JPWO2020255844A1 - Curable compositions, cured products and adhesives - Google Patents

Abstract

In the present invention, an isocyanate prepolymer (A) containing a polyol (a1) containing a polyoxyethylene unit and a polyoxypropylene unit, a polyisocyanate (a2) as essential raw materials, an epoxy resin (B), and the like. The present invention provides a curable composition comprising a curing agent or a curing accelerator (C), a cured product thereof, and an adhesive. This curable composition has excellent moisture and heat resistance, flexibility and toughness, and can be suitably used for adhesive applications.

Description

The present invention relates to a curable composition having excellent moisture and heat resistance properties in a cured product, good flexibility and toughness, and suitable for adhesive use, a cured product thereof, and an adhesive.

In recent years, from the viewpoint of energy saving, lightweight materials such as aluminum, magnesium, and plastic have been adopted as structural materials, and the use of adhesives has been increasing instead of welding by welding in assembly. Adhesives for structures such as automobiles are required to have good adhesiveness between different materials and to withstand changes in temperature and humidity in the usage environment. In order to satisfy these requirements, for example, from the viewpoint that the adhesiveness can be maintained by improving the followability to the base material, the bisphenol type epoxy resin and the urethane-modified epoxy resin or the rubber-modified epoxy resin are used in combination. (See, for example, Patent Document 1). However, when a flexible skeleton is introduced by modifying an epoxy resin, there is an upper limit to the amount of the flexible skeleton introduced, and there are cases where the demand for sophistication cannot be sufficiently satisfied. Furthermore, from the viewpoint of moisture and heat resistance, improvements have been made in that moisture enters the interface between the base material and the cured product due to the hydrophobicity of the cured product (adhesive layer), which tends to cause interfacial peeling. It has been demanded.

Japanese Unexamined Patent Publication No. 2010-185034

Therefore, the problem to be solved by the present invention is to obtain a curable composition, a cured product thereof, and an adhesive which are excellent in moisture and heat resistance characteristics, have good flexibility and toughness, and can be suitably used for adhesive applications. To provide.

As a result of diligent studies to solve the above problems, the present inventors have found that the above problems can be solved by using an isocyanate prepolymer made from a specific polyol as a raw material in combination with an epoxy resin, and completed the present invention. I came to let you.

That is, in the present invention, an isocyanate prepolymer (A) containing a polyol (a1) containing a polyoxyethylene unit and a polyoxypropylene unit, a polyisocyanate (a2) as essential raw materials, and an epoxy resin (B) A curable composition characterized by containing a curing agent or a curing accelerator (C), a cured product thereof, and an adhesive comprising the curable composition.

According to the present invention, it is possible to provide a curable composition, a cured product thereof, and an adhesive, which have good flexibility and toughness in a cured product, are also excellent in moisture and heat resistance characteristics, and are suitable for adhesive use.

Hereinafter, the present invention will be described in detail.
The present invention comprises an isocyanate prepolymer (A) containing a polyoxyethylene unit and a polyoxypropylene unit as essential raw materials, a polyol (a1), a polyisocyanate (a2), an epoxy resin (B), and the like. It is characterized by containing a curing agent or a curing accelerator (C).

The present invention is characterized in that a polyoxyethylene unit and a polyoxypropylene unit coexist in the polyol (a1) as described above. In particular, the inclusion of the polyoxyethylene unit makes it possible to take in some moisture into the adhesive layer (cured product) when used as an adhesive, and as a result, even if peeling occurs, interfacial peeling can occur. Due to the fact that it suppresses and has high cohesive fracture property, it becomes possible to sufficiently perform the function as an adhesive.

The polyoxyethylene unit and the polyoxypropylene unit contained in the polyol (a1) do not have to be present in the same molecule, and for example, a polyol containing only polyoxyethylene and a polyol containing only the polyoxypropylene unit may be used. It may be used in combination and reacted with polyisocyanate (a2) described later.

