JP2016074840A - Two-liquid type curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a two-liquid type curable resin composition, with which incomplete curing does not occur in an adhesive interface of engineering plastics such as a modified polyphenylene ether resin, and which has fast curability characteristic of a radical curing system.SOLUTION: The two-liquid curable resin composition comprises the following (A) to (C) components, where a ratio of pts.mass of the (A) component and total pts.mass of a (meth)acrylic monomer including the (B) component is 8:2 to 5:5. (A) component: a urethane-modified acrylic oligomer and/or an epoxy-modified acrylic oligomer. (B) component: an acrylic monomer having 3 or more acrylic groups in a molecule. (C) component: an aliphatic polyamine which has no ether group but has 2 or more primary amino groups in a molecule, and which is liquid at 25°C.SELECTED DRAWING: None

Description

The present invention relates to a two-component curable resin composition that exhibits good adhesion to a specific engineering plastic such as a modified polyphenylene ether resin.

In recent years, specific engineering plastics have been widely used for the purpose of reducing the weight of vehicles. In particular, the modified polyphenylene ether resin is a material that has received particular attention since the dimensions of the molded product are stable. Epoxy resins, silicone resins, acrylic resins, and the like are used to bond the materials, but each has advantages and disadvantages. Epoxy resins tend to be hardened and exhibit sufficient adhesion, but peeling occurs in reliability tests such as high-temperature and high-humidity tests and heat cycle tests. A typical example of silicone resin is a moisture-curing type, but in pasting applications, it takes time to cure because moisture penetration is slow. Moreover, although the photocurable acrylic resin like patent document 1 also exists from the improvement of workability | operativity, a shadow part becomes uncured.

In addition, a two-component acrylic resin using a metal catalyst and an organic peroxide can be used. The two-component curable resin composition has a fast curing property and is easy to make a cured product having flexibility and flexibility. However, although the cause has not been clarified, it has been found that curing failure occurs on the surface of a specific engineering plastic. Therefore, although the composition is cured, it has been a problem that it does not develop an adhesive force because it peels from the plastic surface.

JP 2012-001648 A

Conventionally, in a two-component type curable resin composition having a rapid curing property of a radical curing system, a curing failure has occurred at the bonding interface of engineering plastics such as a modified polyphenylene ether resin. It was difficult to achieve curability.

As a result of intensive studies to achieve the above object, the present inventors have found that the present invention relates to a two-component curable resin composition that does not cause poor curing at the bonding interface of engineering plastics such as modified polyphenylene ether resins and that cures quickly. The invention has been completed.

The gist of the present invention will be described next. The first embodiment of the present invention includes the components (A) to (C), and the ratio of the total parts by mass of the (meth) acrylic monomer including the components (A) and (B) is 8: 2. It is a two-component curable resin composition that is 5: 5. (Hereinafter, acrylic and methacryl are called (meth) acrylic.)
(A) component: urethane-modified acrylic oligomer and / or epoxy-modified acrylic oligomer (B) component: acrylic monomer having three or more acrylic groups in the molecule (C) component: primary amino group not containing an ether group in the molecule 2 or more aliphatic polyamines that are liquid at 25 ° C

The second embodiment of the present invention is the two-component curable resin composition according to the first embodiment, which does not contain a latent curing agent or curing accelerator.

The third embodiment of the present invention is the two-component curable resin composition according to any one of the first and second embodiments, wherein the component (C) includes an aliphatic polyamine having an alicyclic structure. .

The fourth embodiment of the present invention is the two-component curable resin composition according to any one of the first to third embodiments, which comprises a compound having an epoxy group and an acrylic group in the molecule as the component (D). It is a thing.

In the fifth embodiment of the present invention, the first composition is a composition containing a composition containing (A) component and (B) component, and the second composition is a composition containing (C) component. To a third-part curable resin composition according to any one of the third embodiments.

In a sixth embodiment of the present invention, the composition containing the component (A), the component (B) and the component (D) is the first component, and the composition containing the component (C) is the second component. It is a two-component curable resin composition described in the fourth embodiment.

A seventh embodiment of the present invention is a two-component adhesive used for engineering plastics, comprising the two-component curable resin composition according to any one of the first to sixth embodiments.

In the present invention, good adhesive force is expressed while maintaining fast curability without causing poor curing at the bonding interface of a specific engineering plastic such as a modified polyphenylene ether resin.

