JP2018172565A - Acrylic curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition having excellent heat resistance, adhesive strength after heat exposure and adhesion to an adherend. SOLUTION: 1 to 50 parts by mass of (B) elastomer, 1 to 50 parts by mass of (C) bismaleimide compound, and (D) one or more per molecule with respect to 100 parts by mass of (A) (meth) acrylate monomer. 1 to 50 parts by mass of a poly (meth) acrylate having a radically polymerizable functional group, 5 to 100 parts by mass of a compound containing (E) an alkylene oxide chain and having two or more radically polymerizable functional groups in one molecule, (F). The above problem is solved by a curable resin composition containing 0.1 to 10 parts by mass of a polymerization initiator and 0.01 to 10 parts by mass of a curing accelerator (G). [Selection diagram] None

Description

The present invention relates to a curable resin composition having excellent heat resistance and excellent adhesion strength after heat exposure and adhesion to an adherend.

Acrylic adhesives based on (meth) acrylate monomers and radical polymerization initiators cure in a short time at room temperature, have high adhesive strength and impact strength, and have various properties such as chemical resistance and oil surface adhesion. Excellent. In addition, two-component acrylic adhesives do not require accurate weighing and mixing, and sometimes have excellent workability because they cure at room temperature even with only two-component contact, and are widely used in electronic and electrical materials, vehicles, and construction. It is used.

However, conventional acrylic adhesives have poor heat resistance, and the adhesion strength at high temperatures and the adhesion to the adherend after exposure to heat occur. There is a drawback that it cannot be used for various purposes.

Regarding the improvement of heat resistance of acrylic adhesives, techniques for improving heat resistance using maleimide compounds have been proposed (Patent Documents 1 to 5).

Although the adhesive composition containing a maleimide compound is excellent in shear bond strength after high-temperature heat exposure, there is a drawback that the peel adhesive strength decreases because the maleimide compound is cross-linked by high-temperature heating and the elastic modulus increases. It was. Further, during the adhesion strength test after heating at a high temperature, the interface fracture rate in the adherend / adhesive increased, and the adhesion decreased. As described above, the performance required for applications in which the adhesion site is exposed to high temperature is insufficient.

Therefore, in the industry, the required performance of adhesives, etc., is compatible with both high shear adhesive strength and peel adhesive strength even after high temperature heat exposure, and the fracture state is cohesive failure of the adhesive layer. Is required.

Japanese Patent Laid-Open No. 62-010179 Japanese Patent Laid-Open No. 4-117474 JP-A-4-323282 JP-A-6-057213 JP-A-6-248238

The present invention has been made in view of the above-mentioned problems related to acrylic curable resin compositions containing a conventional maleimide compound, and has high shear bond strength and peel bond strength even after high-temperature heat exposure. An object of the present invention is to provide an acrylic curable resin composition that is compatible with each other and has excellent adhesion such that the fracture state causes cohesive failure of the adhesive layer.

As a result of intensive studies, the inventors of the present invention have developed (D) a poly (meth) acrylate having one or more radical polymerizable functional groups in one molecule, and a conventional acrylic adhesive containing a maleimide compound; E) It has been found that the above-mentioned goal can be achieved by blending a compound containing an alkylene oxide chain and having two or more radically polymerizable functional groups in one molecule, and has completed the present invention.
In this specification, “(meth) acrylate” means “acrylic acid ester” or “methacrylic acid ester”.

That is, in the first invention, (A) 1 to 50 parts by mass of an elastomer, (C) 1 to 50 parts by mass of a bismaleimide compound, and (D) one molecule with respect to 100 parts by mass of (A) (meth) acrylate monomer. 1 to 50 parts by mass of poly (meth) acrylate having one or more radical polymerizable functional groups, (E) 5 to 100 masses of compounds having an alkylene oxide chain and having two or more radical polymerizable functional groups in one molecule Part, (F) 0.1-10 parts by weight of a polymerization initiator, and (G) 0.01-10 parts by weight of a curing accelerator.

In a second invention, (D) is a telechelic poly (meth) acrylate synthesized by a living radical polymerization method and has a number average molecular weight of 5,000 to 40,000. It is curable resin composition of invention.

