007 (trade name; manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene-containing polyoxypropylene polyol) ) And 32.3 g of Desmodur I (trade name; manufactured by Sumika Bayer Urethane Co., Ltd., isophorone diisocyanate), and stirring and mixing in a nitrogen atmosphere for 8 hours at 90 ° C. Polyoxyalkylene resin PB-4 having an isocyanate group was obtained. Thereafter, 82 g of the reaction product SE-4 was added, and the mixture was allowed to react at 90 ° C. for 2 hours while stirring and mixing in a nitrogen atmosphere, so that the curability having a urethane bond, a substituted urea bond and a silicon-containing characteristic group in the molecule. A liquid curable resin B-4 was obtained at room temperature, which is a polyoxyalkylene resin.

(Examples 1-4, Comparative Example 1)
In order to compare the curing rate, the obtained curable resins B-1 to B-4, S303 (trade name: trade name, manufactured by Kaneka Chemical Industry Co., Ltd., methyldimethoxysilyl group-containing polyoxyalkylene), and trifluoride The boron monoethylamine complex was rapidly mixed using a mixer for 30 seconds at the blending ratio shown in Table 1, and the skinning time was measured. The skinning time was determined as the time until the cured film stretched on the surface by finger touch was not transferred to the finger after leaving the curable resin composition in an atmosphere of 23 ° C. and 50-60% relative humidity. . The following skinning time was also obtained by the same method. In the table, for example, 2'30 '' indicates that the skinning time was 2 minutes 30 seconds.

表１の結果より、三フッ化ホウ素モノエチルアミン錯体を用いた場合、分子内にトリメトキシシリル基を含有する硬化性樹脂を用いた実施例１〜４が、分子内にトリメトキシシリル基を含有しない硬化性樹脂を用いた比較例１より、硬化が極めて速いことが分かる。つまり、三フッ化ホウ素モノエチルアミン錯体が、トリメトキシシリル基に対して特に効果を示すことが考えられる。

From the results of Table 1, when a boron trifluoride monoethylamine complex was used, Examples 1 to 4 using a curable resin containing a trimethoxysilyl group in the molecule contained a trimethoxysilyl group in the molecule. It turns out that hardening is very quick from the comparative example 1 using curable resin which does not carry out. That is, it is considered that the boron trifluoride monoethylamine complex is particularly effective for the trimethoxysilyl group.

(Examples 5 to 25, Comparative Examples 2 to 3)
Curable resin B-1 obtained in Synthesis Example 1 or curable resin B-3 obtained in Synthesis Example 3, and KBM603 shown in Table 2 (trade name; manufactured by Shin-Etsu Chemical Co., Ltd., N-β (amino Ethyl) γ-aminopropyltrimethoxysilane) and the curing catalyst were mixed in the blending ratio (parts by weight) shown in Table 1. Mixing was performed quickly using a mixer for 30 seconds, and then the skinning time was measured. The results are shown in Tables 2 and 3.

＊１ 商品名；信越化学工業社製、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン
＊２ 商品名；三共有機化学工業社製、ジブチル錫系化合物
＊３ 商品名；三共有機化学工業社製、ジオクチル錫系化合物
＊４ 商品名；日東化成社製、ポリ（ジブチルスタノキサン）ジシリケート化合物
＊５ 商品名；日東化成社製、ジオクチル錫系化合物

* 1 Product name: Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) γ-aminopropyltrimethoxysilane * 2 Product name: Sankyo Machinery Chemical Co., Ltd., dibutyltin compound * 3 Chemical Industry Co., Ltd., dioctyltin-based compound * 4 Product name; Nitto Kasei Co., Ltd., poly (dibutylstannoxane) disilicate compound * 5 Product name; Nitto Kasei Co., Ltd., dioctyltin-based compound

  From the results of Table 2 and Table 3, when a Lewis acid compound is used as a curing catalyst, a curable resin having a trimethoxysilyl group in the molecule, a trimethoxysilyl group in the molecule and a urethane bond and It can be seen that the curability of the curable resin having a substituted urea bond is much faster than the dialkyl tin catalyst. When a Lewis acid compound is used as the curing catalyst, the curable resin having a urethane group, a substituted urea bond and a tertiary amino group in the molecule has the silicon-containing characteristic group in the molecule and It turns out that hardening is quicker than curable resin which does not have a polar element part. Furthermore, it can be seen that when a titanium chloride or boron trifluoride compound is used as the Lewis acid, an extremely fast curing rate can be obtained.

(Examples 27 to 31, Comparative Examples 4 and 5)
100 parts by weight of the curable resin B-3 obtained in Synthesis Example 3 and 10 parts by weight of Silo Hovic 200 (trade name; manufactured by Fuji Silysia Chemical Ltd., Syria airgel hydrophobized with dimethylsiloxane) in a planetary mixer The resulting mixture was kneaded while being heated and dehydrated at 100 ° C. for 1 hour under reduced pressure, and cooled to room temperature. (Product name: Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane) was added in an amount of 5 parts by weight and the curing catalyst shown in Table 4 was added in the proportion shown in Table 4 (parts by weight), and the mixture was added under reduced pressure for 30 minutes The curable resin composition was obtained by kneading. Each curable resin composition was immediately filled into a sealed container and left at 23 ° C. for 2 weeks or more. Table 4 shows the skinning time of each curable resin composition.

＊６ 商品名；富士シリシア化学社製、ジメチルシロキサンで疎水化処理したシリカエアロゲル
＊７ 商品名；東邦化学工業社製、末端封鎖ポリエチレングリコール
＊８ 商品名；信越化学工業社製、γ−アミノプロピルトリメトキシシラン
＊９ 商品名；三共有機化学工業社製、ジオクチル錫系化合物
表４の結果から、分子内に上記含珪素特性基と、且つ、分子内にウレタン基及び置換尿素結合を含む硬化性樹脂に三フッ化ホウ素系化合物（具体的には三フッ化ホウ素とアミン化合物との錯体）を用いると、ジアルキル錫系化合物を用いるより、硬化が格段に速いことが分かる。また、三フッ化ホウ素系化合物と錫化合物を併用しても、三フッ化ホウ素系化合物による効果で、硬化が非常に速くなることが分かる。

* 6 Product name: manufactured by Fuji Silysia Chemical Co., Ltd., silica aerogel hydrophobized with dimethylsiloxane * 7 Product name: manufactured by Toho Chemical Industry Co., Ltd., end-capped polyethylene glycol * 8 Product name: manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyl Trimethoxysilane * 9 Product name; manufactured by Sansha Kikai Kogyo Co., Ltd., dioctyltin-based compound From the results in Table 4, the above-mentioned silicon-containing characteristic group in the molecule, and the curing containing a urethane group and a substituted urea bond in the molecule When a boron trifluoride compound (specifically, a complex of boron trifluoride and an amine compound) is used as the conductive resin, it can be seen that curing is much faster than when a dialkyltin compound is used. Further, it can be seen that even when a boron trifluoride compound and a tin compound are used in combination, curing is very quick due to the effect of the boron trifluoride compound.

(Synthesis example 5) <Manufacturing method regarding manufacturing method (2) of curable resin (A)>
PML4010 (trade name, polyether polyol, number average molecular weight 10,000, manufactured by Asahi Glass Urethane Co., Ltd.) is added to a synthetic reaction vessel of a curable resin having the above silicon-containing characteristic group in the molecule and having a urethane bond in the molecule. By adding 4.1 g of 100 g and Y-5187 (trade name, γ-isocyanatopropyltrimethoxysilane, manufactured by Nihon Unicar Co., Ltd.) and stirring and mixing in a nitrogen atmosphere, the reaction is carried out at 90 ° C. for 8 hours. A liquid curable resin B-5 was obtained at room temperature, which is a curable polyoxyalkylene resin having a silicon-containing characteristic group and a urethane bond.

(Synthesis example 6) <Manufacturing method regarding manufacturing method (2) of curable resin (A)>
SDX-1690 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., both end-terminated polyethers) is used in a reaction container for a curable resin having the above-mentioned silicon-containing characteristic groups in the molecule and a thiourethane bond in the molecule. In addition, 100 g of a number average molecular weight of 3,000) and 11.3 g of DMDS (trade name manufactured by Maruzen Chemical Co., Ltd., 1,5-dimercapto-3-thiapentane) were added, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 0.5 g of AIBN and 5 g of toluene was added dropwise over 2 hours, and further reacted at the same temperature for 1 hour to synthesize a reaction product PB-6. After the reactant containing the reactant PB-6 is cooled to 70 ° C., 13.7 g of Y-5187 and 0.15 g of triethylamine are added and reacted at 70 ° C. for 8 hours in a nitrogen atmosphere. A liquid curable resin B-6 was produced at room temperature, which is a curable polyoxyalkylene resin having a silicon-containing characteristic group and a thiourethane bond.

(Synthesis example 7) <The manufacturing method regarding the manufacturing method (3) of curable resin (A)>
A synthetic reaction vessel of a curable resin having the above-mentioned silicon-containing characteristic group in the molecule and having a urea bond in the molecule, Jeffamine D-4000 (trade name, manufactured by Sun Techno Japan Co., Ltd., both ends are primary amino groups) 100 g of polyether polyol, number average molecular weight 4,000) and 8.7 g of Y-5187 (Nippon Unicar Corporation trade name, γ-isocyanatopropyltrimethoxysilane) were added and stirred and mixed in a nitrogen atmosphere. By making it react at 70 degreeC for 8 hours, liquid curable resin B-7 which is a curable polyoxyalkylene resin which has a silicon-containing characteristic group and a urea bond in a molecule | numerator was obtained.

