JP2008285539A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition utilizing the reaction of a 5-membered carbonate group with an amino group, and exhibiting practical cured film strength. <P>SOLUTION: The curable resin composition comprises (A) a compound having one or more 5-membered carbonate groups represented by general formula (1) [wherein, X is a residue of the compound (A)] in the molecule, and (B) an aminosilane compound having one or more primary amino groups and a crosslinkable reactive silicon group in the molecule. The main chain of the compound (A) is preferably an oxyalkylene polymer, and the molecular weight of the residue X of the compound (A) is 500 or more. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a curable resin composition containing a curable resin having a five-membered ring carbonate group in the molecule.

  Since the cyclic carbonate group is reactive with an amino group, by reacting a compound having two or more cyclic carbonate groups in the molecule with a polyamine compound having two or more amino groups in the molecule, It can be used as a curable resin. In particular, since a five-membered carbonate group reacts well with a primary amino group at room temperature, a compound having two or more five-membered ring carbonate groups in the molecule and two or more primary amino groups in the molecule. It is known that by combining with a polyamine compound having a group, it can be used as a room temperature curable resin such as an adhesive, a sealing material, a paint, and a coating agent (Patent Document 1 and Non-Patent Document 1).

JP 2005-36081 A J. et al. Polym. Sci. Part A: Polym. Chem. 1993, 312, 2765-2773.

However, although the reaction between the five-membered ring carbonate group and the primary amino group proceeds even at room temperature, the reactivity is not so high. Therefore, when the compound having the five-membered ring carbonate group is a high molecular weight product, a cured product thereof is obtained. Has a low cohesive force and is soft. Therefore, even when it is used as a curable resin such as an adhesive, a sealing material, a paint, and a coating agent, its use is often limited due to the reason that sufficient strength cannot be obtained.
The problem to be solved by the present invention is a curable resin that exhibits practical film strength as an adhesive, a sealing material, a paint, a coating agent, etc. while utilizing the reaction between a 5-membered cyclic carbonate group and an amino group. It is to provide a composition.

  In order to solve such a problem, the present inventors, as a result of intensive research, used a specific primary aminosilane compound as a curing agent, and a compound having two or more five-membered ring carbonate groups in the molecule. It has been found that the film cohesion of the cured product can be increased to a practical level by curing, and the present invention has been completed. The present invention is composed of the following first to eighth inventions.

・・・（１）
（ただし、式中のＸは化合物（Ａ）の残基を表す） That is, the first invention includes a compound (A) having two or more five-membered carbonate groups represented by the following general formula (1) in the molecule, and one or more primary amino groups in the molecule. And an aminosilane compound (B) having a reactive silicon group capable of crosslinking, and a curable resin composition.

... (1)
(However, X in the formula represents a residue of compound (A))

・・・（２）
（ただし、式中のＲは分子量１，０００未満の２価の有機基であり、Ｙは化合物（Ａ）の残基を表す） The second invention relates to the curable resin composition according to the first invention, wherein the compound (A) has a group represented by the following general formula (2) in its molecule. is there.

... (2)
(In the formula, R is a divalent organic group having a molecular weight of less than 1,000, and Y represents a residue of the compound (A)).

  The third invention relates to the curable resin composition according to the first or second invention, wherein the main chain of the compound (A) is an oxyalkylene polymer.

  The fourth invention relates to the curable resin composition according to any one of the first to third inventions, wherein the molecular weight of the residue X or Y of the compound (A) is 500 or more. is there.

・・・（３）
（ただし、式中、Ｒ¹はフェニル基及び炭素数１〜６のアルキル基から選ばれる一種以上の官能基を、Ｒ^２はアミノ基を含んでいてもよい二価の有機基を、Ｗはフェノキシ基及び炭素数１〜６のアルコキシ基から選ばれる一種以上の官能基を、ｎは０、１又は２を、それぞれ表す）

・・・（４）
（ただし、式中、Ｒ^３、Ｒ^４、Ｒ^５は、フェニル基、分子量５００以下のアルキル基、フェノキシ基、及び、炭素数１〜６のアルコキシ基から選ばれる一種以上の基をそれぞれ表し、Ｒ^６は、フェニル基、及び、炭素数１〜６のアルキル基から選ばれる一種以上の基をそれぞれ表す） In the fifth invention, the compound (B) is a condensation reaction product of the compound (b1) represented by the following general formula (3) and the compound (b2) represented by the following general formula (4). The present invention relates to a curable resin composition according to any one of the first to fourth inventions.