When the polyol (a1) is a copolymer of polyoxyethylene and polyoxypropylene, the repeating unit of the polyoxyethylene unit in polyoxyethylene is in the range of 2 to 10, which is the base material when used as an adhesive. It is preferable from the viewpoint of excellent adhesion to polyethylene and excellent balance between mechanical strength and moisture heat resistance.

Further, the molecular weight of the polyoxypropylene unit in the polyol (a1) is preferably in the range of 2000 to 4000 as the number average molecular weight from the same viewpoint.

The mass ratio of the polyoxyethylene unit to the polyoxypropylene unit in the polyol (a1) is in the range of 25/70 to 1/99 from the viewpoint of suppressing interfacial peeling and adhesion to the base material. It is preferable from the viewpoint of ensuring the property and the balance of flexibility and toughness of the cured product, and particularly preferably in the range of 30/70 to 1/99. stomach.

The polyol (a1) may contain units other than polyoxyethylene and polyoxypropylene as long as the effects of the present invention are not impaired. Other units include, for example, aliphatic dihydric alcohols such as tetramethylene glycol, neopentane glycol; glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2- Methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentantriol, 2,3 4-Hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentantriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1 , 2,4-Pentantriol, trihydric alcohols such as trimethylolpropane; erythrit, pentaerythrit, 1,2,3,4-pentantetrol, 2,3,4,5-hexanetetrol, 1,2 , 3,5-Pentantetrol, 1,3,4,5-Hexanetetrol and other tetravalent alcohols; Adnit, Arabit, Xylit and other pentavalent alcohols; Examples thereof include a unit having a single unit or a plurality of repeating units.

The polyol (a1) used in the present invention may contain a polyoxyethylene unit and a polyoxypropylene unit, and other structures are not particularly limited. For example, polyoxyethylene and polyoxypropylene having hydroxyl groups at both ends may be used as they are, and a polyether polyol which is a copolymer of polyoxyethylene and polyoxypropylene and is a compound having 2 to 3 hydroxyl groups. Is preferable. Further, it may be polyoxyethylene, a polyester polyol which is a reaction product of polyoxypropylene and polycarboxylic acid, an ethylene oxide adduct of castor oil, a propylene oxide adduct, or the like.

Among these, it is preferable to use a polyoxyethylene-polyoxypropylene copolymer from the viewpoint of being more excellent in the uniformity of function as an adhesive. In order to adjust the content of the polyoxyethylene unit, it is also preferable to use a mixture of the polyoxyethylene-polyoxypropylene copolymer and polyoxypropylene.

Further, the polyol (a1) preferably contains 2 to 4 functional components, and particularly preferably contains trifunctional components from the viewpoint of excellent adhesion to the base material. The number average molecular weight of the polyol (a1) is preferably in the range of 2000 to 5000, and more preferably in the range of 2000 to 4000.

The polyisocyanate (a2) used in the present invention may be a compound having two or more isocyanate groups in one molecule, and the compound having 2 to 4 isocyanate groups is particularly suitable for adjusting the molecular weight of the isocyanate prepolymer (A). From the viewpoint of ease of use, it is preferable, and diisocyanate is most preferable.

Examples of the polyisocyanate (a2) include propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-methylpentane-2,4-diisocyanate, and octane-3,6-diisocyanate. , 3,3-Dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, lysine diisocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate Isocyanate, metatetramethylxylylene diisocyanate, isophorone diisocyanate (3-isocyanate methyl-3,5,5-trimethylcyclohexylisocyanate), 1,3- or 1,4-bis (isocyanatemethyl) cyclohexane, diphenylmethane-4,4' -Diisocyanate (MDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), hydrogenated tolylene diisocyanate and the like, and mixtures thereof.

Among these, from the viewpoint of easy control of the reaction with the polyol (a1) and easy availability of raw materials, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane-4,4' -It is preferable to use diisocyanate, and it is particularly preferable to use isophorone diisocyanate.

In the present invention, a blocked isocyanate prepolymer obtained by blocking a polyurethane using a polyisocyanate (a2) with a blocking agent (a3) so as to form an excess isocyanate group with respect to a hydroxyl group in the polyol (a1). A polymer is preferable from the viewpoint of better storage stability when the curable composition is obtained.