(Synthesis example 8) <Manufacturing method regarding manufacturing method (3) of curable resin (A)>
A synthetic reaction vessel of a curable resin having the above-mentioned silicon-containing characteristic group in the molecule and a substituted urea bond in the molecule, Jeffamine D-4000 (trade name, manufactured by Sun Techno Japan, both ends are primary amino acids) Base polyether polyol, number average molecular weight 4,000) 100 g and butyl acrylate 4.9 g were added and reacted at 50 ° C. for 10 hours while stirring and mixing in a nitrogen atmosphere, to thereby obtain reactant PB-8. Got. Furthermore, 4.4 g of Y-5187 (Nippon Unicar company name, γ-isocyanatopropyltrimethoxysilane) was added and reacted at 90 ° C. for 10 hours while stirring and mixing in a nitrogen atmosphere. A liquid curable resin B-8 was obtained at room temperature, which is a curable polyoxyalkylene resin having a silicon-containing characteristic group and a substituted urea bond.

(Synthesis example 9) <The manufacturing method regarding the manufacturing method (3) of curable resin (A)>
In a synthetic reaction vessel of a curable resin having the above-mentioned silicon-containing characteristic group in the molecule and having a thiourea bond in the molecule, 53.8 g of 3- (trimethoxysilyl) propylamine and 600 ml of dry THF (tetrahydrofuran) And cooled to 0 ° C. To this solution, 34.2 g of carbon disulfide was added dropwise and stirred at 0 ° C. for 5 hours in a nitrogen atmosphere. Thereafter, 61.9 g of dicyclohexylcarbodiimide dissolved in 180 ml of dry THF and 3 g of triethylamine were added and reacted at 40 ° C. for 5 hours. From the resulting reaction mixture, THF was distilled off under reduced pressure, and the residue was extracted with n-hexane. N-Hexane was distilled off under reduced pressure from the extract, and the residue was distilled under reduced pressure to obtain γ-isothiocyanate propyltrimethoxysilane.
In a separate reaction vessel, 1,000 g of Jeffamine D-4000 (trade name, manufactured by Sun Techno Japan Co., Ltd., polyether polyol having both primary amino groups at both ends, number average molecular weight 4,000) and γ-iso obtained were obtained. A curable polyoxyalkylene resin having silicon-containing characteristic groups and thiourea bonds in the molecule by adding 110.7 g of thiocyanate propyltrimethoxysilane and reacting at 90 ° C. for 8 hours with stirring and mixing in a nitrogen atmosphere. A liquid curable resin B-9 was obtained at room temperature.

(Synthesis example 10) <Manufacturing method regarding manufacturing method (3) of curable resin (A)>
A synthetic reaction vessel of a curable resin having the above-mentioned silicon-containing characteristic group in the molecule and a substituted thiourea bond in the molecule, Jeffamine D-4000 (trade name, manufactured by San Techno Japan, both ends are primary 100 g of amino group polyether polyol, number average molecular weight 4,000) and 3.7 g of methyl acrylate were added and reacted at 50 ° C. for 10 hours with stirring and mixing in a nitrogen atmosphere, whereby reactant PB- 10 was obtained. Furthermore, 5.5 g of γ-isothiocyanate propyltrimethoxysilane obtained in Synthesis Example 5 was added and reacted at 90 ° C. for 8 hours while stirring and mixing in a nitrogen atmosphere, so that a silicon-containing characteristic group was formed in the molecule. And a curable resin B-10 which is a curable polyoxyalkylene resin having a thiourea bond at room temperature.

(Synthesis example 11) <Manufacturing method regarding manufacturing method (6) of curable resin (A)>
500 g of toluene was put into a synthetic reaction vessel of a curable resin having the above silicon-containing characteristic group in the molecule and an amide bond in the molecule . Thereafter, 100 g of methyl methacrylate, 100 g of butyl acrylate, 30 g of lauryl methacrylate, 20 g of acrylamide, 40 g of diacetone acrylic amide (trade name, manufactured by Kyowa Hakko Kogyo Co., Ltd.), KBM503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ- 20 g of methacryloxypropyltrimethoxysilane), 10 g of KBM803 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-mercaptopropyltrimethoxysilane), V-65 (trade name, manufactured by Wako Pure Chemical Industries, Ltd., 2, A monomer solution was prepared by mixing 3 g of 2′-azobis (2,4-dimethylvaleronitrile). The monomer solution was added dropwise over 2 hours while heating to 100 ° C. in a nitrogen atmosphere, and the reaction was further performed for 1 hour. Thereafter, a polymerization initiator solution in which V-651 g was dissolved in 20 g of toluene was dropped over 10 minutes, and the reaction was further performed for 4 hours. Thereafter, toluene was distilled off under reduced pressure to obtain a liquid curable resin B-11 at room temperature which is a curable vinyl polymer having a silicon-containing characteristic group and an amide bond in the molecule.

(Synthesis example 12) <Manufacturing method regarding manufacturing method (4) of curable resin (A)>
SDX-1690 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., a polyether having allyl groups at both ends , having a silicon-containing characteristic group in the molecule and a hydroxyl group in the molecule) Number average molecular weight 3,000) was added to 100 g and DMDS (trade name, 1,5-dimercapto-3-thiapentane) manufactured by Maruzen Chemical Co., Ltd., and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of AIBN 0.5 g and toluene 2.5 g was added dropwise over 1 hour, and further reacted at the same temperature for 2 hours to synthesize a reaction product PB-12. After cooling the reaction product containing the reaction product PB-12 to 70 ° C., 18.9 g of TSL8350 and 0.15 g of triethylamine are added, and the reaction is carried out at 70 ° C. for 8 hours in a nitrogen atmosphere. A liquid curable resin B-12, which is a curable polyoxyalkylene resin having a characteristic group and a hydroxyl group, was produced at room temperature.

(Synthesis example 13) <The manufacturing method regarding the manufacturing method (5) of curable resin (A)>
A synthetic reaction vessel of a curable resin having the above-mentioned silicon-containing characteristic group in the molecule and a secondary amino group in the molecule is Jeffamine D-4000 (trade name, manufactured by Sun Techno Japan Co., Ltd. 100 g of a polyether polyol having a secondary amino group, number average molecular weight of 4,000) and 11.7 g of KBM5103 (trade name; γ-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) are added and stirred under a nitrogen atmosphere. By reacting at 50 ° C. for 10 hours while mixing, a curable liquid B-13 at room temperature, which is a curable polyoxyalkylene resin having a silicon-containing characteristic group and a secondary amino group in the molecule, was obtained. .

(Synthesis example 14) <Manufacturing method regarding manufacturing method (6) of curable resin (A)>
500 g of toluene was placed in a synthetic reaction vessel of a curable resin having the above-mentioned silicon-containing characteristic group in the molecule and a tertiary amino group in the molecule . Thereafter, 100 g of methyl methacrylate, 100 g of butyl acrylate, 30 g of lauryl methacrylate, 20 g of light ester DM (trade name, tertiary amino group-containing acrylate compound) manufactured by Kyoeisha Chemical Co., Ltd., light ester DE (Kyoeisha Chemical Co., Ltd.) Product name, tertiary amino group-containing acrylic ester compound) 20 g, KBM503 (trade name, Shin-Etsu Chemical Co., Ltd., γ-methacryloxypropyltrimethoxysilane) 20 g, KBM803 (trade name, Shin-Etsu Chemical Co., Ltd.) Monomer solution by mixing 10 g of γ-mercaptopropyltrimethoxysilane) and 3 g of V-65 (trade name, 2,2′-azobis (2,4-dimethylvaleronitrile) manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator Was prepared. The monomer solution was added dropwise over 2 hours while heating to 100 ° C. in a nitrogen atmosphere, and the reaction was further performed for 1 hour. Thereafter, a polymerization initiator solution in which V-651 g was dissolved in 20 g of toluene was dropped over 10 minutes, and the reaction was further performed for 4 hours. Thereafter, toluene was distilled off under reduced pressure to obtain a liquid curable resin B-14 at room temperature which is a curable vinyl polymer having a silicon-containing characteristic group and a tertiary amino group in the molecule.

(Examples 32-44, Comparative Examples 6 and 7)
Curable resins B-5 to B-14 obtained in Synthesis Examples 5 to 14, Silyl S303 (trade name; manufactured by Kaneka Chemical Co., Ltd., polyoxyalkylene having a hydrolyzable silyl group) and MA440 (trade name; A mixture of a polyoxyalkylene having a hydrolyzable silyl group and an acrylic polymer having a hydrolyzable silyl group) manufactured by Kaneka Chemical Industry Co., Ltd. was charged into the planetary mixer at the ratio shown in Table 5 and was subjected to reduced pressure. After kneading while heating and dehydrating at 100 ° C. for 1 hour and cooling to room temperature, 5 parts by weight of Shellsol TK (trade name; manufactured by Shell Chemicals Japan, isoparaffin), KBM903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ−) 1 part by weight of aminopropyltrimethoxysilane) and the curing catalyst shown in Table 3 were added at the blending ratio (parts by weight) shown in Table 3, and kneaded for 30 minutes under reduced pressure. Each obtain a curable resin composition. Each curable resin composition was quickly filled into a sealed container and left at 23 ° C. for at least 2 weeks. Table 5 shows the skinning time of each curable resin composition.