3rd invention is the curable resin composition of 1st or 2nd invention, wherein the average added mole number n of the alkylene oxide chain of (E) is n = 10 or more.

A fourth invention is the curable resin composition according to any one of the first to third inventions, wherein the alkylene oxide chain of (E) is an ethylene oxide chain.

A fifth invention is the curable resin composition according to any one of the first to fourth inventions, wherein (E) is ethoxylated bisphenol A di (meth) acrylate.

The sixth invention is a two-pack type first to fifth invention in which the first agent contains at least (F) a polymerization initiator and the second agent contains at least (G) a curing accelerator. Any curable resin composition.

The seventh invention is an adhesive composition comprising the curable resin composition of any one of the first to sixth inventions.

The curable resin composition according to the present invention has an effect of achieving both high shear adhesive strength and peel adhesive strength even after being subjected to heat exposure and excellent adhesion to an adherend.

Hereinafter, the present invention will be described in detail.

(A) (meth) acrylate monomer is not particularly limited, but (i) monofunctional (meth) acrylate and (ii) (meth) acrylate having a hydroxy group, (iii) polyfunctionality other than component (E) (Meth) acrylate can be used.

(I) Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl ( (Meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, 2-methylbutyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) Acrylate, n-octyl (meth) acrylate, 2-methylhexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-butylhexyl (meth) acrylate, isooctyl (meth) acrylate, isopentyl (meth) acrylate , Isononyl (meth) acrylate, isodecyl (meth) acrylate, n-nonyl (meth) acrylate, n-decyl (meth) acrylate, lauryl (meth) acrylate, hexadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofur Furyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxy (meth) acrylate, phenoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate , Dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, (3-ethyloxetane-3-yl) methyl (meth) acrylate , Adamantyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethyl (meth) acrylamide, (meth) acryloylmorpholine, isopropyl (meth) acrylamide, diethyl (meth) ) Acrylamide, dimethylaminopropyl (meth) acrylamide and the like.

(Ii) Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylamide and the like. It is done.

(Iii) Polyfunctional (meth) acrylates other than component (E) include 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Examples include tetra (meth) acrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

The (meth) acrylate monomers (i) to (iii) may be used alone or in combination of two or more. In these, it is desirable to include (ii) (meth) acrylate which has a hydroxyl group from a viewpoint of sclerosis | hardenability and adhesiveness. Among the (meth) acrylates having a hydroxy group, 2-hydroxyethyl (meth) acrylate and / or 2-hydroxypropyl (meth) acrylate are preferable, and 2-hydroxyethyl (meth) acrylate is more preferable.

When (i), (ii) and (iii) are used in combination, the proportion of (i) is preferably 20 to 95 parts by mass in 100 parts by mass of the total amount of (A) from the viewpoint of curability and adhesiveness. To 90 parts by mass is more preferable. The proportion of (ii) is preferably 5 to 80 parts by mass and more preferably 10 to 70 parts by mass in 100 parts by mass of the total amount of (A). The ratio of (iii) is preferably less than 50 parts by mass and more preferably less than 30 parts by mass in 100 parts by mass of the total amount of (A). If the amount exceeds 50 parts by mass, the curing shrinkage rate increases and the adhesion to the adherend may be reduced.

(B) Elastomer refers to a polymer substance having rubber-like elasticity or a polymer substance that becomes a rubber elastic body by cross-linking and / or chain extension reaction, which may be solid or liquid, but is dissolved in a (meth) acrylate monomer. It is desirable to be able to do it.

Examples of such elastomers include styrene-butadiene rubber, butadiene rubber, isoprene rubber, ethylene propylene rubber, acrylonitrile-butadiene rubber, carboxyl-terminated butadiene nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, butyl rubber, ethylene rubber, acrylic rubber, Examples thereof include ethylene acrylic rubber, chlorosulfonated polyethylene rubber, urethane rubber, epichlorohydrin rubber and the like, and one or more of these may be used.

Among these, acrylonitrile-butadiene rubber is preferable from the viewpoint of adhesiveness.