The reaction between the polyol (a1) and the polyisocyanate (a2) is not particularly limited, and may be carried out by a normal urethanization reaction. For example, the reaction temperature is 40 to 140 ° C., preferably 60 to 130 ° C., and various urethane polymerization catalysts for accelerating the reaction, such as dioctyl tin dilaurate, dibutyl tin dilaurate, first tin octoate, and stanas octoate. , Organic metal compounds such as lead octylate, lead naphthenate and zinc octylate, and tertiary amine compounds such as triethylenediamine and triethylamine can be used.

The excess amount of the isocyanate group with respect to the hydroxyl group in the polyol (a1) is in the range of 2.05 to 3.50 mol of the isocyanate group with respect to 1 mol of the hydroxyl group, so that the molecular weight of the obtained prepolymer is adjusted. It is preferable from the viewpoint of ease of use and reduction of unreacted polyisocyanate.

The excess isocyanate group is preferably blocked with a blocking agent (a3) as described above, and examples of the blocking agent (a3) include malonic acid diester (diethyl malonate, etc.), acetylacetone, and acetoacetic acid. Active methylene compounds such as esters (ethyl acetoacetate, etc.); oxime compounds such as acetoxime, methyl ethyl keto oxime (MEK oxime), methyl isobutyl keto oxime (MIBK oxime); methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, heptyl alcohol. , Hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, stearyl alcohol and other monohydric alcohols or isomers thereof; methyl glycol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, butyl diglycol and the like. Glycol derivatives; amine compounds such as dicyclohexylamine; phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tertiary butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol, etc. Bivalent phenolic compounds such as valent phenolic compounds, resorcin, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, naphthol; ε-caprolactone, ε-caprolactam, etc. May be good.

Among these, a monovalent phenol compound is preferable, and an alkyl group having 1 to 8 carbon atoms is particularly preferable, from the viewpoint that it does not easily affect the reaction when the cured product is obtained after the curable composition is prepared. It is preferably an alkylphenol having, and from the viewpoint of safety, it is most preferable to use pt-butylphenol.

The blocking reaction can be carried out by a known reaction method, and the amount of the blocking agent (a3) used is usually 1 to 2 equivalents, preferably 1.05 to 1.5 equivalents, relative to the free isocyanate group. be.

The blocking reaction with the blocking agent (a3) usually involves adding the blocking agent (a3) in the final reaction of the polymerization of the polyurethane, but the blocking agent (a3) is used at any stage of the polymerization of the polyurethane. Can also be added and reacted to obtain a blocked isocyanate prepolymer.

As a method of adding the blocking agent (a3), a method such as adding at the end of a predetermined polymerization, adding at the beginning of polymerization, adding a part at the beginning of polymerization, and adding the rest at the end of polymerization is possible. However, it is preferably added at the end of polymerization. In this case, the isocyanate% may be used as a reference as a guideline at the end of the predetermined polymerization. The reaction temperature when the blocking agent is added is usually 50 to 150 ° C, preferably 60 to 120 ° C. The reaction time is usually about 1 to 7 hours. At the time of the reaction, it is also possible to add the urethane polymerization catalyst to accelerate the reaction. In addition, an arbitrary amount of plasticizer may be added during the reaction.

The weight average molecular weight of the isocyanate prepolymer (A) in the present invention is preferably in the range of 4000 to 15000 from the viewpoint of good handling when the curable composition is used as an adhesive, and particularly 5000 to 10000. It is preferably in the range of.

In the present invention, the number average molecular weight (Mn) of the polyol is a calculated value from the hydroxyl value and the number of functional groups, and the other weight average molecular weight (Mw) is measured by gel permeation chromatography (GPC) under the following conditions. Value.