... (3)
(Wherein, R ¹ represents one or more functional groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms, R ² represents a divalent organic group that may contain an amino group, and W represents One or more functional groups selected from a phenoxy group and an alkoxy group having 1 to 6 carbon atoms, n represents 0, 1 or 2 respectively)

... (4)
(However, in the formula, R ³ , R ⁴ and R ⁵ each represent one or more groups selected from a phenyl group, an alkyl group having a molecular weight of 500 or less, a phenoxy group, and an alkoxy group having 1 to 6 carbon atoms, R ⁶ represents one or more groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms.

  Further, the sixth invention further uses a polyamine compound (C) having two or more primary amino groups in the molecule, and the curing according to any one of the first to fifth inventions The present invention relates to a conductive resin composition.

  The seventh invention further relates to a curable resin composition according to any one of the first to sixth inventions, characterized by using a crosslinkable reactive silicon group condensation catalyst (D). is there.

  The eighth invention is characterized in that the condensation catalyst (D) of the reactive silicon group capable of crosslinking is one or more compounds selected from organometallic compounds and boron halide compounds. The present invention relates to a curable resin composition according to the invention.

  The curable resin composition according to the present invention has an effect of expressing a practical cured film strength by reacting and curing a compound having a specific five-membered ring carbonate group and a specific aminosilane compound. It is.

  Hereinafter, the best mode for carrying out the present invention will be described in detail. In addition, this invention is not limited only to these illustrations, Of course, a various change can be added in the range which does not deviate from the summary of this invention.

[Compound (A) having a five-membered ring carbonate group]
In the present invention, the compound (A) having a five-membered ring carbonate group (hereinafter sometimes simply referred to as “compound (A)”) has a five-membered ring carbonate group represented by the above general formula (1). A compound having two or more in a molecule.
Compound (A) can be prepared, for example, by reaction of diol with phosgene (reference, B. M. Trost and D. M. T. Chan., J. Org. Chem., 48, 3346 (1983), etc.), oxirane, etc. Reaction with β-lactone (T. Nishikubo, T. Iizuka, M. Iida and N. Isobe, Tetrahedron Lett., 27, 3741 (1986)), reaction with oxirane and carbon dioxide (WJ Peppel, Ind. Eng. Chem., 50, 767 (1958), N. Kihara and T. Endo, Macromolecules, 25, 4824 (1992)) and the like.

・・・（５） Among the compounds (A), those having a urethane bond and a five-membered ring carbonate group in the molecule represented by the general formula (2) are those containing an isocyanate group-containing urethane prepolymer (a1) and glycerin carbonate (the following general formula It can also be synthesized by a reaction with formula (5)).

... (5)

Isocyanate group-containing urethane prepolymer (a1) The isocyanate group-containing urethane prepolymer (a1) can be synthesized from the polyol compound (i) and the polyisocyanate compound (ii) by a conventionally known method.

-About polyol compound (i) As polyol compound (i), conventionally well-known polyol compounds, such as polyether polyol, polyester polyol, and polyolefin polyol, are illustrated. These polyols may be used individually by 1 type, and may use 2 or more types together as needed.

  More specifically, the polyether polyol preferably has a number average molecular weight of 500 to 30,000, and particularly preferably 1,000 to 20,000. Further, polyether polyols having 2 or more functional groups are preferred, and specific examples thereof include homopolymers such as polyoxyethylene, polyoxypropylene, polyoxybutylene, polyoxyhexylene, polyoxytetramethylene, ethylene oxide, Examples thereof include a copolymer obtained by ring-opening copolymerization of two or more kinds of monoepoxides selected from the group consisting of propylene oxide, butylene oxide, hexylene oxide and tetrahydrofuran. In particular, a polyoxypropylene polyol having 2 to 6 functional groups is preferable, and specific examples thereof include polyoxypropylene diol and polyoxypropylene triol.