The amount of (B) used is 1 to 50 parts by mass, preferably 3 to 35 parts by mass, based on 100 parts by mass of (A), from the viewpoint of solubility in (meth) acrylate monomers and adhesiveness. -25 mass parts is more preferable. If it is less than 1 part by mass, the adhesiveness may be reduced, and if it exceeds 50 parts by mass, the viscosity is high and the workability may be reduced.

(C) A bismaleimide compound is a compound having two maleimide groups in the molecule. Such a bismaleimide compound is not particularly limited, but 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6′-bismaleimide- ( 2,2,4-trimethyl) hexane, bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, bis (4- Maleimidophenyl) sulfone, bismaleimidomethyl ether and the like, and one or more of them may be used.

The usage-amount of (C) is 1-50 mass parts with respect to (A) 100 mass parts, 1-30 mass parts is preferable, and 5-15 mass parts is more preferable. If it is less than 1 part by mass, the heat resistance may be insufficient, and if it exceeds 50 parts by mass, the peel adhesion strength may be reduced.

(D) The poly (meth) acrylate having one or more radically polymerizable functional groups per molecule may be liquid or solid, but it is desirable that it can be dissolved or dispersed in the (A) (meth) acrylate monomer.

“Poly (meth) acrylate” means a homopolymer or copolymer of a (meth) acrylic acid ester, and is not particularly limited, but is reactive or soluble or dispersible in (A). And those having a molecular weight of about 5,000 to 40,000 are preferably used.

The “radically polymerizable functional group” refers to a vinyl group, a propenyl group, an allyl group, a (meth) acryloyl group, and the like. From the viewpoint of curability, a (meth) acryloyl group and a vinyl group are preferable, and a (meth) acryloyl group is more preferable.

Such poly (meth) acrylates are commercially available and can be used. Specific examples of commercially available products include macromonomer series such as AA-6 and AB-6 (manufactured by Toagosei Co., Ltd., poly (meth) acrylate having one radical polymerizable functional group in the molecule), RC100C, RC200C, KANEKA XMAP series such as RC310C (manufactured by Kaneka Corporation, telechelic poly (meth) acrylate having two radically polymerizable functional groups in the molecule) can be used, and even if one or more of these are used Good.

Among these, the XMAP series manufactured by Kaneka Corporation is preferably used from the viewpoints of heat resistance and adhesion. The XMAP series is a telechelic poly (meth) acrylate produced by the living radical polymerization method, and its polydispersity is close to 1, so its viscosity is lower than that of poly (meth) acrylate having the same number average molecular weight. Excellent workability. Moreover, since the functionalization rate of the molecular terminal is high and it is efficiently incorporated inside the polymer, it has excellent heat resistance.

The usage-amount of (D) is 1-50 mass parts with respect to (A) 100 mass parts, 3-30 mass parts is preferable, and 5-15 mass parts is more preferable. If the amount is less than 1 part by mass, the adhesion may be reduced and the cohesive failure rate may be reduced in the adhesion strength test after heat exposure. If the amount exceeds 50 parts by mass, the compatibility may be reduced and the resin composition may be separated. There is.

(E) As a compound having an alkylene oxide chain and having two or more radically polymerizable functional groups in one molecule, addition of polyalkylene oxide di (meth) acrylate, alkylene oxide addition of bisphenol A, bisphenol S or bisphenol F Di (meth) acrylates with aromatic ring structures such as di (meth) acrylates, oxyalkylenated trimethylolpropane (meth) acrylate, oxyalkylenated glycerin (meth) acrylate, oxyalkylenated pentaerythritol (meth) acrylate Oxyalkylenated polyfunctional (meth) acrylates such as these may be mentioned, and one or more of these may be used.

The alkylene oxide chain preferably has an average added mole number n of alkylene oxide per molecule of n = 10 or more from the viewpoint of peel adhesion strength. The alkylene oxide chain monomer unit is preferably ethylene oxide and / or propylene oxide, and the alkylene oxide chain may be a homopolymer, a block copolymer or a random copolymer. However, an ethylene oxide chain is more preferable from the viewpoint of adhesion.