＊１０ 商品名；鐘淵化学工業社製、分子内に上記含珪素特性基を有するポリオキシアルキレン
＊１１ 商品名；鐘淵化学工業社製、加水分解性シリル基を有するポリオキシアルキレンと加水分解性シリル基を有するアクリル重合体との混合物
＊１２ 商品名；シェルケミカルズジャパン、イソパラフィン
＊１３ 商品名；信越化学工業社製、γ−アミノプロピルトリメトキシシラン
＊１４ 商品名；日東化成社製、ポリ（ジブチルスタノキサン）ジシリケート化合物

* 10 Product name: manufactured by Kaneka Chemical Industry Co., Ltd., polyoxyalkylene having the above-mentioned silicon-containing characteristic group in the molecule * 11 Product name: manufactured by Kaneka Chemical Industry Co., Ltd., polyoxyalkylene having hydrolyzable silyl group and hydrolysis Mixture with acrylic polymer having a functional silyl group * 12 Product name; Shell Chemicals Japan, Isoparaffin * 13 Product name; Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane * 14 Product name; Nitto Kasei Co., Ltd. (Dibutylstannoxane) disilicate compound

As shown in Table 5, when a curable resin having the silicon-containing characteristic group in the molecule and the polar element portion in the molecule is used, it is more preferable to use a boron trifluoride monoethylamine complex. It can be seen that curing is much faster than using a compound.
From the results of Tables 1 to 5, it has at least one silicon-containing characteristic group selected from the group consisting of hydrolyzable silyl group and silanol group in the molecule, and urethane bond, thiourethane bond, urea bond in the molecule , Thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group and tertiary amino group at least one type of bond and / or curable It can be seen that when a Lewis acid and / or its complex (B) is added to the resin (A) as a curing catalyst, a curable resin composition having a very high curing rate can be prepared.

Hereinafter, the present invention will be described in detail with reference to examples.
<Examples and comparative examples relating to curable resins having silicon-containing characteristic groups in the molecule and having at least one urethane bond, substituted urea bond and / or tertiary amino group in the molecule >
(Synthesis of secondary amino group-containing hydrolyzable alkoxysilane compound)
Each compound shown in Table 6 was mixed at a ratio (parts by weight) shown in Table 6 under a nitrogen atmosphere and reacted at 40 ° C. for 7 days to give three kinds having a secondary amino group (—NH—). Hydrolyzable alkoxysilane compounds (silylating agents) (reactant 1-A, reactant 1-B, reactant 1-C) were synthesized.

＊１５ 商品名；信越化学工業社製、γ−アミノプロピルトリメトキシシラン
＊１６ 商品名；信越化学工業社製、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン
（イソシアネート基とチオウレタン結合とを有する重合性ビニルモノマーの合成）
アリルメルカプタン１５７．２ｇと、トリレンジイソシアネート（住化バイエルウレタン社製、商品名「スミジュールＴ−８０」）１７４．２ｇとを、窒素雰囲気下にて混合し、４０℃で２４時間反応させて、イソシアネート基とチオウレタン結合とを有する重合性ビニル化合物（反応物２−Ａ）を合成した。

* 15 Product name: Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane * 16 Product name: Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) γ-aminopropyltrimethoxysilane (isocyanate group and thiourethane bond) Of a polymerizable vinyl monomer having
157.2 g of allyl mercaptan and 174.2 g of tolylene diisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name “Sumijoule T-80”) are mixed in a nitrogen atmosphere and reacted at 40 ° C. for 24 hours. Then, a polymerizable vinyl compound (reactant 2-A) having an isocyanate group and a thiourethane bond was synthesized.

(Synthesis of polymerizable vinyl monomer having silicon-containing characteristic group and substituted urea bond, thiourethane bond, urethane bond or Michael atom group derived from Michael addition reaction)
Each compound shown in Table 7 was mixed in each proportion (parts by weight) shown in Table 7 under a nitrogen atmosphere and reacted at 50 ° C. for 7 days to obtain three hydrolyzable silyl group-containing polymerizable vinyl monomers ( Reactant 3-A, reactant 3-B, and reactant 3-C) were synthesized. Reactant 3-A, Reactant 3-B, and Reactant 3-C are hydrolyzable silyl group-containing polymerizable vinyl monomers each having a nitrogen-containing atomic group derived from a Michael addition reaction in the molecule. In addition, each compound shown in Table 7 was mixed in each proportion (part by weight) shown in Table 7 under a nitrogen atmosphere and reacted at 40 ° C. for 24 hours to obtain two hydrolyzable silyl group-containing polymerizable vinyls. Monomers (reactant 3-D, reactant 3-E) were synthesized. Reactant 3-D is a hydrolyzable silyl group-containing polymerizable vinyl monomer having a urethane bond in the molecule, and Reactant 3-E is a hydrolyzable silyl group-containing polymerizable vinyl monomer having a thiourethane bond in the molecule. It is.

＊１７ 商品名：共栄化学社製、２−ヒドロキシ−３−アクリロイロキシプロピルメタクリレート
＊１８ 商品名：共栄化学社製、トリメチロールプロパントリアクリレート
＊１９ 商品名：日本サイテックインダストリー社製、ｍ−イソプロペニルα，αジメチルベンジル イソシアネート
＊２０ 商品名；信越化学工業社製、γ−アミノプロピルトリメトキシシラン

* 17 Product name: manufactured by Kyoei Chemical Co., Ltd., 2-hydroxy-3-acryloyloxypropyl methacrylate * 18 Product name: manufactured by Kyoei Chemical Co., Ltd., trimethylolpropane triacrylate * 19 Product name: manufactured by Nippon Cytec Industry Co., Ltd., m-iso Propenyl α, α-dimethylbenzyl isocyanate * 20 Product name; γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.

( Synthesis of a curable resin having a silicon-containing characteristic group in the molecule and having at least one urethane bond, substituted urea bond and / or tertiary amino group in the molecule )
(Synthesis Examples 15-18)
The polyol compound and isocyanate compound shown in Table 8 were reacted at 90 ° C. for 10 hours while being stirred and mixed in a nitrogen atmosphere at each ratio (part by weight) shown in Table 8. Next, the obtained reaction product and the silylating agent shown in Table 8 were reacted at 90 ° C. for 1 hour while stirring and mixing in the respective proportions (parts by weight) shown in Table 8 in a nitrogen atmosphere, and four kinds were obtained. Liquid curable resins (curable resin B-15, curable resin B-16, curable resin B-17, and curable resin B-18) were synthesized.

＊２１ 商品名：旭硝子ウレタン社製、ポリプロピレングリコール
＊２２ 商品名：武田薬品工業社製、ポリプロピレングリコール
＊２３ 商品名：旭電化工業社製、ポリエステルポリオール
＊２４ 商品名：三菱化学社製、ポリテトラメチレングリコール
＊２５ 商品名：住化バイエルウレタン社製、イソホロンジイソシアネート
＊２６ 商品名：住化バイエルウレタン社製、トリレンジイソシアネート
＊２７ 商品名：信越化学工業社製、Ｎ−フェニル−γ−アミノプロピルトリメトキシラン

* 21 Product name: Asahi Glass Urethane Co., Ltd., polypropylene glycol * 22 Product name: Takeda Pharmaceutical Co., Ltd., polypropylene glycol * 23 Product name: Asahi Denka Kogyo Co., Ltd., polyester polyol * 24 Product name: Mitsubishi Chemical Co., Ltd., Polytetra Methylene glycol * 25 Product name: Sumika Bayer Urethane Co., Ltd., Isophorone diisocyanate * 26 Product name: Sumika Bayer Urethane Co., Ltd., tolylene diisocyanate * 27 Product name: Shin-Etsu Chemical Co., Ltd., N-phenyl-γ-aminopropyl Trimethoxylane

(5) Synthesis of silicon-containing characteristic group-containing vinyl polymer (Synthesis Examples 19 to 23)
Silylated urethane resin (reactant 4-A, reactant 4-B, reactant 4-C or reactant 4-D) shown in Table 9 as a reaction solvent is added to n-butyl acrylate and hydrolyzable silyl Group-containing polymerizable vinyl monomer (reactant 3-A, reactant 3-B, reactant 3-C, reactant 3-D or reactant 3-E), lauryl mercaptan as a chain transfer agent, and polymerization initiation 5 hours while heating a monomer mixed solution having a blending ratio (parts by weight) shown in Table 9 consisting of 2,2′-azobisisobutyronitrile (AIBN) as an agent to 100 ° C. in a nitrogen atmosphere Over 5 hours, and allowed to react for 2 hours to obtain 5 types of mixed resin liquids (curable resin B-19, cured) of a vinyl polymer containing a silicon-containing characteristic group and liquid curable resins B-15 to B-18. Resin B-20, curable resin B-21, curable resin B-2 2, curable resin B-23) was synthesized.