  As a commercially available product of polyether polyol, manufactured by Asahi Denka Kogyo Co., Ltd .; P-2000, P-3000, manufactured by Asahi Glass Co., Ltd .; PML-3005, PML-3010, PML-3012, PML-4002, PML-4012, PML -4015, PML-5005, manufactured by Sumika Bayer Urethane Co., Ltd .; Sumiphen 3600, Sumiphen 3700, SBU-Polyol 0319 (all are trade names) and the like are exemplified.

  As the polyester polyol, a polymer obtained by polycondensation of one or more dicarboxylic acids such as maleic acid, adipic acid, sebacic acid and phthalic acid and one or more diols, ε-caprolactam Examples thereof include ring-opening polymers obtained by ring-opening polymerization of valerolactone and the like, and active hydrogen compounds such as castor oil having two or more active hydrogens. Usually, those having a molecular weight of 50 to 25,000 are used.

  Examples of the polyolefin polyol include a polyol having an ethylene / α-olefin skeleton and a polyol having a polyisobutylene skeleton.

  In addition, the main chain skeleton of the polyol compound (i) is obtained by polymerizing a polyol compound having an acrylic skeleton, a polyol compound containing an organic group having a fluorine atom, a silicon atom, a sulfur atom or a rosin skeleton, or a diene monomer. Polyol compounds having a polybutadiene skeleton and / or a polyisoprene skeleton, and the like, and an appropriate polyol compound may be used depending on the purpose of use and the required performance.

Among the polyol compounds exemplified above, the main chain skeleton (that is, the residue X or Y) of the compound (A) is polyoxyalkylene, which improves the flexibility of the resulting cured film, and various base materials. This is preferable because the adhesion to the surface is improved. Furthermore, by containing polyethylene oxide, that is, a ring-opening polymer of ethylene oxide (specifically, an oxyethylene group (—OCH ₂ CH ₂ —)) as its repeating structural unit, an acrylic base material is obtained. This is particularly preferable because the adhesion to the resin is greatly improved.
In addition, it is more preferable to select the polyol compound (i) such that the molecular weight of the main chain skeleton (that is, the residue X or Y) of the compound (A) is 500 or more because these effects are further clarified.

-Polyisocyanate Compound (ii) The polyisocyanate compound (ii) is a compound having at least two isocyanate groups (or isothiocyanate groups) in the molecule and a modified product thereof. Specific examples include aliphatic polyisocyanate compounds, alicyclic polyisocyanate compounds, araliphatic polyisocyanate compounds, and aromatic polyisocyanate compounds. More specifically, hexamethylene diisocyanate, isophorone diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3- or 1,4-xylylene diisocyanate, m-tetra Examples include, but are not limited to, methylxylylene diisocyanate, lysine diisocyanate, lysine triisocyanate, phenyl diisothiocyanate, and modified trimers thereof.

[Aminosilane compound (B)]
In the present invention, the aminosilane compound (B) (hereinafter sometimes simply referred to as “compound (B)”) has one or more primary amino groups and crosslinkable reactive silicon groups in the molecule. It is an aminosilane compound. In the moisture curable resin composition according to the present invention, the aminosilane compound (B) works as a curing agent and effectively cures the curable resin composition.
The curing mechanism is not clear, but is presumed as follows. When the compound (A) and the compound (B) are mixed, the five-membered ring carbonate group of the compound (A) reacts with the primary amino group of the compound (B). Furthermore, since the compound (B) has a crosslinkable reactive silicon group, it is considered that these are also hydrolytically condensed by moisture. It is presumed that the film cohesive force of the cured product becomes higher than before due to the complex occurrence of these curing reactions.

  As the compound (B), a compound (b1) represented by the following general formula (3), a condensation product of the compound (b1), or a compound (b2) represented by the following general formula (4) and the compound (b1) And a condensation reaction product. Among these, the condensation product of the compound (b1) and the condensation reaction product of the compound (b1) and the compound (b2) represented by the following general formula (4) are more preferable, and the condensation of the compound (b1) Of the product and the condensation reaction product of the compound (b1) and the compound (b2) represented by the following general formula (4), two or more compounds (b1) and one or more compounds (b2) A condensation reaction product is particularly preferred. This is because the condensation product has a plurality of primary amino groups in the molecule, so that the reaction probability between the compound (A) and the compound (B) is improved.