Measuring device; HLC-8220GPC manufactured by Tosoh Corporation
Column; TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ TSK-GEL SuperHZM-M x 4 manufactured by Tosoh Corporation
Detector; RI (Differential Refractometer)
Data processing; Multi-station GPC-8020modelII manufactured by Tosoh Corporation
Measurement conditions; column temperature 40 ° C
Solvent tetrahydrofuran
Flow velocity 0.35 ml / min Standard; Monodisperse polystyrene sample; 0.2 mass% tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100 μl)

The epoxy resin (B) used in the present invention is not particularly limited, and various ones can be used. When used as an adhesive, it is preferably an epoxy resin that is liquid at room temperature. For example, a bisphenol type or biphenol type epoxy resin such as a tetramethylbiphenol type epoxy resin, a bisphenol A type epoxy resin, or a bisphenol F type epoxy resin; Butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylpropan triglycidyl ether, glycerin triglycidyl ether and other aliphatic polyol polyglycidyl ethers; diglycidyl aniline, resorcinol diglycidyl ether, hydrogenation Ring structure-containing polyglycidyl compounds such as bisphenol A diglycidyl ether; ring structure-containing monofunctional glycidyl compounds such as alkylphenol monoglycidyl ether; polyglycidyl ester compounds such as neodecanoic acid glycidyl ester and the like can be mentioned. Of these, a bisphenol type or biphenol type epoxy resin is preferably used because a cured product having excellent flexibility and toughness can be obtained, and a bisphenol type epoxy resin is preferable from the viewpoint of industrial availability. In particular, the ratio of the bisphenol type epoxy resin to the total mass of the epoxy resin (B) is preferably 50% by mass or more, and more preferably 70% by mass or more.

Examples of the bisphenol type or biphenol type epoxy resin include those obtained by using various bisphenol compounds or biphenol compounds and epihalohydrin as resin raw materials. Specifically, the following structural formula (1)

［式中Ｘはそれぞれ独立に下記構造式（２−１）〜（２−８）

[X in the formula are independent of the following structural formulas (2-1) to (2-8).

（式中、Ｒ^２はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基の何れかであり、Ｒ^３はそれぞれ独立に炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基の何れかである。）
の何れかで表される構造部位であり、ｎは０以上の整数である。］
で表されるものが挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。

(In the formula, R ² is independently any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and R ³ is independently having 1 to 4 carbon atoms. It is either an alkyl group or an alkoxy group having 1 to 4 carbon atoms.)
It is a structural part represented by any of, and n is an integer of 0 or more. ]
The one represented by is mentioned. Each of these may be used alone, or two or more types may be used in combination.

X in the structural formula (1) is a structural site represented by any of the structural formulas (2-1) to (2-8), and a plurality of Xs existing in the molecule are the same structural site. It may be present, or it may be a different structural part. Above all, the structural portion represented by the general formula (2-1) or (2-2) is preferable because it is excellent in flexibility and toughness in the cured product.

The epoxy equivalent of the bisphenol type or biphenol type epoxy resin is preferably in the range of 150 to 250 g / eq, and is more preferably in the range of 160 to 200 g / eq because it is particularly excellent in flexibility and toughness in a cured product. preferable.

As described above, the bisphenol type or biphenol type epoxy resin can be produced by a method using various bisphenol compounds or biphenol compounds and epihalohydrin as resin raw materials. Specific production methods include, for example, a method of further reacting a diglycidyl ether compound obtained by reacting a bisphenol compound or a biphenol compound with an epihalohydrin with a bisphenol compound or a biphenol compound (method 1), or a bisphenol compound or a biphenol. Examples thereof include a method of directly obtaining an epoxy resin by reacting a compound with epihalohydrin (method 2).

The bisphenol compound or biphenol compound used in the method 1 or 2 is, for example, the following structural formulas (3-1) to (3-8).

（式中、Ｒ^２はそれぞれ独立に水素原子、炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基の何れかであり、Ｒ^３はそれぞれ独立に炭素原子数１〜４のアルキル基、炭素原子数１〜４のアルコキシ基の何れかである。）
の何れかで表される化合物などが挙げられる。これらはそれぞれ単独で用いても良いし、２種類以上を併用しても良い。中でも、硬化物における柔軟性と靱性に優れることから、前記一般式（３−１）又は（３−２）で表される化合物が好ましい。

(In the formula, R ² is independently any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and R ³ is independently having 1 to 4 carbon atoms. It is either an alkyl group or an alkoxy group having 1 to 4 carbon atoms.)
Examples thereof include compounds represented by any of the above. Each of these may be used alone, or two or more types may be used in combination. Among them, the compound represented by the general formula (3-1) or (3-2) is preferable because it is excellent in flexibility and toughness in the cured product.