Among the compounds having an ethylene oxide chain, di (meth) acrylate (ethoxylated bisphenol A di (meth) acrylate) of an ethylene oxide adduct of bisphenol A is particularly preferred from the viewpoint of the balance between shear bond strength and peel bond strength. Used for.

(E) The usage-amount is 5-100 mass parts with respect to (A) 100 mass parts, 10-80 mass parts is preferable and 20-60 mass parts is more preferable. If it is less than 5 parts by mass, the peel adhesion strength may be lowered, and if it exceeds 100 parts by mass, the water resistance and heat-and-moisture resistance may be deteriorated.

(F) The polymerization initiator is not particularly limited as long as it is a compound that generates radicals upon contact with heat, light, or (G) a curing accelerator. Examples of such compounds include organic peroxides, An azo compound etc. are mentioned.

Examples of organic peroxides include hydrones such as cumene hydroperoxide, tert-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide. Peroxides, ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, di-tert-butyl peroxide, tert-butyl-α-cumyl peroxide, di-α-cumyl peroxide, 1, 4 (or 1 , 3) -bis [(tert-butylperoxy) isopropyl] benzene, 1,1-bis (tert-butylperoxy) cyclohexane and other dialkyl peroxides, isobutyryl peroxide, bis (3,5,5 Trimethyl hexanoyl) peroxide, diacyl peroxides such as benzoyl peroxide and the like

Examples of the azo compound include 1,1′-azobis- (cyclohexane-1-carbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropyl). Pionitrile), 2,2′-azobis (isobutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like.

The usage-amount of (F) is 0.1-10 mass parts with respect to (A) 100 mass parts, 0.2-8 mass parts is preferable, and 0.5-5 mass parts is more preferable. If it is less than 0.1 parts by mass, sufficient curability may not be obtained, and if it exceeds 10 parts by mass, storage stability may be deteriorated.

(G) Although it does not specifically limit as a hardening accelerator, The well-known compound which reacts with (F) and accelerates | stimulates generation | occurrence | production of a radical can be used. Examples of such compounds include transition metal salts, tertiary amines, thiourea derivatives and the like.

Examples of transition metal salts include metal soaps such as cobalt octylate, cobalt naphthenate, copper octylate, copper naphthenate, zinc octylate, zinc naphthenate, copper acetylacetonate, titanium acetylacetonate, and chromium acetylacetonate. Examples thereof include metal chelates such as narate, iron acetylacetonate, cobalt acetylacetonate, and vanadylacetylacetonate.

Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N, N-dimethyl-p-toluidine and the like.

Examples of thiourea derivatives include methylthiourea, dibutylthiourea, ethylenethiourea, acetyl-2-thiourea, benzoylthiourea, N, N-diphenylthiourea, N, N-diethylthiourea, N, N-dibutylthiourea, Examples include tetramethylthiourea.

The usage-amount of (G) is 0.01-10 mass parts with respect to (A) 100 mass parts, 0.05-5 mass parts is preferable, and 0.1-1 mass part is more preferable. If the amount is less than 0.01 part by mass, a sufficient curing accelerating effect may not be obtained, and if it is 10 parts by mass or more, storage stability may be deteriorated.

The curable resin composition according to the present invention is a room temperature curable curable resin composition that cures at room temperature by containing (G), but heat curable curing that promotes decomposition of (F) by heating. The resin composition can also be used. In such a case, (G) may not be included.

In this invention, in the range which does not impair the effect, you may contain other well-known components in an adhesive agent. Specific examples of other components include radical polymerizable monomers other than acrylics such as vinyl monomers, various additives (thickeners, thixotropic agents, dispersants, flame retardants, fillers, antioxidants, Surface modifiers, plasticizers, UV absorbers, adhesion-imparting agents, antifoaming agents, polymerization inhibitors, inorganic fine particles, toners, etc.).