・・・（３）
（ただし、式中、Ｒ¹はフェニル基及び炭素数１〜６のアルキル基から選ばれる一種以上の官能基を、Ｒ^２は第２級アミノ基を含んでいてもよい二価の有機基を、Ｗはフェノキシ基及び炭素数１〜６のアルコキシ基から選ばれる一種以上の基を、ｎは０、１又は２を、それぞれ表す）

・・・（４）
（ただし、式中、Ｒ^３、Ｒ^４、Ｒ^５は、フェニル基、分子量５００以下のアルキル基、フェノキシ基、及び、炭素数１〜６のアルコキシ基から選ばれる一種以上の基をそれぞれ表し、Ｒ^６は、フェニル基、及び、炭素数１〜６のアルキル基から選ばれる一種以上の基をそれぞれ表す）

... (3)
(In the formula, R ¹ represents one or more functional groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms, and R ² represents a divalent organic group which may contain a secondary amino group. W represents one or more groups selected from a phenoxy group and an alkoxy group having 1 to 6 carbon atoms, and n represents 0, 1 or 2, respectively.

... (4)
(However, in the formula, R ³ , R ⁴ and R ⁵ each represent one or more groups selected from a phenyl group, an alkyl group having a molecular weight of 500 or less, a phenoxy group, and an alkoxy group having 1 to 6 carbon atoms, R ⁶ represents one or more groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms.

Compound (b1) Specific examples of compound (b1) include 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldiethoxysilane, N -(2-aminoethyl) -3-propyltrimethoxysilane, N- (2-aminoethyl) -3-propylmethyldimethoxysilane, N- (2-aminoethyl) -3-propyltriethoxysilane, N- ( 2-aminoethyl) -3-propylmethyldiethoxysilane, 4-amino-3-dimethylbutyltrimethoxysilane, 4-amino-3-dimethylbutylmethyldimethoxysilane, 4-amino-3-dimethylbutyltriethoxysilane, 4-amino-3-dimethylbutylmethyldiethoxysilane, [ Examples include primary amino group-containing aminosilane compounds such as 2-aminoethyl- (2′-aminoethyl)]-3-aminopropyltrimethoxysilane. In addition, since the curing mechanism of the moisture curable resin composition according to the present invention is presumed as described above, any compound having a reactive silicon group that can crosslink with a primary amino group may be used. So-called ketimine silane compounds such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine are also substantially contained in the compound (B) or (b1). Of these, it is preferable to use 3-aminopropyltrimethoxysilane or N- (2-aminoethyl) -3-propyltrimethoxysilane from the viewpoint of easy availability.

Compound (b2) Specific examples of compound (b2) include methyltrimethoxysilane, dimethyldimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, Examples include 3-mercaptopropyltrimethoxysilane and 3-ureidopropyltrimethoxysilane. Of these, methyltrimethoxysilane and dimethyldimethoxysilane are preferably used from the viewpoint of easy condensation reaction with the compound (b1).

  The compound (b1) alone or the condensation product of the compound (b1) and the compound (b2) may be synthesized by a conventionally known method. Specifically, a method of reacting the compound (b1) with water or a method of reacting the compound (b1) and the compound (b2) with water can be mentioned. Compound (b1) alone or a condensation product of compound (b1) and compound (b2) is commercially available, and they can be used in the present invention. Commercially available products include aminosilane silyl groups such as MS3301 (trade name, manufactured by Chisso Corporation), MS3302 (trade name, manufactured by Chisso Corporation), X-40-2651 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) alone or others. And a compound partially condensed with the alkoxysilane compound.