Regarding the above method 1, the reaction ratio between the bisphenol compound or the biphenol compound and these diglycidyl ether compounds is preferably in the mass ratio of 50/50 to 5/95. The reaction temperature is preferably about 120 to 160 ° C., and a reaction catalyst such as tetramethylammonium chloride may be used.

In the present invention, in order to further improve the flexibility and toughness of the obtained cured product, as the epoxy resin (B), a bisphenol type or biphenol type epoxy resin and a flexible epoxy such as a urethane-modified epoxy resin and a rubber-modified epoxy resin are used. It is preferable to use a resin together.

The structure of the urethane-modified epoxy resin is not particularly limited as long as it is a resin having a urethane bond and two or more epoxy groups in the molecule. A urethane bond-containing compound having an isocyanate group obtained by reacting a polyhydroxy compound with a polyisocyanate and a hydroxy group-containing epoxy compound can be efficiently introduced into one molecule of a urethane bond and an epoxy group. It is preferable that the resin is obtained by reacting with.

Examples of the polyhydroxy compound used in producing the urethane-modified epoxy resin include polyether polyols, polyester polyols, adducts of hydroxycarboxylic acids and alkylene oxides, polybutadiene polyols, polyolefin polyols and the like. The molecular weight of the polyhydroxy compound is preferably in the range of 300 to 5000, particularly 500 to 2000, as a weight average molecular weight from the viewpoint of excellent balance between flexibility and curability.

The polyisocyanate used in producing the urethane-modified epoxy resin is not particularly limited as long as it is a compound having two or more isocyanate groups. For example, an aliphatic polyisocyanate, an aromatic polyisocyanate, and a polyisocyanate having an aromatic hydrocarbon group can be mentioned. Of these, aromatic polyisocyanates are preferable. Examples of the aromatic polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate.

By the above reaction, a urethane prepolymer containing a free isocyanate group at the terminal is obtained. Urethane is reacted with an epoxy resin having at least one hydroxyl group in one molecule (for example, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of aliphatic polyhydric alcohol and glycidol). A modified epoxy resin is obtained.

The urethane-modified epoxy resin preferably has an epoxy equivalent of 200 to 250 g / eq.

The rubber-modified epoxy resin is not particularly limited as long as it is an epoxy resin having two or more epoxy groups and a rubber skeleton. Examples of the rubber forming the skeleton include polybutadiene, acrylonitrile butadiene rubber (NBR), and carboxyl group-terminated NBR (CTBN). The rubber-modified epoxy resin can be used alone or in combination of two or more.

The rubber-modified epoxy resin preferably has an epoxy equivalent of 200 to 350 g / eq. The rubber-modified epoxy resin is not particularly limited in its production. For example, it can be produced by reacting rubber and epoxy in a large amount of epoxy. The epoxy (for example, epoxy resin) used in producing the rubber-modified epoxy resin is not particularly limited.

In the present invention, the curable composition further contains a curing agent or a curing accelerator (C).

As the curing agent or curing accelerator (C), those generally used for curing epoxy resins can be widely used, for example, polyamine compounds, amide compounds, acid anhydrides, and phenolic hydroxyl group-containing resins. , Phosphorus compound, imidazole compound, imidazoline compound, urea compound, organic acid metal salt, Lewis acid, amine complex salt and the like.