In the present invention, an acidic compound having a (meth) acryloyl group can be used for the purpose of improving adhesiveness. Examples of acidic compounds having a (meth) acryloyl group include (meth) acrylic acid, (meth) acrylate monomers containing a carboxyl group such as 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxy. Examples thereof include (meth) acrylate monomers containing a phosphoric acid group such as ethyl acid phosphate. These acidic compounds having a (meth) acryloyl group are included in the (A) (meth) acrylate monomer in a broad sense. When using the acidic compound which has a (meth) acryloyl group, the usage-amount of the acidic compound which has a (meth) acryloyl group has a preferable 0.01-10 mass part among 100 weight part of (A) (meth) acrylate monomers. 0.1 to 5 parts by mass is more preferable. If it is less than 0.01 part by mass, a sufficient effect of imparting adhesiveness may not be obtained, and if it exceeds 10 parts by mass, the storage stability may be deteriorated.

In the present invention, a polymerization inhibitor can be used for the purpose of improving storage stability. Examples of polymerization inhibitors include 2,6-di-tert-butyl-p-cresol, hydroquinone, methylhydroquinone, 4-methoxyphenol, 4-tert-butylcatechol, tert-butylhydroquinone, 1,4-benzoquinone, 1,1-diphenyl-2-picrylhydrazyl free radical, 2,2,6,6-tetramethyl-1-piperazinyloxyl free radical, 4-hydroxy-2,2,6,6-tetramethyl- Examples include 1-piperazinyloxyl free radical and phenothiazine. 0.01-3 mass parts is preferable with respect to 100 mass parts (A), and, as for the usage-amount of a polymerization inhibitor, 0.05-2 mass parts is more preferable. If the amount is less than 0.01 part by mass, a sufficient storage stability improving effect may not be obtained, and if it exceeds 3 parts by mass, the curability may be lowered.

In the present invention, various fillers can be used for the purpose of imparting viscosity, thixotropy and dispersion stability. Examples of such fillers include, but are not limited to, Aerosil series such as Aerosil 130, Aerosil 200, Aerosil 300, Aerosil R-812, Aerosil R-972, Aerosil RX200, Aerosil RX300 (made by Nippon Aerosil, Fume Dosilica).

The curable resin composition according to the present invention can be used as a two-pack type. Although it does not specifically limit as a method of setting it as a two-pack type, What mixed the components other than (F) and (G) is divided into two, (F) is made into 1st agent, (G) is made into 2nd agent. The method of adding each is mentioned. In this case, the two liquids may be mixed and cured at the time of use, or may be cured by separately applying and contacting both agents to the adherend.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these.

(Examples 1-9)
As a component (A), MMA (Mitsubishi Gas Chemical Co., Ltd., methyl methacrylate) and light ester HO-250 (N) (trade name, manufactured by Kyoeisha Chemical Co., Ltd., 2-hydroxyethyl methacrylate) were prepared.
Nipol 1043 (trade name, manufactured by Nippon Zeon Co., Ltd., acrylonitrile-butadiene rubber) was prepared as the component (B).
As component (C), BMI (trade name, manufactured by Kay Kasei Co., Ltd., 4,4′-diphenylmethane bismaleimide) was prepared.
As a component (D), RC100C (trade name, manufactured by Kaneka Corporation, polyacrylate having acryloyl groups at both ends of the molecule, number average molecular weight 5,000 to 40,000) was prepared.
As component (E), Miramer M2301 (trade name, manufactured by Miwon, ethoxylated bisphenol A dimethacrylate, average added mole number of ethylene oxide n = 30) was prepared.
Park mill H-80 (trade name, manufactured by NOF Corporation, cumene hydroperoxide 80% solution) was prepared as the component (F).
As component (G), nursem vanadyl (trade name, manufactured by Nippon Chemical Industry Co., Ltd., vanadyl acetylacetonate) was prepared.
Aerosil 200 (trade name, manufactured by Nippon Aerosil Co., Ltd., fumed silica) was prepared as a dispersion stabilizer.
Components (A) and (B) were mixed at the blending ratio shown in Table 1, and stirred with a high-speed disperser until (B) was completely dissolved. All the remaining components were added to the obtained elastomer monomer solution and mixed uniformly with a planetary stirrer to prepare a curable resin composition.

(Comparative Examples 1-4)
A curable resin in the same manner as in Example 1 except that one of the components (B), (C), (D), and (E) was removed from the composition of Example 1 as described in Table 2. A composition was prepared.