(Examples 45 to 53 and Comparative Examples 8 and 9)
Chromium resins B-15 to B-23 were charged into a planetary mixer in the proportions (parts by weight) shown in Table 10, kneaded while being heated and dehydrated at 100 ° C. for 1 hour under reduced pressure, and cooled to room temperature. In addition, a curing catalyst shown in Table 10 dissolved in 2 parts by weight of Hisolv MTM (manufactured by Toho Chemical Co., Ltd., trade name) was added at a ratio (parts by weight) shown in Table 10 and kneaded for 30 minutes under reduced pressure. A seed curable resin composition was obtained.
<Curing test>
Each of the above curable resin compositions was quickly filled into a sealed container and allowed to stand at 23 ° C. for 2 weeks or longer, and then the skinning time was measured. The results are shown in Table 10 and Table 11.

＊２８ 商品名；東邦化学工業社製、末端封鎖ポリエチレングリコール

* 28 Product name; manufactured by Toho Chemical Industry Co., Ltd., end-capped polyethylene glycol

＊２９ 商品名：日東化成社製、ジブチル錫塩と正珪酸エチルとの反応生成物
＊３０ 商品名：日東化成社製、ジブチル錫ジアセチルアセトナート
表１０及び表１１の結果から分かるように、実施例４５〜５３で示される本発明にかかる硬化性樹脂組成物は、比較例８及び９で示される硬化性樹脂組成物に比べて、皮張り時間が格段に短い。

* 29 Product name: manufactured by Nitto Kasei Co., Ltd., reaction product of dibutyltin salt and normal ethyl silicate * 30 Product name: manufactured by Nitto Kasei Co., Ltd., dibutyltin diacetylacetonate The curable resin composition according to the present invention shown in Examples 45 to 53 has a significantly shorter skin time than the curable resin compositions shown in Comparative Examples 8 and 9.

(Example 54 and Comparative Example 10)
The curable resin B-19 and filler (silica aerogel made by Fuji Silysia Chemical Co., Ltd., hydrophobized with dimethylsiloxane, trade name “Silophobic 200”) in the proportions (parts by weight) shown in Table 12 are planetary. The mixture was put into a mixer, kneaded while heating and dehydrating at 100 ° C. for 1 hour under reduced pressure, cooled to room temperature, and then a silane coupling agent (trade names “KBM-903” and “Shellsol TK” manufactured by Shin-Etsu Chemical Co., Ltd.). ") The curing catalyst shown in Table 12 dissolved in 2 parts by weight was added in the ratio (parts by weight) shown in Table 12, and kneaded for 30 minutes under reduced pressure to obtain two types of moisture-curable adhesive compositions. It was. The above moisture-curing adhesive composition is filled into an aluminum laminate tube with a capacity of 250 ml using a hermetic filling device and left at 23 ° C. for 2 weeks or more, and then the skinning time and adhesive strength are measured. did. The skinning time was also measured after the aluminum laminated tube was stored in an atmosphere of 50 ° C. for one month. The adhesive strength was measured by the following method. The results are shown in Table 12.

<Adhesive strength>
Apply 0.2 g of moisture curable adhesive composition uniformly on the application surface (25 mm × 25 mm) of the asada material (25 mm × 100 mm) and immediately apply the asada material, stainless steel plate or acrylic plate (both 25 mm × 25 mm). After bonding and curing at 23 ° C. and a relative humidity of 50 to 60% for 7 days, the tensile shear bond strength (N / mm ² ) was measured according to JIS K 6850.

  As can be seen from Table 12, the moisture curable adhesive composition according to the present invention shown in Example 54 has a significantly shorter skinning time than the moisture curable adhesive composition shown in Comparative Example 10. . In addition, the moisture curable adhesive composition according to the present invention shown in Example 54 using a boron trifluoride monoethylamine complex is a moisture curable adhesive composition as in the case of using an organic tin compound. It turns out that sufficient adhesive strength is expressed.

(Synthesis Example 24)
In a reaction vessel, 222.4 g of KBM603 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane) and 172.2 g of methyl acrylate were placed under a nitrogen atmosphere. While stirring and mixing, the reaction product SE-24 was obtained by reacting at 80 ° C. for 10 hours.
In another reaction vessel, 900 g of PML4010 (trade name; manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000), PR5007 (trade name; manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene-containing polyoxypropylene polyol) ) And 100 g of Desmodur I (trade name; manufactured by Sumika Bayer Urethane Co., Ltd., isophorone diisocyanate) are allowed to react at 90 ° C. for 8 hours while stirring and mixing in a nitrogen atmosphere, so that an isocyanate group is present in the molecule. A curable resin PB-24, which is a curable polyoxyalkylene resin having the following, was obtained. Thereafter, 110 g of the reaction product SE-24 was added, and the mixture was allowed to react at 90 ° C. for 2 hours while stirring and mixing in a nitrogen atmosphere, thereby having a urethane bond, a substituted urea bond and a silicon-containing characteristic group in the molecule. A liquid curable resin B-24 was obtained at room temperature, which is a polyoxyalkylene resin .

(Synthesis Example 25)
In a reaction container, 206.4 g of KBM602 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane) and 172.2 g of methyl acrylate were placed under a nitrogen atmosphere. While stirring and mixing, the reaction product SE-25 was obtained by reacting at 80 ° C. for 10 hours.
In another reaction vessel, 900 g of PML4010 (trade name; manufactured by Asahi Glass Urethane Co., Ltd., polyoxypropylene polyol, number average molecular weight 10,000), PR5007 (trade name; manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyethylene-containing polyoxypropylene polyol) ) And 100 g of Desmodur I (trade name; manufactured by Sumika Bayer Urethane Co., Ltd., isophorone diisocyanate) are allowed to react at 90 ° C. for 8 hours while stirring and mixing in a nitrogen atmosphere, so that an isocyanate group is present in the molecule. A curable resin PB-25, which is a curable polyoxyalkylene resin having the following, was obtained. Thereafter, 104 g of the reaction product SE-25 was added, and the mixture was allowed to react at 90 ° C. for 2 hours while stirring and mixing in a nitrogen atmosphere, thereby having a urethane bond, a substituted urea bond and a silicon-containing characteristic group in the molecule. A liquid curable resin B-25 was obtained at room temperature, which is a polyoxyalkylene resin .

(Synthesis of hydrolyzable alkoxysilane compound having secondary amino group)
In a reaction vessel, 100.1 g of ethyl acrylate and 163.3 g of KBM902 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropylmethyldimethoxysilane) were placed and reacted at 23 ° C. for 7 days with stirring in a nitrogen atmosphere. Reactant 4-A was obtained. Similarly, 200.2 g of ethyl acrylate and 222.4 g of KBM603 were placed in a reaction vessel and reacted at 23 ° C. for 7 days under stirring in a nitrogen atmosphere to obtain a reaction product 4-B.
(Synthesis of hydrolyzable silyl group-containing polymerizable vinyl monomer having secondary amino group)
A reaction vessel was charged with 100.1 g of ethyl acrylate and 57.1 g of allylamine and allowed to react for 7 days at 50 ° C. with stirring in a nitrogen atmosphere to obtain a reaction product 5-A.

(Synthesis of compounds having an isocyanate group and a substituted urea bond, thiourethane bond or urethane bond)
The compounds shown in Table 13 or the reactant 5-A obtained in Synthesis Example 2 and Sumidur T-80 (trade name: manufactured by Sumika Bayer Urethane Co., Ltd., tolylene diisocyanate) are shown in Table 13 in parts (parts by weight). And reacted for 7 days at 40 ° C. with stirring under a nitrogen atmosphere to obtain reactant 6-A, reactant 6-B, reactant 6-C and reactant 6-D.

(Synthesis of compounds having an isocyanate group and a substituted urea bond, thiourethane bond or urethane bond)
Using the compounds shown in Table 14 and the reactants 4-A or 4-B in the proportions (parts by weight) shown in Table 14, they were reacted at 50 ° C. for 7 days with stirring in a nitrogen atmosphere to produce reactants 7-A and reactions. The product 7-B, the reactant 7-C, the reactant 7-D and the reactant 7-E were obtained. Similarly, using the compounds and reactants 4-A or 4-B and reactants 6-A, 6-B, 6-C, or 6-D shown in Table 14 in the proportions (parts by weight) shown in Table 14. The reaction was carried out at 40 ° C. for 1 day with stirring under a nitrogen atmosphere, and the reactant 7-E, reactant 7-F, reactant 7-G, reactant 7-H, reactant 7-I and reactant 7-J were reacted. Got.