The polyamine compound is, for example, trimethylenediamine, ethylenediamine, N, N, N', N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N, N, N', N'-tetramethyl. Propylenediamine, tetramethylenediamine, pentandiamine, hexamethylenediamine, trimethylhexamethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N-dimethylcyclohexylamine, diethylenetriamine, triethylenetetramine, tetra Ethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis (2-dimethyl) Aminoethyl) Ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethylaminohexanol and other aliphatic amine compounds;

Piperazine, piperazine, mentandiamine, isophoronediamine, methylmorpholin, ethylmorpholin, N, N', N "-tris (dimethylaminopropyl) hexahydro-s-triazine, 3,9-bis (3-aminopropyl) -2, 4,8,10-Tetraoxyspiro (5,5) undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis (4-aminocyclohexyl) methane, N, N'-dimethylpiperazine, 1,8-diazabicyclo -[5.4.0] -Alicyclic and heterocyclic amine compounds such as undecene (DBU);

Aromatic amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, picolin, α-methylbenzylmethylamine Compound;

Epoxy compound-added polyamines, Michael-added polyamines, Mannig-added polyamines, thiourea-added polyamines, ketone-blocking polyamines, dicyandiamides, guanidines, organic acid hydrazides, diaminomaleonitriles, amineimides, boron trifluoride-piperidin complexes, boron trifluoride-mono Examples thereof include modified amine compounds such as ethylamine complexes.

Examples of the amide compound include dicyandiamide and polyamide amine. The polyamide amine includes, for example, an aliphatic dicarboxylic acid such as succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, and azelaic acid, a carboxylic acid compound such as fatty acid and dimer acid, and an aliphatic polyamine or polyoxyalkylene. Examples thereof include those obtained by reacting a polyamine having a chain or the like.

The acid anhydrides include, for example, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydro. Phthalic anhydride and the like can be mentioned.

Examples of the phenolic hydroxyl group-containing resin include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), and naphthol aralkyl resin. Trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyphenol compound in which phenol nuclei are linked by bismethylene groups) , Biphenyl-modified naphthol resin (polyhydric naphthol compound in which phenol nuclei are linked by bismethylene group), aminotriazine-modified phenol resin (polyvalent phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring modification Examples thereof include polyhydric phenol compounds such as novolak resin (polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).

The phosphorus compound is, for example, an alkylphosphine such as ethylphosphine or butylphosphine, a first phosphine such as phenylphosphine; a dialkylphosphine such as dimethylphosphine or dipropylphosphine; a second phosphine such as diphenylphosphine or methylethylphosphine; , Triethylphosphine, third phosphine such as triphenylphosphine and the like.

The imidazole compounds include, for example, imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethyl imidazole, 2-ethyl imidazole, 3-ethyl imidazole, 4 -Ethyl imidazole, 5-ethyl imidazole, 1-n-propyl imidazole, 2-n-propyl imidazole, 1-isopropyl imidazole, 2-isopropyl imidazole, 1-n-butyl imidazole, 2-n-butyl imidazole, 1-isobutyl Imidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4- Methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-Phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole Isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4, Examples thereof include 5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride and the like.

Examples of the imidazoline compound include 2-methylimidazoline and 2-phenylimidazoline.

The urea compound is, for example, p-chlorophenyl-N, N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -N, N-dimethylurea, N- (3). -Chloro-4-methylphenyl) -N', N'-dimethylurea and the like can be mentioned.

In the present invention, the ratio of the isocyanate prepolymer (A) to the epoxy resin (B) is usually (A) / (from the viewpoint of being more excellent in the balance between the flexibility, toughness and moist heat resistance of the obtained cured product. The mass ratio represented by B) is in the range of 5/95 to 40/60, and more preferably in the range of 10/90 to 30/70. The blending amount of the epoxy resin (B) and the curing agent or curing accelerator (C) is 1 mol of the epoxy group of the epoxy resin (B) when a curing agent having a functional group capable of reacting with the epoxy group is used. On the other hand, it is preferable to add the functional group in the curing agent in a ratio of 0.5 to 1.1 mol. When a curing accelerator is used, it is preferably blended in a proportion of 0.5 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (B).

In addition, the curable composition of the present invention includes organic solvents, ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, flame retardants, plasticizers, silane coupling agents, organic beads, inorganic fine particles, and the like. It may contain an inorganic filler, a rheology control agent, a defoaming agent, an antifogging agent, a coloring agent and the like. Any amount of these various components may be added depending on the desired performance.