Details of the present invention will be described below. The component (A) that can be used in the present invention is a urethane-modified acrylic oligomer and / or an epoxy-modified acrylic oligomer. Even a mixture of the solid and liquid component (A) can be used as long as it is liquid at 25 ° C. From the viewpoint of curability, those having two or more acrylic groups in the molecule are preferable. A urethane-modified oligomer having a methacryl group also exists, but in the present invention, it is not preferable because of low curability. Moreover, the compound which has both an epoxy group and an acryl group in a molecule | numerator does not correspond to (A) component.

The urethane-modified acrylic oligomer that can be used in the present invention is a polyfunctional isocyanate for polyols of various skeletons such as polyethers, polyesters, polycarbonates, polybutadienes and other dienes, and hydrogenated dienes such as hydrogenated polybutadienes as the main chain. Although it can synthesize | combine by making the compound which has a urethane bond by making a compound react and has a hydroxyl group and an acryl group with respect to the residual isocyanate, it is not limited to these.

Specific examples of the urethane-modified acrylic oligomer include Nippon Synthetic Chemical Co., Ltd., such as UN-1255, UN-9200A and UN-9000PEP from Negami Kogyo Co., Ltd., U-200PA and UA-160TM from Shin-Nakamura Chemical Co., Ltd. Examples include, but are not limited to, TEAI-1000 manufactured by Nippon Soda Co., Ltd., such as the company's purple light series UV-3000B and UV-3700B.

The epoxy-modified acrylic oligomer that can be used in the present invention can be synthesized by ring-opening polymerization of acrylic acid or the like to the glycidyl group of the polyfunctional glycidyl ether compound, but is not limited thereto. As the main chain of the polyfunctional glycidyl ether, those having various skeletons such as bisphenol A type, bisphenol F type, and novolak phenol type can be used.

Specific examples of the epoxy-modified acrylic oligomer include, but are not limited to, epoxy esters 3000A and 3002A manufactured by Kyoeisha Chemical Co., Ltd., and EBECRYL 3700 manufactured by Daicel Ornex Co., Ltd.

An acrylic oligomer other than a urethane-modified acrylic oligomer and / or an epoxy-modified acrylic oligomer has low curability and may not form a cured product.

The component (B) that can be used in the present invention is an acrylic monomer having 3 or more acrylic groups in the molecule. The acrylic monomer is a compound having a molecular weight of 1000 or less and having the ability to dilute the component (A). Even a mixture of the solid and liquid component (B) can be used as long as it is liquid at 25 ° C. The skeleton is not particularly limited. Although there are compounds having 3 or more methacryl groups in the molecule, they cannot be used in the present invention because of their low curability.

As component (B), trimethylolpropane triacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate, dipentaerythritol hexaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate Examples thereof include, but are not limited to, acrylate and EO-modified trimethylolpropane triacrylate.

Specific products of the component (B) include Shin-Nakamura Chemical Co., Ltd. A-TMPT, A-9300-1CL, A-9300, etc., Kyoeisha Chemical Co., Ltd. Light Acrylate TMP-A, TMP-3EO -A, TMP-6EO-A, PE-3A, PE-4A, DPE-6A and the like can be mentioned, but are not limited thereto.

In the present invention, (meth) acrylic monomers other than the component (B) can be used. The (meth) acrylic monomer other than the component (B) is a compound having 1 or 2 (meth) acrylic groups in the molecule. As specific examples, (meth) acrylic monomers having an alicyclic structure include dimethylol tricyclodecane di (meth) acrylate, isobornyl (meth) acrylate and the like (meth) acrylates having an alkylene oxide structure such as ethoxylation. Examples thereof include, but are not limited to, bisphenol A di (meth) acrylate and triethylene glycol di (meth) acrylate.

In this invention, it is preferable that the ratio of the mass part of (A) component and the total mass part of the (meth) acryl monomer containing (B) component is 8: 2 to 5: 5. If it is the said range, the sclerosis | hardenability in 25 degreeC atmosphere of this invention is favorable. Moreover, it is preferable that the ratio of (B) component in the whole (meth) acryl monomer containing (B) component is 40-100 mass%, Most preferably, it is 50-100 mass%.