(Examples 10 and 11)
As component (C), BMI-70 (trade name, manufactured by Kay Kasei Co., Ltd., bis- (3-ethyl-5-methyl-4-maleimidophenyl) methane) and BMI-80 (trade name, Kay Kasei) 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane) was prepared. A curable resin composition was prepared in the same manner as in Example 1 except that the component (C) was changed from that in Example 1 to that shown in Table 3.

(Examples 12 and 13, Comparative Examples 5 and 6)
As component (D), RC200C (trade name, manufactured by Kaneka Corporation, polyacrylate having an acryloyl group at both ends of the molecule, number average molecular weight 5,000 to 40,000), AA-6 (trade name, manufactured by Toagosei Co., Ltd., A polyacrylate having one methacryloyl group at the end of the molecule, a number average molecular weight of 6,000) was prepared. For comparison, AS-6 (trade name, manufactured by Toagosei Co., Ltd., polystyrene having one methacryloyl group at the end of the molecule, number average molecular weight 6,000) and Alfon UP-1080 (trade name, manufactured by Toagosei Co., Ltd., A polyacrylate having no radically polymerizable functional group and a number average molecular weight of 6,000 were prepared. A curable resin composition was prepared in the same manner as in Example 1 except that the component (D) was changed from the composition of Example 1 to that shown in Table 3.

(Examples 14 to 17, Comparative Examples 7 and 8)
As component (E), NK ester 14G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polyethylene glycol dimethacrylate, average added mole number of ethylene oxide n = 14), NK ester 23G (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., Polyethylene glycol dimethacrylate, average addition mole number of ethylene oxide n = 23), NK ester APG-700 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd., polypropylene glycol diacrylate, average addition mole number of propylene oxide n = 12), Fancryl FA-3218M (trade name, manufactured by Hitachi Chemical Co., Ltd., ethoxylated bisphenol A dimethacrylate, average added mole number of ethylene oxide n = 18) was prepared. For comparison, EXENOL 1020 (trade name, manufactured by Asahi Glass Co., Ltd., polypropylene glycol having no radical polymerizable functional group) and EXENOL 430 (trade name, manufactured by Asahi Glass Co., Ltd., polypropylene glycol having no radical polymerizable functional group) were prepared. A curable resin composition was prepared in the same manner as in Example 1 except that the component (E) was changed from the composition of Example 1 to that shown in Table 4.

(Example 18)
As component (F), Nyper NS (trade name, manufactured by NOF Corporation, 40% suspension of benzoyl peroxide) was prepared. Moreover, N, N-dimethyl-p-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was prepared as the component (G). A curable resin composition was prepared in the same manner as in Example 1 except that the component (F) and the component (G) were changed from those in Example 1 to those described in Table 4.

(Examples 19 and 20)
As component (A), light ester BZ (trade name, manufactured by Kyoeisha Chemical Co., Ltd., benzyl methacrylate), light ester IB-X (trade name, manufactured by Kyoeisha Chemical Co., Ltd., isobornyl methacrylate), light ester THF (trade name, Kyoeisha) Chemical Company, Tetrahydrofurfuryl Methacrylate) and Light Ester P-1M (trade name, manufactured by Kyoeisha Chemical Co., Ltd., 2- (meth) acryloyloxyethyl acid phosphate) were prepared. A curable resin composition was prepared in the same manner as in Example 1 except that the component (A) was changed from that in Example 1 to that shown in Table 5.

About said curable resin composition, following preparation 1 and 2 were performed immediately after preparation, and adhesive strength and adhesiveness were measured.

(Test 1: Tensile shear bond strength)
Conforms to JIS K 6850. A curable resin composition is applied to a steel plate (SPCC-SB, 100 mm × 25 mm × 1.5 mm), and an appropriate amount of glass beads (diameter 0.2 mm) is placed on the bonded portion in order to make the bonding thickness uniform. The laminate was bonded to a sheet of steel with an adhesion area of 12.5 × 25 mm. After curing for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, it was placed in an oven at 220 ° C. and heated for 30 minutes. The sample was taken out in a 23 ° C. environment and allowed to stand until it reached 23 ° C., and then the tensile shear bond strength was measured at a temperature of 23 ° C. and a relative humidity of 50% at a tensile rate of 5 mm / min. The adhesive surface after the fracture was visually observed to examine the cohesive failure rate.