In the curable composition of the present invention, the isocyanate prepolymer (A), the epoxy resin (B), the curing agent or the curing accelerator (C), and various optional components are added to a pot mill, a ball mill, a bead mill, a roll mill, a homogenizer. , Super mill, homodisper, universal mixer, Banbury mixer, kneader and the like can be prepared by uniformly mixing.

The use of the curable composition of the present invention is not particularly limited, and it can be used in various applications such as paints, coating agents, molding materials, insulating materials, sealing agents, sealing agents, and fiber binding agents. Among them, by taking advantage of the excellent flexibility and toughness of the cured product, it can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft, and the space industry. Even when the adhesive of the present invention is used for adhering different materials such as between metal and non-metal, high adhesiveness can be maintained without being affected by changes in the temperature environment, and peeling or the like occurs. hard. Further, the adhesive of the present invention can be used not only for structural members but also as an adhesive for general office work, medical use, carbon fiber, electronic material, etc., and as an adhesive for electronic material, for example, build-up Interlayer adhesives for multilayer substrates such as substrates, adhesives for joining optical components, adhesives for bonding optical disks, adhesives for mounting printed wiring boards, die bonding adhesives, adhesives for semiconductors such as underfills, underfills for BGA reinforcement Examples thereof include a fill, an anisotropic conductive film, and an adhesive for mounting such as an anisotropic conductive paste.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Synthesis example 1
Under a nitrogen atmosphere, a polyether polyol (Actcol ED-28 number average molecular weight (Mn): 4000 functional groups: 2 ) 834 parts by mass and 96 parts by mass of isophorone diisocyanate (IPDI) are mixed, 0.1 part of Neostan U-820 is added as a catalyst, and the mixture is reacted at 80 ° C. for 5 hours, and then paratershary butylphenol (PTBP) as a blocking agent. ) 70 parts by mass was charged and reacted at 90 ° C. for 5 hours to obtain a blocked isocyanate prepolymer (1).

Synthesis Examples 2 to 10
Blocked isocyanate prepolymers (2)-(10) were obtained from the compounding compositions in Table 1 with the same formulation as in Synthesis Example 1.

Compounds in Table 1 ED-28: PE-PP polyol manufactured by MCNS (Mn: 4000, number of functional groups: 2)
EP-450: PE-PP polyol manufactured by MCNS (Mn: 3800, number of functional groups: 3)
EP-530: PE-PP polyol manufactured by MCNS (Mn: 3300, number of functional groups: 3)
D-3000: PP polyol manufactured by MCNS (Mn: 3000, number of functional groups: 2)
D-1500: PP polyol manufactured by MCNS (Mn: 1500 functional groups: 2)
T-4000: PP polyol manufactured by MCNS (Mn: 4000, number of functional groups: 3)
T-3000: PP polyol manufactured by MCNS (Mn: 3000, number of functional groups: 3)
T-2000: PP polyol manufactured by MCNS (Mn: 2000, number of functional groups: 3)
T-1500: PP polyol manufactured by MCNS (Mn: 1500 functional groups: 3)
IPDI: Isophorone diisocyanate manufactured by Sumika Cobestro Urethane HMDI: Hexamethylene diisocyanate manufactured by Tosoh Co., Ltd. TDI: Tolylene diisocyanate manufactured by MCNS Co., Ltd. T-80

Example 1
Block isocyanate prepolymer (1) synthesized in Synthesis Example 1 25 parts by mass, bisphenol A type epoxy resin EPICLON 850 75 parts by mass manufactured by DIC Co., Ltd., rubber-modified epoxy resin EPICLON TSR-601 9 parts by mass manufactured by DIC Co., Ltd., curing agent 5 parts by mass of dicyandiamide (DICY), 1 part by mass of 3,4-dichlorophenyl-N, N-dimethylurea (DCMU) as a curing accelerator, and _{10 parts by mass of calcium carbonate (CaCO 3} ) as a filler are mixed to form a curable composition. I got the thing (1). With respect to this curable composition (1), the cured product cured at 170 ° C. for 30 minutes was subjected to an adhesiveness evaluation and a moist heat resistance test according to the following. The results are shown in Table 2.