The component (C) that can be used in the present invention is an aliphatic polyamine that is liquid at 25 ° C. and does not contain an ether group in the molecule and has two or more primary amino groups. The aliphatic structure may be a chain or a ring. The primary amino group does not include an aromatic amino group such as aniline. Particularly preferred is the component (C) having a cyclic aliphatic group, and it is preferable to add it because the curability is improved. Although a clear cause has not been clarified, aromatic polyamines and polyamines having an ether group in the molecule are not preferred because curability decreases. Moreover, it is preferable that it is liquid at 25 degreeC from a viewpoint of handling.

Specific examples of the component (C) include 1,3-bisaminomethylcyclohexane, triethylenetetramine, diethylenetriamine, ethylenediamine, and 4,4′-methylenebis (cyclohexylamine), but are not limited thereto. Absent. Further, the component (C) having crystallinity can be used after being dissolved in the liquid component (C) at 25 ° C.

It is presumed that the component (A) and the component (B) are polymerized by Michael addition to the component (C) as in Formula 1. Here, when only a compound having two acryl groups in the molecule is used, it is polymerized in a straight chain, and therefore, it becomes like a thermoplastic resin that dissolves when heated. Therefore, by adding the component (B), it is considered that a cured product that does not dissolve by heating is formed by taking a branched structure.

Since the present invention is a two-component curable resin composition, the reaction starts at 25 ° C., and therefore a latent curing agent or latent curing accelerator, that is, a powdery curing agent or curing accelerator is reacted. Therefore, it is preferable not to include the compound. There is a possibility that the storage stability of adding the compound to the component (A) is lowered. In addition, when the compound is added to the component (C) in advance, the compound may be dissolved and the reactivity may be changed. Specific examples of the compound include dicyandiamide, an imidazole compound, a hydrazide compound, an amine adduct compound of an amine compound and an epoxy resin, and the like.

In the present invention, other acrylic monomers and acrylic oligomer acrylic compounds can also be used. (Hereinafter, acrylic monomers are simply referred to as monomers, and acrylic oligomers are also simply referred to as oligomers.) Examples of acrylic compounds having a chain or cyclic aliphatic group include dimethylol tricyclodecane diacrylate and isobornyl acrylate. Examples of the product include, but are not limited to, light acrylate DCP-A and IB-XA manufactured by Kyoeisha Co., Ltd. Examples of acrylic compounds having an alkylene oxide group include triethylene glycol dimethacrylate, bisphenol A ethylene oxide adduct diacrylate, bisphenol A propylene oxide adduct diglycidyl ether acrylic acid adduct, ethoxylated bisphenol A dimethacrylate, etc. Examples of such products include, but are not limited to, Shin-Nakamura Chemical Co., Ltd. 3G, BPE-80N, and Kyoeisha Chemical Co., Ltd. Light Acrylate BP-4EAL.

Particularly preferred is a compound having an epoxy group and an acrylic group in the molecule as the component (D). Specific examples include glycidyl methacrylate and 4-hydroxybutyl acrylate glycidyl ether, but are not limited thereto. As products of compounds having an epoxy group and an acrylic group in the molecule, Blemmer G manufactured by Nippon Oil & Fats Co., Ltd., 4-hydroxybutyl acrylate glycidyl ether manufactured by Nippon Kasei Co., Ltd., etc. However, it is not limited to these. There is also UVACURE 1561 manufactured by Daicel Ornex Co., Ltd., but this product is made by adding acrylic acid to a bisphenol-type epoxy resin having two epoxy groups in the molecule and modifying it. A mixture of completely added acrylic oligomer and half added acrylic acid.

As other components, an epoxy resin having only an epoxy group in the molecule, an antioxidant, or the like may be added.

Examples of the epoxy resin include, but are not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and novolak phenol type epoxy resin. Specific examples include jER807 manufactured by Mitsubishi Chemical Corporation.

Various types of antioxidants are known, and examples thereof include thioether series, phosphorus series, hindered phenol series, monoacrylate phenol series, and nitroxide series. Of these, hindered phenol compounds as shown below are preferred.

Specific examples of the thioether antioxidant include MARK PEP-36 and MARK AO-23 manufactured by ADEKA Corporation.

Specific examples of phosphorus antioxidants include Irgafos 38, Irgafos 168, and Irgafos P-EPQ manufactured by BASF.