(Test 2: T-type peel adhesion strength)
Conforms to JIS K 6854-3. A curable resin composition is applied to a steel plate (SPCC-SD, 150 mm × 25 mm × 0.5 mm), and an appropriate amount of glass beads (diameter 0.2 mm) is placed on the bonded portion in order to make the bonding thickness uniform. Bonded to a sheet of steel. After curing for 24 hours in an environment of a temperature of 23 ° C. and a relative humidity of 50%, it was placed in an oven at 220 ° C. and heated for 30 minutes. The specimen was taken out in a 23 ° C. environment and allowed to stand until it reached 23 ° C., and then the T-peeling adhesive strength was measured at a temperature of 23 ° C. and a relative humidity of 50% at a tensile rate of 100 mm / min. The adhesive surface after peeling was visually observed to investigate the cohesive failure rate.

In Test 1, the tensile shear bond strength was 10 MPa or more and the cohesive failure rate was 100%, and in Test 2, the T-type peel adhesive strength was 80 N / 25 mm and the cohesive failure rate was 100%. Test results and pass / fail judgments are shown in each table.

In Examples 1 to 20, both Test 1 and Test 2 had high adhesive strength, and the cohesive failure rate was 100%. In Comparative Example 1, the adhesive strength was significantly reduced, and the cohesive failure rate was also reduced. In Comparative Example 2, the shear bond strength decreased. In Comparative Example 3, the cohesive failure rate significantly decreased. In Comparative Example 4, the cohesive failure rate decreased. From the above, only when the components (B), (C), (D), and (E) coexist, both high shear adhesion strength and peel adhesion strength are achieved even after high-temperature heat exposure, and It can be seen that the high adhesiveness in which the fracture state becomes cohesive failure is exhibited. Further, Comparative Examples 6 to 8 indicate that it is important for the components (D) and (E) to have radically polymerizable functional groups for the expression of adhesion and peel adhesion strength. Further, Comparative Example 5 shows that when the main chain is polystyrene, the adhesion is lowered, and it is important that the main chain of the component (D) is poly (meth) acrylate.

The curable resin composition of the present invention is compatible with both high shear adhesive strength and peel adhesive strength even after high-temperature heat exposure, and excellent adhesion so that the fracture state is cohesive failure of the adhesive layer. It is also applicable and useful as an adhesive that requires high heat resistance such that the part is exposed to high temperatures.

Claims (7)

(A) For 100 parts by weight of (meth) acrylate monomer,
(B) 1-50 parts by mass of elastomer,
(C) 1-50 parts by mass of a bismaleimide compound,
(D) 1 to 50 parts by mass of poly (meth) acrylate having one or more radically polymerizable functional groups per molecule;
(E) 5 to 100 parts by mass of a compound containing an alkylene oxide chain and having two or more radically polymerizable functional groups in one molecule;
(F) 0.1 to 10 parts by mass of a polymerization initiator, and
(G) A curable resin composition comprising 0.01 to 10 parts by mass of a curing accelerator.
The curability according to claim 1, wherein the component (D) is a telechelic poly (meth) acrylate synthesized by a living radical polymerization method and has a number average molecular weight of 5,000 to 40,000. Resin composition.
3. The curable resin composition according to claim 1, wherein the average added mole number n of the alkylene oxide chain of the component (E) is n = 10 or more.
The curable resin composition according to any one of claims 1 to 3, wherein the alkylene oxide chain of the component (E) is an ethylene oxide chain.
The curable resin composition according to claim 1, wherein the component (E) is ethoxylated bisphenol A di (meth) acrylate.
The curability according to any one of claims 1 to 5, wherein the first agent contains at least (F) a polymerization initiator and the second agent contains at least (G) a curing accelerator. Resin composition.
An adhesive composition comprising the curable resin composition according to claim 1.