Adhesiveness evaluation <Tensile shear test>
The tensile shear strength was measured using AUTOGRAPH AG-XPlus 100 kN manufactured by Shimadzu Corporation under the condition of 25 ° C. by the JIS K6859 (adhesive creep rupture test) method.
<T-shaped peeling test>
The peel strength was measured using AUTOGRAPH AG-IS 1 kN manufactured by Shimadzu Corporation under the condition of 25 ° C. by the JIS K6854-3 (adhesive peeling adhesive strength test) method.

Moisture and heat resistance test After conducting a moisture and heat resistance test for 2 weeks under the conditions of 50 ° C and 90% for the test pieces prepared in the above <tensile shear test> and <T-shaped peeling test>, the tensile shear strength and peeling are performed with the same testing machine. The intensity was measured.

Confirmation of fracture state The fracture state of the test piece <T-shaped peeling test> after performing the moisture resistance test for 2 weeks under the above conditions of 50 ° C. and 90% was evaluated. The evaluation is performed at the rate of cohesive failure (%), and the higher the rate, the better the state of failure.

Example 2-10
The same evaluation was carried out for the curable composition blended in the same manner as in Example 1 except that the blocked isocyanate prepolymer shown in Table 2 was used instead of the blocked isocyanate prepolymer (1) of Example 1. The evaluation results are summarized in Table 2.

Comparative Synthesis Examples 1-3
Blocked isocyanate prepolymers (1')-(3') for comparison were obtained from the compounding compositions in Table 3 with the same formulation as in Synthesis Example 1.

Comparative Examples 1 to 3
The same evaluation was carried out for the curable composition blended in the same manner as in Example 1 except that the blocked isocyanate prepolymer shown in Table 4 was used instead of the blocked isocyanate prepolymer (1) of Example 1. The evaluation results are summarized in Table 4.

Claims (13)

A polyol (a1) containing a polyoxyethylene unit and a polyoxypropylene unit, an isocyanate prepolymer (A) containing a polyisocyanate (a2) as an essential raw material, and an isocyanate prepolymer (A).
Epoxy resin (B) and
A curable composition comprising a curing agent or a curing accelerator (C). Polyurethane made of polyisocyanate (a2) is blocked by a blocking agent (a3) so that the isocyanate prepolymer (A) becomes an excess isocyanate group with respect to the hydroxyl group in the polyol (a1). The curable composition according to claim 1, which is a blocked isocyanate prepolymer. The curable composition according to claim 2, wherein the blocking agent (a3) is a monovalent phenol compound. The curable composition according to any one of claims 1 to 3, wherein the polyol (a1) is a polyether polyol. The curable composition according to any one of claims 1 to 4, wherein the polyol (a1) is a polyoxyethylene-polyoxypropylene copolymer. The curable composition according to any one of claims 1 to 5, wherein the polyol (a1) contains a trifunctional component. The curable composition according to any one of claims 1 to 6, wherein the mass ratio of the polyoxyethylene unit to the polyoxypropylene unit in the polyol (a1) is in the range of 30/70 to 1/99. The curable composition according to any one of claims 1 to 7, wherein the polyisocyanate (a2) is a diisocyanate. The curable composition according to any one of claims 1 to 8, wherein the number average molecular weight of the polyol (a1) is in the range of 2000 to 5000. The curable composition according to any one of claims 1 to 9, wherein the epoxy equivalent of the epoxy resin (B) is in the range of 150 to 250 g / eq. Claims 1 to 10 in which the ratio of the isocyanate prepolymer (A) to the epoxy resin (B) used is in the range of 10/90 to 30/70 as the mass ratio represented by (A) / (B). The curable composition according to any one of the above. A cured product of the curable composition according to any one of claims 1 to 11. An adhesive comprising the curable composition according to any one of claims 1 to 11.