Specific examples of the hindered phenol compound include the following. 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, mono (or di- or tri) (α-methylbenzyl) phenol, 2,2′- Methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4 , 4′-thiobis (3-methyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, triethylene glycol bis- [3- (3 -T-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphene) L) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) 3,5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl) Til-4-hydroxybenzyl) benzene, bis (3,5-di-tert-butyl-4-hydroxybenzylphosphonate ethyl) calcium, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanate Nurate, 2,4-2,4-bis [(octylthio) methyl] o-cresol, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, Tris (2,4-di-t-butylphenyl) phosphite, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) ) Phenyl] -2H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-tert-butyl) -5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di -T-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t-octylphenyl) -benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzo) Triazol-2-yl) -4-hydroxyphenyl] propionate-polyethylene glycol (molecular weight about 300) condensate, hydroxyphenylbenzotriazole derivative, 2- (3,5-di-t-butyl-4-hydroxybenzyl) 2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), 2,4-di-t- Butylphenyl-3,5-di -t- butyl-4-hydroxybenzoate, and the like. In terms of product names, Nocrack 200, Nocrack M-17, Nocrack SP, Nocrack SP-N, Nocrack NS-5, Nocrack NS-6, Nocrack NS-30, Nocrack 300, Nocrack manufactured by Ouchi Shinsei Chemical Co., Ltd. NS-7, Nocrack DAH, MARK AO-30, MARK AO-40, MARK AO-50, MARK AO-60, MARK AO-616, MARK AO-635, MARK AO-658, MARK AO manufactured by ADEKA Corporation -80, MARKAO-15, MARK AO-18, MARK 328, MARK AO-37, AO-26, BASF IRGANOX-245, IRGANOX-259, IRGANOX-565, IRGANOX-1010, IRGANOX-1024 IRGANOX-1035, IRGANOX-1076, IRGANOX-1081, IRGANOX-1098, IRGANOX-1222, IRGANOX-1330, IRGANOX-1425WL, and the like, but are not limited thereto.

Specific examples of monoacrylate phenolic antioxidants include 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate (trade name: Sumilizer GM), 2 , 4-di-t-amyl-6- [1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl] phenyl acrylate and the like.

Specific examples of nitroxide antioxidants include 2,2,6,6-substituted-1-piperidinyloxy radicals and 2,2,5,5-substituted-1-pyrrolidinyloxy radicals, cyclic hydroxyamines, etc. The nitroxy free radicals from are illustrated. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable. Specific nitroxy free radical compounds include, but are not limited to, 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1- Piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1, Examples include 1,3,3-tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical, and the like. Instead of the nitroxy free radical, a stable free radical such as a galvinoxyl free radical may be used.

Moreover, you may use antioxidant together with a light stabilizer. Specific examples of the light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate as the Sanol series. The effect is further exhibited by the combined use, and the heat resistance may be particularly improved. Note that Tinuvin C353 and Tinuvin B75 manufactured by BASF, in which an antioxidant and a light stabilizer are previously mixed, may be used.

Additives such as organic fillers, inorganic fillers, plasticizers, and solvents may be blended in order to adjust the properties so long as the pot life and the physical properties of the cured product of the present invention are not impaired.

The present invention is suitable for use for the purpose of bonding, fixing, and sealing when assembling electronic parts such as automobiles, electrical parts, sensors, and motors. In particular, since the present invention is a room temperature curing type, it is not necessary to perform photocuring with an ultraviolet irradiation device or heat curing with a hot air drying furnace, and it is possible to secure a pot life until it is cured quickly and cured. Can be shortened and work efficiency can be improved.

EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, this invention is not limited only to these Examples. (Hereinafter, the two-component curable resin composition is also simply referred to as a composition.)