  As described above, compound (B) reacts with compound (A). In addition to this, the reactive silicon group present in the compound (B) is also hydrolyzed and condensed by moisture to give a final cured product in which they are combined and cured. Therefore, what obtains a desired cured film physical property should just be selected suitably for a compound (B). In addition, the compound (B) may be used alone or in combination of two or more. Although the compounding quantity of a compound (B) is not specifically limited, Preferably the primary amino group in a compound (B) is 0.5-10. With respect to 1 mol of 5-membered ring carbonate groups in a compound (A). It is 0 mol, More preferably, it is 0.7-5.0 mol, Most preferably, it is 0.9-3.0 mol. When the addition amount of the compound (B) is less than 0.5 mol with respect to 1 mol of the five-membered carbonate group in the compound (A), the effect as a curing agent is not sufficient, and when it exceeds 10.0 mol In some cases, the function (A) may be impaired, or a good cured product property may not be obtained.

[About Polyamine Compound (C)]
In the present invention, the polyamine compound (C) (hereinafter sometimes simply referred to as “compound (C)”) is a polyamine compound having two or more primary amino groups in the molecule. The compound (C) reacts with the five-membered ring carbonate group of the compound (A) to function as a curing agent, and further effectively cures the curable resin composition synergistically with the aminosilane compound (B).
Specific examples of the polyamine compound (C) include ethylenediamine, diethylenetriamine, triethylenediamine, pentaethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,4-diaminobutane, , 9-Diaminononane, norbornanediamine, isophoronediamine, ATU (3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5.5] undecane), CTU guanamine, dodecanoic acid Dihydrazide, hexamethylenediamine, m-xylylenediamine, bis (aminopropyl) piperazine, N- (3-aminopropyl) -1,3-propanediamine, bis (3-aminopropyl) ether 2-hydroxyethylaminopropylamine The formula H ₂ N (C ₂ H ₄ NH) _n H (n ≧ 5) represented by a compound (trade name: Polyate, manufactured by Tosoh Corporation), Sun Techno Japan Co., Ltd. Jeffamine EDR-148, etc. And polyamine compounds having a plurality of amino groups in the molecule, such as polyoxyalkylene.

When the polyamine compound (C) is used as a curing agent for the compound (A) in combination with the aminosilane compound (B), the curing of the compound (A) is further effectively promoted, and the film cohesion of the cured product is further increased. Can be improved. That is, the effect appears as a result of high adhesive strength when, for example, the curable resin composition of the present invention is applied as an adhesive. Although the mechanism is not clear, when the compound (A) and the compound (B) react and cure, the compound (C) also reacts with the compound (A) at the same time. As a result, the molecular weight increases, and as a result, it is presumed that high cured film cohesive force can be obtained.
The compound (C) may be appropriately selected in order to obtain desired cured film properties. In addition, the compound (C) may be used alone or in combination of two or more. Although the compounding quantity of a compound (C) is not specifically limited, Preferably the primary amino group in a compound (C) is 0.01-3. With respect to 1 mol of 5-membered carbonate groups in a compound (A). It is 0 mol, More preferably, it is 0.1-2.0 mol, Most preferably, it is 0.2-1.0 mol. When the addition amount of the compound (C) is less than 0.01 mol with respect to 1 mol of the five-membered carbonate group in the compound (A), the effect of adding the compound (C) may not be sufficient. If it exceeds the mole, the compound (A) may not be sufficiently cured.

[Condensation catalyst (D)]
In the present invention, the reactive silicon group condensation catalyst (D) is a compound that promotes the reaction between the five-membered carbonate group and the primary amino group or the condensation of the reactive silicon group. Specifically, amine compounds such as dibutylamine, triethylamine, 1,8-diazabicyclo [5.4.0] undec-7-ene, acid compounds such as isostearic acid and phosphoric acid, dimethyltin laurate, dibutyltin dimethoxide , Dioctyl tin versatate, dibutyl bismuth laurate, titanium alkoxide, zirconium alkoxide, organometallic compounds such as aluminum chelate compounds, metal halide compounds such as aluminum chloride, zirconium chloride, titanium chloride, boron trifluoride monoethylamine complex And boron halide compounds such as boron trifluoride piperidine complex and boron trichloride dimethyl sulfide complex, and onium salt compounds such as sulfonium salt and iodonium salt, but are not limited thereto. Among these, organometallic compounds, halogenated metal compounds, and boron halide compounds are more preferred because of their high catalytic activity, and organometallic compounds, boron halides are preferred because of their high stability. Of these compounds, the compounds are particularly preferred. As a compounding quantity of a condensation catalyst (D), 0.001-20 mass parts is preferable with respect to 100 mass parts of compounds (B), 0.01-10 mass parts is more preferable, 0.1-5 mass parts is 0.1-5 mass parts Particularly preferred.