＊３１ 商品名：共栄社化学社製、２−ヒドロキシ−３−アクリロイロキシプロピルメタクリレート＊３２ 商品名：共栄社化学社製、トリメチロールプロパンアクリレート
＊３３ 商品名：日本サイテックインダストリー社製、ｍ−イソプロペニル−α、α′−ジメチルベンジルイソシアネート
＊３４ 商品名：昭和電工社製、２−イソシアネートエチルメタクリレート
＊３５ 商品名：信越化学工業社製、γ−アミノプロピルトリメトキシシラン

* 31 Product name: Kyoeisha Chemical Co., Ltd., 2-hydroxy-3-acryloyloxypropyl methacrylate * 32 Product name: Kyoeisha Chemical Co., Ltd., trimethylolpropane acrylate * 33 Product name: Nihon Cytec Industry Co., Ltd., m-isopropenyl -Α, α'-dimethylbenzyl isocyanate * 34 Product name: Showa Denko, 2-isocyanatoethyl methacrylate * 35 Product name: Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane

(Synthesis of polymerizable vinyl monomer having silicon-containing characteristic group and hydroxyl group in the molecule)
In a reaction vessel, 114 g of allyl glycidyl ether, 196 g of KBM803 and 1 g of triethylamine were added, and the mixture was reacted for 7 days at 50 ° C. with stirring in a nitrogen atmosphere to obtain a reaction product 5.
(Synthesis Examples 26 to 39)
The curable resin B-24 or B-25 obtained in Synthesis Example 24 or 25 was used as a reaction solvent, and in the blending ratio (parts by weight) shown in Table 15 and Table 16, n-butyl acrylate, reactant 5-A , Reactants 7-A to 7-J, lauryl mercaptan and AIBN, and in some cases, KBM503 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-methacryloxypropyltrimethoxysilane) was added for 5 hours. The solution was added dropwise and reacted at 100 ° C. for 2 hours to synthesize liquid curable resins B-26 to B-39 at room temperature.

(Examples 55 to 70)
100 g of each of the curable resins B-24 to B-39 obtained in Synthesis Examples 24 to 39 was put in a planetary mixer together with 40 g of MR-10G (trade name: methacrylic acid resin powder manufactured by Soken Chemical Co., Ltd.). After dehydrating and kneading at 100 ° C. under reduced pressure, 0.5 g of KBM903 and 0.2 g of BF ₃ piperidine complex were added and kneaded to obtain a curable resin composition. These curable resin compositions are quickly filled into a sealed container and left at 23 ° C. for 2 weeks or more, then cured at a temperature of 23 ° C. and a relative humidity of 50 to 60%, and the time to reach the skin is measured. The results are shown in Table 17. Also, using these curable resin compositions, 0.2 g of moisture curable adhesive composition was uniformly applied and bonded to stainless steel (SUS304 2B) (25 mm × 100 mm) as an adherend, and the relative temperature was 23 ° C. After curing for 7 days at a humidity of 50 to 60%, the tensile shear bond strength (N / mm ² ) was measured in accordance with JIS K 6850.

(Comparative Examples 11 and 12)
100 g of each of curable resins B-24 and B-25 was placed in a planetary mixer together with 40 g of MR-10G (trade name: manufactured by Soken Chemical Co., Ltd., methacrylic acid resin powder), and heated and dehydrated and kneaded at 100 ° C. under reduced pressure. Thereafter, 0.5 g of KBM903 and 0.2 g of Neostan U-303 (trade name, manufactured by Nitto Kasei Co., Ltd., dialkyltin bis (triethoxysilicate)) were added and kneaded to obtain a curable resin composition. These curable resin compositions are quickly filled into a sealed container and left at 23 ° C. for 2 weeks or more, then cured at a temperature of 23 ° C. and a relative humidity of 50 to 60%, and the time to reach the skin is measured. The results are shown in Table 17. Further, using these curable resin compositions, 0.2 g of a moisture curable adhesive composition was uniformly applied and bonded to stainless steel (SUS304 2B) (25 mm × 100 mm) as an adherend, and the relative humidity at 23 ° C. After curing at 50 to 60% for 7 days, the tensile shear bond strength (N / mm ² ) was measured according to JIS K 6850.

表１７における実施例５５と比較例１１、及び、実施例５６と比較例１２の結果から、本発明にかかる硬化性樹脂に対して三フッ化ホウ素ピペリジン錯体を硬化触媒に用いると、ジアルキル錫系化合物と比較して、硬化が非常に速いことが分かる。その理由は、各実施例で得られた硬化性樹脂組成物の硬化性樹脂には上記極性要素部分があるために、ＢＦ₃のピペリジン錯体がこれらの極性基等の近傍に呼び込まれ、硬化速度が速くなったものと考えられる。

From the results of Example 55 and Comparative Example 11 in Table 17 and Example 56 and Comparative Example 12, when a boron trifluoride piperidine complex was used as a curing catalyst for the curable resin according to the present invention, a dialkyltin-based compound was used. It can be seen that curing is very fast compared to the compound. The reason is that since the curable resin of the curable resin composition obtained in each example has the above polar element portion, the piperidine complex of BF ₃ is called in the vicinity of these polar groups and cured. It is thought that the speed has increased.

(Example 71) (Comparative Example 13)
100 parts by weight of curable resin B-24 and 50 parts by weight of white glaze CCR (trade name: manufactured by Shiraishi Kogyo Co., Ltd., calcium carbonate) were heated and dehydrated at 100 ° C. under reduced pressure, cooled to room temperature, and ancamine K-54 (product) Name, manufactured by Air Products, epoxy resin curing agent) 5 parts by weight, KBM903 3 parts by weight, boron trifluoride piperidine complex (Example 71) 0.1 parts by weight or Stan No. 1.5 parts by weight of 918 (Comparative Example 13) was added and kneaded for 30 minutes under reduced pressure to prepare agent A. On the other hand, 50 parts by weight of Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin) and 40 parts by weight of white glossy CCR were kneaded to prepare B agent. The above agent A and agent B are filled into an aluminum laminate tube having a capacity of 250 ml using a hermetic filling device and left at 23 ° C. for 2 weeks or more, and then the agent A and agent B are in a ratio of 2: 1. Two kinds of curable resin compositions were obtained by mixing (weight ratio). The skinning time of these curable resin compositions was measured. The results are shown in Table 18.

(Example 72) (Comparative example 14)
100 parts by weight of curable resin B-24, 50 parts by weight of Epicoat 828, and 40 parts by weight of white glossy CCR were heated and dehydrated at 100 ° C. under reduced pressure, cooled to room temperature, and Versamine 15N (trade name, manufactured by Cognis Japan, 15 parts by weight of ketimine compound), 3 parts by weight of KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane), and 0.1 part by weight of boron trifluoride piperidine complex (Example 72) Department or Stan No. 1.5 parts by weight of 918 (Comparative Example 14) was added and kneaded for 30 minutes under reduced pressure to obtain two curable resin compositions. These curable resin compositions were filled in an aluminum laminate tube having a capacity of 250 ml using a hermetic filling device, and allowed to stand at 23 ° C. for 2 weeks or more, and then the skinning time was measured. The results are shown in Table 18.

(Example 73) (Comparative Example 15)
After 100 parts by weight of the curable resin B-31 was heated and dehydrated at 100 ° C. under reduced pressure, it was cooled to room temperature, 5 parts by weight of ancamine K-54, and 0.1% of boron trifluoride piperidine complex (Example 73). Parts by weight or stan no. 1.5 parts by weight of 918 (Comparative Example 15) was added and kneaded for 30 minutes under reduced pressure to prepare agent A. The agent A and Epicoat 828 were filled into an aluminum laminate tube having a capacity of 250 ml using a hermetic filling device and left at 23 ° C. for 2 weeks or more, and then the Agent A and Epicoat 828 were in a ratio of 2: 1. Two kinds of curable resin compositions were obtained by mixing (weight ratio). The skinning time of these curable resin compositions was measured. The results are shown in Table 18.

(Example 74) (Comparative Example 16)
100 parts by weight of curable resin B-31, 50 parts by weight of Epicoat 828, and 40 parts by weight of white glossy CCR were heated and dehydrated at 100 ° C. under reduced pressure, cooled to room temperature, and Versamine 15N (trade name, manufactured by Cognis Japan, 15 parts by weight of ketimine compound), KBM403 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane), 0.1 part by weight of boron trifluoride piperidine complex (Example 74) or Stan No. . 1.5 parts by weight of 918 (Comparative Example 16) was added and kneaded for 30 minutes under reduced pressure to obtain two types of curable resin compositions. These curable resin compositions were filled in an aluminum laminate tube having a capacity of 250 ml using a hermetic filling device, and allowed to stand at 23 ° C. for 2 weeks or more, and then the skinning time was measured. The results are shown in Table 18.

表１８の結果から明らかなように、より少量の三フッ化ホウ素ピペリジン錯体を硬化触媒として用いた実施例７１〜実施例７４の硬化性樹脂組成物の皮張り時間は、通常量の有機錫化合物（スタンＮｏ．９１８）を硬化触媒として用いた比較例１３〜比較例１６の硬化性樹脂組成物の皮張り時間に比べて大きな違いがない。つまり、三フッ化ホウ素ピペリジン錯体を用いた場合、硬化が速いことが分かる。その理由は、これら硬化性樹脂は、樹脂の分子主鎖に上記極性要素部分を有するため、ＢＦ₃のピペリジン錯体がこれらの極性基等の近傍に呼び込まれ、硬化速度が速くなったものと考えられる。

As is apparent from the results in Table 18, the skinning time of the curable resin compositions of Examples 71 to 74 using a smaller amount of boron trifluoride piperidine complex as the curing catalyst is the usual amount of organotin compound. There is no significant difference compared to the skinning time of the curable resin compositions of Comparative Examples 13 to 16 using (Stan No. 918) as the curing catalyst. That is, it turns out that hardening is quick when a boron trifluoride piperidine complex is used. The reason is that these curable resins have the above polar element part in the molecular main chain of the resin, so that the piperidine complex of BF ₃ is called in the vicinity of these polar groups and the curing rate is increased. Conceivable.