[Other ingredients]
Any conventionally known compound or substance can be added to the curable resin composition according to the present invention. For example, hydrophilic or hydrophobic silica-based powders, calcium carbonate powders, clay powders, organic powders such as acrylic, fillers such as organic and inorganic balloons, tackifiers such as phenolic resins, Thixotropic agents such as amide wax, dehydrating agents such as calcium oxide, diluents, plasticizers, flame retardants, functional oligomers, hindered amine compounds, hindered phenol compounds, 3- (2,2,6,6-tetra Anti-aging agents such as methylpiperidi-4-yloxy) propyltriethoxysilane, ultraviolet absorbers such as benzotriazole compounds, pigments, titanate coupling agents, aluminum coupling agents, drying oils and the like can be blended.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to an Example.

[Preparation of Compound (A)]
(Synthesis Example 1)
Actol P-28 (polyoxypropylene diol, molecular weight 5000, trade name, manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) 800 g and isophorone diisocyanate 94.2 g were stirred at 50 ppm with respect to Actol P-28 under a nitrogen atmosphere. The reaction was carried out at 80 ° C. for 3 hours in the presence of dioctyltin diversate. Thereafter, 55.9 g of glycerin carbonate (manufactured by Ube Industries, Ltd.) was added, and the mixture was further reacted at the same temperature for 7 hours to obtain a compound (A-1) having a five-membered ring carbonate group. After completion of the reaction, IR measurement was performed, and no characteristic absorption (2265 cm ⁻¹ ) attributed to the isocyanate group was observed. The viscosity of the compound (A-1) at 23 ° C. was 70,000 mPa · s (BH viscometer, No. 7 rotor, 10 revolutions).

(Synthesis Example 2)
150 g of compound (A-1) obtained in Synthesis Example 1 and 13.4 g of Silaace S360 (trade name, 3-aminopropyltrimethoxysilane, manufactured by Chisso Corporation) were stirred at 90 ° C. while stirring in a nitrogen atmosphere. Compound (P-1) was obtained by reacting for a period of time. The viscosity of the curable resin composition (P-1) at 23 ° C. was 188,000 mPa · s (BH viscometer, No. 7 rotor, 10 revolutions).

[Preparation of Compound (B)]
(Synthesis Example 3)
An aminosilane compound in which reactive silicon groups are partially oligomerized by stirring and mixing 100 g of Saila Ace S360 (trade name, 3-aminopropyltrimethoxysilane manufactured by Chisso Corporation) and 10 g of water and reacting at room temperature for 6 hours. (B-1) was obtained.

[Preparation of curable resin composition and measurement of adhesive strength]
(Examples 1-9, Comparative Examples 1-3)
Each component was mixed at the blending ratio shown in Tables 1 to 3, and the adhesive strength of each curable resin composition was measured.
As the adherend, a stainless plate (thickness 1.5 mm, width 25 mm, length 100 mm) and an ABS plate (thickness 3 mm, width 25 mm, length 100 mm) were used. Each curable resin product (about 0.1 g) was uniformly applied to an area of 25 mm × 25 mm on the stainless steel plate surface, and the adherends were bonded to each other with an area of 12.5 mm × 25 mm. Each bonded specimen was cured at 23 ° C. and 50% relative humidity for 7 days, and then the tensile shear bond strength (N / mm ² ) was measured according to JIS K 6850. The measurement results of the respective tensile shear bond strengths are shown in Tables 1 and 2.

The details of the raw materials used in the table are as follows.
“KBM903”: trade name manufactured by Shin-Etsu Chemical Co., Ltd., 3-aminopropyltrimethoxysilane “KBM603”: tradename of Shin-Etsu Chemical Co., Ltd., N- (2-aminoethyl) -3-aminopropyltrimethoxysilane “ MS3301 ": trade name manufactured by Chisso Corporation, aminosilane compound" NBDA "having a primary amino group: trade name manufactured by Mitsui Chemicals, Inc., norbornanediamine" Neostan U-830 ": trade name, manufactured by Nitto Kasei Corporation, dioctyltin Diversate "A-Link15": Nippon Unicar Co., Ltd. trade name, silane compound having secondary amino group, N-ethyl-aminoisobutyltrimethoxysilane

  As is clear from the results in Table 1, the curable resin composition according to the present invention uses the aminosilane compound (B) having a primary amino group as a curing agent (Examples 1 to 5). It can be seen that the compound (A) is sufficiently cured and the adhesive strength is extremely higher than when the secondary amino group-containing silane compound is used as a curing agent (Comparative Example 1).

As is apparent from the results in Table 2, when the aminosilane compound (B) having a primary amino group and the polyamine compound (C) are used in combination as a curing agent (Example 6), only the polyamine compound (C) is used. It can be seen that the adhesive strength is further improved as compared with the case of using a curing agent (Comparative Example 2).
Further, when an organotin compound or a boron halide compound that can be a condensation catalyst (D) of a reactive silicon group is used for the compound (A) and the aminosilane compound (B) (Examples 7 and 8), It can be seen that the adhesive strength is improved. Further, even when only the condensation catalyst (D) is used, the compound (A) cannot be cured (Comparative Examples 3 and 4).
Moreover, the adhesive strength is improved more effectively by pre-reacting a curable resin having one or more five-membered ring carbonate groups with an aminosilane compound having a primary amino group at a high temperature (Example 9). I understand that. In addition, the compounding quantity of the compound (P-1) in Table 2 and Example 9 is converted so that the compounding quantity of the compound (A-1) contained in the compound (P-1) is equal to 20 g of Example 1. It is.

  The curable resin composition according to the present invention can be used for all applications in which a conventional two-component curable resin composition has been used. For example, it can be used as an adhesive, a sealing material, a paint, a coating material, a sealing material, a casting material, a coating material, and the like.

Claims (8)

Compound (A) having two or more five-membered ring carbonate groups represented by the following general formula (1) in the molecule,
A curable resin composition comprising an aminosilane compound (B) having one or more primary amino groups and a crosslinkable reactive silicon group in the molecule.

... (1)
(However, X in the formula represents a residue of compound (A)) The curable resin composition according to claim 1, wherein the compound (A) has a group represented by the following general formula (2) in the molecule.

... (2)
(In the formula, R is a divalent organic group having a molecular weight of less than 1,000, and Y represents a residue of the compound (A)).   The curable resin composition according to claim 1 or 2, wherein the main chain of the compound (A) is an oxyalkylene polymer.   The curable resin composition according to any one of claims 1 to 3, wherein the molecular weight of the residue X or Y of the compound (A) is 500 or more. The compound (B) is a condensation reaction product of a compound (b1) represented by the following general formula (3) and a compound (b2) represented by the following general formula (4): Curable resin composition in any one of 1-4.

... (3)
(In the formula, R ¹ represents one or more functional groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms, and R ² represents a divalent organic group which may contain a secondary amino group. W represents one or more groups selected from a phenoxy group and an alkoxy group having 1 to 6 carbon atoms, and n represents 0, 1 or 2, respectively.

... (4)
(However, in the formula, R ³ , R ⁴ and R ⁵ each represent one or more groups selected from a phenyl group, an alkyl group having a molecular weight of 500 or less, a phenoxy group, and an alkoxy group having 1 to 6 carbon atoms, R ⁶ represents one or more groups selected from a phenyl group and an alkyl group having 1 to 6 carbon atoms.   Furthermore, the polyamine compound (C) which has a 2 or more primary amino group in the molecule | numerator is used, The curable resin composition in any one of Claims 1-5 characterized by the above-mentioned.   Furthermore, the crosslinking catalyst (D) of the reactive silicon group which can be bridge | crosslinked is used, The curable resin composition in any one of Claims 1-6 characterized by the above-mentioned.   8. The curable resin composition according to claim 7, wherein the crosslinkable reactive silicon group condensation catalyst (D) is one or more compounds selected from organometallic compounds and boron halide compounds. object.