<Examples and comparative examples relating to curable resins having a silicon-containing characteristic group in the molecule and at least a hydroxyl group in the molecule >
(Synthesis Example 40)
In a reaction vessel, 100 g of DMDS (trade name, manufactured by Maruzen Chemical Co., Ltd., 1,5-dimercapto-3-thiapentane), 80 g of TSL8350 (trade name, manufactured by GE Toshiba Silicone Co., Ltd., γ-glycidoxypropyltrimethoxysilane) and After adding 1.0 g of 2,4,6-tris (dimethylaminomethyl) phenol and reacting at 50 ° C. for 7 days under a nitrogen atmosphere, unreacted components were distilled off under reduced pressure to obtain a reaction product PB-40. Was synthesized.
In a reaction vessel, 100 g of SDX-1690 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyalkylene having an allyl group at both ends, number-average molecular weight 3,000) and 25 g of reactant PB-40 were placed in a nitrogen atmosphere. The temperature was raised to ° C. Subsequently, a mixed solution of 1 g of 2,2′-azobisisobutyronitrile (AIBN) and 5 g of toluene was dropped over 2 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-40 was manufactured at room temperature.

(Synthesis Example 41)
DMDO (trade name, manufactured by Maruzen Chemical Co., Ltd., 1,8-dimercapto-3,6-dioxaoctane) 100 g, TSL8350 (trade name, manufactured by GE Toshiba Silicone Co., Ltd., γ-glycidoxypropyltrimethoxysilane) ) And 1.0 g of 2,4,6-tris (dimethylaminomethyl) phenol were added and reacted at 40 ° C. for 10 days in a nitrogen atmosphere, and then unreacted components were distilled off under reduced pressure. The product PB-41 was synthesized.
In a reaction vessel, 100 g of SDX-1690 and 26 g of the reaction product PB-41 were placed, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Subsequently, a mixed solution of 5 g of AIBN and 20 g of toluene was dropped over 2 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-41 was manufactured at room temperature.

(Synthesis Example 42)
100 g of SDX-1690 and 11 g of DMDO were added to the reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Subsequently, a mixed solution of 1 g of AIBN and 5 g of toluene was dropped over 2 hours. Furthermore, it was made to react at the same temperature for 1 hour, and the reaction material PB-42 was synthesize | combined.
After the reaction product containing the reaction product PB-42 was cooled to 70 ° C., 18.9 g of TSL8350 and 0.2 g of 2,4,6-tris (dimethylaminomethyl) phenol were added, and the reaction product was maintained at 70 ° C. in a nitrogen atmosphere. For 10 hours to produce a curable resin B-42 that is liquid at room temperature.

(Synthesis Example 43)
500 g of polytail HA (trade name, manufactured by Mitsubishi Chemical Co., Ltd., polyolefin polyol) was placed in a reaction vessel, and a 28 wt% methanol solution of sodium methoxide was added in an amount of 1. with respect to the number of hydroxyl groups in 1 mol of polytail. It added so that it might become 05 times mole, and stirred for 30 minutes at 120 degreeC. Next, after methanol removal reaction under reduced pressure, 36 g of allyl chloride was added and reacted for 1 hour. Unreacted components were distilled off under reduced pressure, and by-product inorganic substances and the like were removed and purified to obtain a terminal allylated hydrocarbon polymer PB-43.
100 g of terminal allylated hydrocarbon polymer PB-43 and 16 g of KBM803 (trade name; Shin-Etsu Chemical Co., Ltd., mercaptosilane compound) were placed in a reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Subsequently, a mixed solution of 1 g of AIBN and 5 g of toluene was dropped over 2 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-43 was manufactured at room temperature.

(Synthesis Example 44)
In a reaction vessel, 100 g of 1,2-ethanedithiol, 248 g of TSL8350 (trade name, manufactured by GE Toshiba Silicone, γ-glycidoxypropyltrimethoxysilane) and 1.0 g of triethylamine were added at 50 ° C. in a nitrogen atmosphere. After reacting for 7 days, unreacted 1,2-ethanedithiol was distilled off under reduced pressure at 100 ° C. to obtain a reaction product PB-44.
In a reaction vessel, 100 g of SDX-1690 and 14 g of the reaction product PB-44 were placed, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Subsequently, a mixed solution of 1 g of AIBN and 5 g of toluene was dropped over 2 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-44 was manufactured at room temperature.

(Examples 75 to 89)
100 g of each of the curable resins B-40 to B-44 obtained in Synthesis Examples 40 to 44 was put in a planetary mixer together with 40 g of MR-10G (trade name: methacrylic acid resin powder, manufactured by Soken Chemical Co., Ltd.). After dehydrating and kneading at 100 ° C. under reduced pressure, 0.5 g of KBM903 and 0.2 g of BF ₃ piperidine complex were added and kneaded to obtain a curable resin composition. These curable resin compositions were allowed to stand at 23 ° C. for 2 weeks or more, then cured at a temperature of 23 ° C. and a relative humidity of 50 to 60%, and the time required for skinning was measured. The results are shown in Table 19.

(Comparative Example 16)
After 100 g of curable resin B-40 and 40 g of MR-10G (trade name: manufactured by Soken Chemical Co., Ltd., methacrylic acid resin powder) were put together in a planetary mixer and heated and dehydrated and kneaded at 100 ° C. under reduced pressure, KBM903 was changed to 0. 0.5 g, Neostan U-303 (trade name, manufactured by Nitto Kasei Co., Ltd., dialkyltin bis (triethoxysilicate)) was added and kneaded to obtain a curable resin composition. These curable resin compositions are quickly filled into a sealed container and left at 23 ° C. for 2 weeks or more, then cured at a temperature of 23 ° C. and a relative humidity of 50 to 60%, and the time to reach the skin is measured. The results are shown in Table 19.

表１９の記載から明らかなように、各実施例で得られた硬化性樹脂組成物の硬化性樹脂にはヒドロキシル基があるために、ＢＦ₃のピペリジン錯体がこれらの極性基等の近傍に呼び込まれ、通常用いられる錫系触媒と比較して大幅に硬化速度が速くなったものと考えられる。

As is clear from the description in Table 19, since the curable resin of the curable resin composition obtained in each example has a hydroxyl group, the piperidine complex of BF ₃ is called in the vicinity of these polar groups. Therefore, it is considered that the curing rate is significantly increased as compared with a tin-based catalyst that is usually used.

<Examples and comparative examples relating to curable resins having a silicon-containing characteristic group in the molecule and at least a sulfide bond or a thiourethane bond in the molecule >
(Synthesis Example 45)
Under a nitrogen atmosphere, 222 g of isophorone diisocyanate (IPDI) was added to the reaction vessel, and 222 g of A-link15 (trade name, manufactured by Nihon Unicar Co., Ltd., N-ethyl-aminoisobutyltrimethoxysilane) was added dropwise while stirring. . After completion of the dropwise addition, reaction was performed at 80 ° C. for 2 hours to obtain a reaction product PB-45-A. Separately, 77 g of DMDS (trade name, manufactured by Maruzen Chemical Co., Ltd., 1,5-dimercapto-3-thiapentane) was added to the reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Thereafter, 222 g of the reactant PB-45-A was dropped while stirring, and the mixture was reacted at 90 ° C. for 10 hours to obtain a reactant PB-45-B.
200 g of SDX-1690 (trade name, manufactured by Asahi Denka Kogyo Co., Ltd., polyoxyalkylene having an allyl group at both ends, number average molecular weight of 3,000) and 68 g of PB-45-B were placed in a reaction vessel under a nitrogen atmosphere. The temperature was raised to ° C. Next, a mixed solution of 2 g of 2,2′-azobisisobutyronitrile (AIBN) and 10 g of toluene was dropped over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-45 was manufactured at room temperature.

(Synthesis Example 46)
In a reaction vessel, 98 g of ethyl acrylate and KBM903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane) at a rate of 179 g were mixed at 23 ° C. for 7 days while mixing in a nitrogen atmosphere. PB-46-A was synthesized.
Under a nitrogen atmosphere, 80 g of 2,4-tolylene diisocyanate (TDI) was added to the reaction vessel, and 138 g of the reaction product PB-46-A was added dropwise while stirring. After completion of the dropwise addition, the reaction product was reacted at 80 ° C. for 2 hours to obtain a reaction product PB-46-B. Separately, 77 g of DMDS was charged into the reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Then, while stirring, 110 g of the reactant PB-46-B was dropped and reacted at 90 ° C. for 10 hours to obtain a reactant PB-46-C.
200 g of SDX-1690 and 55 g of the reaction product PB-46-C were placed in a reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-46 was manufactured at room temperature.

(Synthesis Example 47)
In a reaction vessel, 200.0 g of ethyl acrylate and KBM603 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) -γ-aminopropyltrimethoxysilane) were mixed at a ratio of 220.0 g in a nitrogen atmosphere. The reaction product PB-47-A was synthesized by reacting at 23 ° C. for 7 days.
Under a nitrogen atmosphere, 80.0 g of TDI was added to the reaction vessel, and 210.0 g of the reaction product PB-47-A was dropped while stirring. After completion of the dropping, the reaction product was reacted at 80 ° C. for 2 hours to obtain a reaction product PB-47-B. Separately, 77 g of DMDS was charged into the reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Then, while stirring, 290.0 g of the reaction product PB-47-B was added dropwise and reacted at 90 ° C. for 10 hours to obtain a reaction product PB-47-C.
200 g of SDX-1690 and 77.0 g of the reaction product PB-47-C were placed in a reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-47 was manufactured at room temperature.

(Synthesis Example 48)
In a reaction vessel, 72.0 g of dimethyl maleate, 86.5 g of phenylmaleimide, and KBM903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-aminopropyltrimethoxysilane) at a ratio of 179 g in a nitrogen atmosphere, The reaction product PB-48-A was synthesized by reacting at 23 ° C. for 7 days.
Under a nitrogen atmosphere, 87 g of TDI was charged into the reaction vessel, and 169 g of the reaction product PB-48-A was added dropwise while stirring. After completion of the dropwise addition, the reaction product was reacted at 80 ° C. for 2 hours to obtain a reaction product PB-48-B. Separately, 36 g of DMDS was added to the reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Thereafter, 128 g of the reactant PB-48-B was dropped while stirring, and the mixture was reacted at 90 ° C. for 10 hours to obtain a reactant PB-48-C.
In a reaction vessel, 200 g of SDX-1690 and 68 g of the reaction product PB-48-C were placed, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-48 was manufactured at room temperature.

(Synthesis Example 49)
117 g of KBM5103 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., γ-acryloxypropyltrimethoxysilane) and 89.5 g of KBM903 were reacted in a reaction vessel at 23 ° C. for 7 days while mixing in a nitrogen atmosphere. The reaction product PB-49-A was synthesized.
Under a nitrogen atmosphere, 87 g of TDI was charged into the reaction vessel, and 207 g of the reaction product PB-49-A was added dropwise while stirring. After completion of dropping, the reaction product was reacted at 80 ° C. for 2 hours to obtain a reaction product PB-49-B. Separately, 36 g of DMDS was added to the reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Thereafter, while stirring, 137 g of the reaction product PB-49-B was dropped and reacted at 90 ° C. for 10 hours to obtain a reaction product PB-49-C.
In a reaction vessel, 200 g of SDX-1690 and 85 g of the reaction product PB-49-C were put, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-49 was manufactured at room temperature.

(Synthesis Example 50)
Under a nitrogen atmosphere, 77 g of 2-aminoethanethiol was added to the reaction vessel, and 86 g of methyl acrylate was added dropwise while stirring. After completion of dropping, the reaction was allowed to proceed at 40 ° C. for 48 hours. Further, Y-5187 (trade name, manufactured by Nihon Unicar Co., Ltd., γ-isocyanatopropyltrimethoxysilane) at a ratio of 203 g was reacted at 23 ° C. for 7 days while mixing in a nitrogen atmosphere to obtain a reaction product PB-50. Was synthesized.
Under a nitrogen atmosphere, 300 g of polyoxyalkylene having an allyl group at both ends (number average molecular weight 8,000) and 25 g of the reactant PB-50 were placed in a reaction vessel, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-50 was manufactured at room temperature.

(Synthesis Example 51)
Under a nitrogen atmosphere, 154 g of DMDS was added to the reaction vessel, and while stirring, Y-5187 was dropped and mixed under a nitrogen atmosphere of 100 g. Furthermore, after making it react at 50 degreeC for 10 days, unreacted DMDS was depressurizingly distilled at 120 degreeC, and reaction product PB-51 was obtained.
Under a nitrogen atmosphere, 300 g of polyoxyalkylene having an allyl group at both ends (number average molecular weight 8,000) and 25 g of the reactant PB-51 were placed in a reaction vessel, and the temperature was raised to 90 ° C. under a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-51 was manufactured at room temperature.

(Synthesis Example 52)
In a nitrogen atmosphere, 57 g of allylamine was added to the reaction vessel, and 86 g of methyl acrylate was added dropwise while stirring. After completion of dropping, the reaction product was reacted at 40 ° C. for 48 hours to obtain a reaction product PB-52-A.
Separately, 111 g of IPDI was added to the reaction vessel under a nitrogen atmosphere, and 128 g of KBM573 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-γ-aminopropyltrimethoxysilane) was added dropwise. After completion of the dropping, the reaction product was reacted at 50 ° C. for 10 days to obtain a reaction product PB-52-B. Under a nitrogen atmosphere, 238 g of the reaction product PB-52-A was added to the reaction vessel, and 72 g of the reaction product PB-52-B was added dropwise. Furthermore, it was made to react at 50 degreeC for 7 days, and reactant PB-52-C was obtained.
In a reaction vessel, 62 g of reactants PB-52-C and 15 g of DMDS were mixed in a nitrogen atmosphere, and the temperature was raised to 90 ° C. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was dropped over 3 hours to obtain a reaction product PB-52-D.
300 g of polyoxyalkylene having an allyl group at both ends (number average molecular weight 8,000) and 55 g of the reaction product PB-52-D were added, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-52 was manufactured at room temperature.

(Synthesis Example 53)
In a nitrogen atmosphere, 400 g of polyoxyalkylene having an allyl group at both ends (number average molecular weight: 8,000) and 21 g of KBM803 were placed in a reaction vessel, heated to 90 ° C., and then a mixed solution of 2 g of AIBN and 10 g of toluene was added for 2 hours. It was hung and dropped. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-53 was manufactured at room temperature.

(Synthesis Example 54)
In a nitrogen atmosphere, 114 g of allyl glycidyl ether and 221 g of A-Link 15 were added to the reaction vessel and reacted at 50 ° C. for 14 days to obtain a reaction product PB-54-A.
154 g of DMDS and 160 g of the reactant PB-54-A were mixed and stirred, and the temperature was raised to 90 ° C. Subsequently, a mixed solution of 2 g of AIBN and 10 g of toluene was dropped over 3 hours, and then unreacted DMDS was distilled off under reduced pressure to obtain a reaction product PB-54-B.
300 g of polyoxyalkylene having an allyl group at both ends (number average molecular weight: 8,000) and 32 g of reactant PB-54-B were placed in a reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-54 was manufactured at room temperature.

(Synthesis Example 55)
In a nitrogen atmosphere, 114 g of allyl glycidyl ether, 196 g of KBM803, and 1 g of ancamine K54 (trade name, manufactured by Air Product Co., Ltd., epoxy resin curing agent) were added to the reaction vessel and reacted for 7 days at 50 ° C. -55-A was obtained.
300 g of polyoxyalkylene having an allyl group at both ends (number average molecular weight: 8,000) and 24 g of DMDS were placed in a reaction vessel, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and reactant PB-55-B was obtained.
Subsequently, 22 g of the reactant PB-55-A and 300 g of the reactant PB-55-B were mixed and stirred, and the temperature was raised to 90 ° C. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was dropped over 3 hours, and then the temperature was raised to 90 ° C. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-55 was manufactured at room temperature.

(Synthesis Example 56)
Under a nitrogen atmosphere, 57 g of allylamine was added to the reaction vessel, and 86 g of methyl acrylate was added dropwise while stirring. After completion of the dropwise addition, the reaction product was reacted at 40 ° C. for 48 hours to obtain a reaction product PB-56-A.
Under a nitrogen atmosphere, 72 g of the reactant PB-56-A was charged into the reaction vessel, and 118 g of KBM403 was added dropwise while stirring. After completion of the dropwise addition, the reaction product was reacted at 50 ° C. for 10 days to obtain a reaction product PB-56-B.
Under a nitrogen atmosphere, 154 g of DMDS and 180 g of the reactant PB-56-B were mixed and stirred in a reaction vessel, and the temperature was raised to 90 ° C. Subsequently, a mixed solution of 2 g of AIBN and 10 g of toluene was dropped over 3 hours, and then unreacted DMDS was distilled off under reduced pressure to obtain a reaction product PB-56-C.
300 g of polyoxyalkylene having an allyl group at both ends (number average molecular weight 8,000) and 35 g of the reaction product PB-56-C were added, and the temperature was raised to 90 ° C. in a nitrogen atmosphere. Next, a mixed solution of 2 g of AIBN and 10 g of toluene was added dropwise over 3 hours. Furthermore, it was made to react at the same temperature for 1 hour, and liquid curable resin B-56 was manufactured at room temperature.

(Synthesis Example 57)
100 g of toluene was placed in the reaction vessel. Separately, 100 g of butyl acrylate, 10 g of lauryl methacrylate, 30 g of KBM503 (trade name, γ-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), V-65 (product of Wako Pure Chemical Industries, Ltd.) as a polymerization initiator A monomer solution was prepared by mixing 1.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile). The monomer solution was added dropwise over 1 hour while heating to 100 ° C. under a nitrogen atmosphere, and the reaction was further continued for 1 hour. Thereafter, a polymerization initiator solution in which V-650.5 g was dissolved in 20 g of toluene was dropped over 10 minutes, and the reaction was further continued for 4 hours. Then, toluene was depressurizingly distilled and liquid curable resin B-57 was obtained at room temperature.

(Examples 80 to 92)
100 g of each of the curable resins B-45 to B-57 obtained in Synthesis Examples 45 to 57 was hydrophobized with 40 g of MR-10G (trade name: methacrylic acid resin powder, manufactured by Soken Chemical Co., Ltd.) and dimethylsiloxane. Silica airgel R-812 (trade name: manufactured by Nippon Aerosil Co., Ltd.) and 0.03 g were put into a planetary mixer and heated and dehydrated and kneaded at 100 ° C. under reduced pressure, and 0.5 g of KBM803 and boron trifluoride piperidine complex were changed to 0. .2 g was added and kneaded to obtain a curable resin composition. These curable resin compositions are quickly filled into a sealed container, left at 23 ° C. for 2 weeks or more, then cured at a temperature of 23 ° C. and a relative humidity of 50 to 60%, and the time until skinning is measured. The results are shown in Table 20.

(Comparative Example 17)
Silica airgel R-812 (hydrophobic-treated with 40 g of MR-10G (trade name: methacrylic acid resin powder, manufactured by Soken Chemical Co., Ltd.) and dimethylsiloxane, 100 g of each of curable resin B-47 obtained in Synthesis Example 47 (Product name: manufactured by Nippon Aerosil Co., Ltd.) 0.03 g and put into a planetary mixer, and after heat dehydration kneading at 100 ° C. under reduced pressure, 0.5 g of KBM803 and 0.2 g of Neostan U-303 were added and kneaded. A curable resin composition was obtained. These curable resin compositions are quickly filled into a sealed container, left at 23 ° C. for 2 weeks or more, then cured at a temperature of 23 ° C. and a relative humidity of 50 to 60%, and the time until skinning is measured. The results are shown in Table 20.

  As is clear from the results described in Table 20, it can be seen that the resin compositions shown in Examples 80 to 92 according to the present invention have a short skinning time. Further, it is considered that the reason why the curing is extremely slow in Comparative Example 17 is that Neostann U-303, which is a dialkyltin compound, has been deactivated by the thiol group of KBM803 (mercaptosilane). That is, by using a boron trifluoride compound, a mercaptosilane compound can be used as an adhesion-imparting agent without being delayed in curing. This is very useful in industry. So far, mercaptosilane compounds are known to have a great adhesion-imparting effect (especially for metals), but they can be used in practice because they use a general organotin compound with a delay in curing. There wasn't. By the technique of the present invention, a mercaptosilane compound can be used as an adhesion-imparting agent, and it has become possible to prepare a curable resin composition having very good adhesion to various metals.

(Synthesis Example 58)
In a reaction container, 100 g of S203 (trade name, manufactured by Kaneka Chemical Co., Ltd., polyoxyalkylene having a methyldimethoxysilyl group) and 400 g of toluene were added. Thereafter, 30 g of butyl acrylate, 30 g of lauryl methacrylate, 10 g of KBM503 (trade name, γ-methacryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), V-65 (product of Wako Pure Chemical Industries, Ltd.) as a polymerization initiator 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile)) was mixed to prepare a monomer solution. The monomer solution was added dropwise over 1 hour while heating to 100 ° C. under a nitrogen atmosphere, and the reaction was further continued for 1 hour. Thereafter, a polymerization initiator solution in which V-650.5 g was dissolved in 20 g of toluene was dropped over 10 minutes, and the reaction was further continued for 4 hours. Thereafter, toluene was distilled off under reduced pressure to obtain a liquid curable resin B-58 at room temperature which is a mixture of a curable polyoxyalkylene polymer and a curable vinyl polymer.

(Examples 93 to 97 and Comparative Example 18)
The curable resin B-24 or curable resin B-58 was put into a planetary mixer, kneaded while being heated and dehydrated at 100 ° C. for 1 hour under reduced pressure, cooled to room temperature, and then the raw materials shown in Table 21 were used. Were added in proportions (parts by weight) shown in Table 21, and kneaded for 30 minutes under reduced pressure to obtain six types of moisture-curable adhesive compositions. The viscosity of each moisture curable resin composition was measured using a B-type viscometer at 23 ° C. The results are shown in Table 21.
The above moisture-curing adhesive composition is filled into an aluminum laminate tube with a capacity of 250 ml using a hermetic filling device and left at 23 ° C. for 2 weeks or more, and then the skinning time and adhesive strength are measured. did. The adhesive strength was measured by the following method. The results are shown in Table 21.

<Adhesive strength>
0.2 g of moisture-curable adhesive composition was uniformly applied to a coated surface (25 mm × 25 mm) of a mild steel plate (25 mm × 100 mm), and immediately bonded with an acrylic plate (25 mm × 25 mm), 23 ° C., relative humidity After curing at 50 to 60% for 7 days, the tensile shear bond strength (N / mm ² ) was measured according to JIS K 6850.

＊３６ 商品名：旭硝子社製商品名、トリアルコキシシリル基を有するポリオキシアルキレン
＊３７ 商品名：綜研化学社製、アルコキシシリル基を含有するアクリルオリゴマー
＊３８ 商品名：信越化学工業社製、アルコキシシリル基を含有するシリコーンオリゴマー
＊３９ 商品名：信越化学工業社製、Ｎ−β（アミノエチル）γ−アミノプロピルトリメトキシシラン
＊４０ 商品名：信越化学工業社製、γ−メルカプトプロピルトリメトキシシラン
＊４１ 商品名：日東化成社製、ジオクチル錫ジネオデカノエート

* 36 Product name: Asahi Glass Co., Ltd., polyoxyalkylene having trialkoxysilyl group * 37 Product name: Soken Chemical Co., Ltd., acrylic oligomer containing alkoxysilyl group * 38 Product name: Shin-Etsu Chemical Co., Ltd., alkoxy Silicone oligomer containing silyl group * 39 Product name: Shin-Etsu Chemical Co., Ltd., N-β (aminoethyl) γ-aminopropyltrimethoxysilane * 40 Product name: Shin-Etsu Chemical Co., Ltd., γ-mercaptopropyltrimethoxysilane * 41 Product name: Nitto Kasei Co., Ltd., Dioctyltin Dineodecanoate

  As is apparent from the results described in Table 21, it can be seen that the skinning time is remarkably faster by using boron trifluoride monoethylamine complex as the curing catalyst. Further, in Comparative Example 18, KBM803 (mercaptosilane compound) deactivated the organotin catalyst Neostan U-830, resulting in a decrease in the curing rate, and a sufficient curing state was achieved under conditions of 23 ° C. relative humidity 50-60% for 7 days. It is guessed that it did not reach.

  The curable resin composition of the present invention can be used for paints, adhesives, sealants, casting materials, coating materials and the like. When using the above composition as an adhesive, for example, for general household use, construction interior use, industrial lines such as automobiles, audio equipment, and electronic equipment, civil engineering field work such as adhesion of water-stopping materials in tunnel shield construction It can be used for various purposes such as use.

Claims (10)

In the molecule, a silicon-containing characteristic group comprising one or more groups selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the following formula (1) (in the following formula (1), n = Moisture curable at 23 ° C., comprising a curable resin (A) which is liquid at room temperature containing at least a silicon-containing characteristic group which is 0) and a Lewis acid and / or its complex (B) Resin composition.

X represents a hydroxyl group or a hydrolyzable group, R ¹ represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and n represents 0, 1, or 2. A silicon-containing characteristic group consisting of one or more groups selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the following formula (1) in the molecule, and a urethane bond, a thiourethane bond in the molecule, One or more bonds selected from the group consisting of urea bond, thiourea bond, substituted urea bond, substituted thiourea bond, amide bond, sulfide bond, hydroxyl group, secondary amino group and tertiary amino group and / or A curable resin composition comprising a curable resin (A) containing a group and a Lewis acid and / or a complex (B) thereof.

X represents a hydroxyl group or a hydrolyzable group, R ¹ represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms, and n represents 0, 1, or 2. The ratio of one or more groups selected from the group consisting of a hydrolyzable silyl group and a silanol group represented by the above formula (1) (provided that n = 0 in the above formula (1)) is a curable resin. It is 10 to 100% per silicon-containing characteristic group consisting of one or more groups selected from the group consisting of hydrolyzable silyl groups and silanol groups represented by the above formula (1). The curable resin composition according to either 1 or 2.   Curable resin (A) in any one of Claims 1-3, Lewis acid and / or its complex (B), the hydrolyzable silyl group and silanol which are represented by said Formula (1) in a molecule | numerator A silicon-containing characteristic group composed of one or more groups selected from the group consisting of a group, an aminosilane compound (C) containing an amino group in the molecule, and / or represented by the above formula (1) in the molecule. It contains a silicon-containing characteristic group consisting of one or more groups selected from the group consisting of a hydrolyzable silyl group and a silanol group, and a mercaptosilane compound (D) containing a mercapto group in the molecule. Curable resin composition.   The curable resin composition according to any one of claims 1 to 4, wherein the Lewis acid of the Lewis acid and / or its complex (B) is a Lewis acid selected from metal chlorides.   The curable resin composition according to claim 1, wherein the Lewis acid and / or its complex (B) is boron trifluoride and / or its amine complex.   The said Lewis acid and / or its complex (B) are contained 0.001 weight part-10 weight part per 100 weight part of the said curable resin (A), The Claim 1-6 characterized by the above-mentioned. Curable resin composition. 0.001 part by weight to 10 parts by weight of the Lewis acid and / or its complex (B) per 100 parts by weight of the curable resin (A), and other than the Lewis acid and / or its complex (B) The curable resin composition according to claim 1, comprising 0.01 to 10 parts by weight of the curing catalyst (E).   The curable resin composition according to claim 8, wherein the curing catalyst (E) is a dioctyltin-based catalyst.   A moisture-curable adhesive composition comprising the curable resin composition according to claim 1.