[Examples 1 to 29, Comparative Examples 1 to 11, References 1 to 9]
In order to prepare the composition, the following components were prepared.
Component (A): Urethane-modified acrylic oligomer and / or epoxy-modified acrylic oligomer / urethane acrylate oligomer (molecular weight: 15000) (UN-9200A, manufactured by Negami Kogyo Co., Ltd.)
-Urethane acrylate oligomer (molecular weight: 2700) (U-200PA Shin-Nakamura Chemical Co., Ltd.)
・ Polyester urethane acrylate oligomer (molecular weight: 18000) (purple light UV-3000B, manufactured by Nippon Synthetic Chemical Co., Ltd.)
-Urethane acrylate oligomer (molecular weight: 5000) (UN-9000PEP, manufactured by Negami Kogyo Co., Ltd.)
-Hydrogenated polybutadiene urethane acrylate oligomer (molecular weight: 2000) (TEAI-1000 manufactured by Nippon Soda Co., Ltd.)
-Bisphenol A propylene oxide 2-mole adduct diglycidyl ether acrylic acid adduct (molecular weight: 500) (epoxy ester 3002A manufactured by Kyoeisha Chemical Co., Ltd.)
Component (A ′): Oligomer / acryloyl-terminated polyacrylate other than component (A) (molecular weight: 24000) (RC100C manufactured by Kaneka Corporation)
・ Acryloyl-terminated polyacrylate (molecular weight: 18000) (RC200C, manufactured by Kaneka Corporation)
(B) Component: Acrylic monomer / trimethylolpropane triacrylate having 3 or more acrylic groups in the molecule (A-TMPT, Shin-Nakamura Chemical Co., Ltd.)
・ Ethoxylated isocyanuric acid triacrylate (A-9300, Shin-Nakamura Chemical Co., Ltd.)
Ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate (A-9300-1CL, Shin-Nakamura Chemical Co., Ltd.)
Other monomer dimethylol tricyclodecane diacrylate (Light acrylate DCP-A manufactured by Kyoeisha Chemical Co., Ltd.)
・ Ethoxylated bisphenol A dimethacrylate (BPE-80N, Shin-Nakamura Chemical Co., Ltd.)
・ Triethylene glycol dimethacrylate (3G Shin-Nakamura Chemical Co., Ltd.)
-Ethylene oxide adduct diacrylate of bisphenol A (Light acrylate BP-4EAL, manufactured by Kyoeisha Chemical Co., Ltd.)
Component (C): aliphatic polyamine, 1,3-bisaminomethylcyclohexane (BAC) which is liquid at 25 ° C. and has 2 or more primary amino groups and does not contain an ether group in the molecule (viscosity (25 ° C.): 9. 1 mPa · s) (1,3-BAC manufactured by Mitsubishi Gas Chemical Co., Inc.)
Triethylenetetramine (TETA) (Viscosity (25 ° C.): 19.4 mPa · s) (TETA Mitsui Chemicals Fine Co., Ltd.)
・ Diethylenetriamine (DETA) (viscosity (25 ° C.): 5.6 mPa · s) (diethylenetriamine manufactured by Mitsui Chemicals Fine Co., Ltd.)
・ Ethylenediamine (EDA) (Viscosity (25 ° C.): 1.6 mPa · s) (Ethylenediamine Mitsui Chemicals Fine Co., Ltd.)
・ 4,4'-methylenebis (cyclohexylamine) (PACM) (with crystallinity) (AMICURE PACM manufactured by Air Products)
Component (C ′): Amine other than Component (C) Polyoxyalkylenediamine (Repeat: n = 2.5) (Viscosity (25 ° C.): 9.4 mPa · s) (Jeffamine D-230 Mitsui Chemicals Fine Co., Ltd.) Company-made)
Diethyltoluenediamine (DETDA) (viscosity (25 ° C.): 155 mPa · s) (manufactured by ETHACURE100 TDA ALBEMALLE)
Component (D): Compound having an epoxy group and an acrylic group in the molecule, a mixture of an epoxy acrylate oligomer and a bisphenol A type epoxy resin (UVACURE 1561 manufactured by Daicel Ornex Co., Ltd.)
・ Glycidyl methacrylate (Blemmer G, Nippon Oil & Fats Co., Ltd.)
Other components ・ Bisphenol F type epoxy resin (jER807, manufactured by Mitsubishi Chemical Corporation)
Tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionic acid] pentaerythritol (ADK STAB AO-60 manufactured by ADEKA Corporation)
Bis [2-methyl-4- (3-ndodecylthiopropionyloxy) -5-tert-butylphenyl] sulfide and 4- [4-hydroxy-3-tert-butyl-6-methylphenylthio] -2 -T-Butyl-5-methylphenyl-3-dodecyltylopropanoate mixture (Adeka Stub AO-26 manufactured by ADEKA Corporation)

[Examples 1 to 29, Comparative Examples 1 to 11]
In order to prepare agent A, component (A) or component (A ′), component (B), and other monomers are weighed and charged into a stirring vessel. Stir for 30 minutes to make agent A. B agent shall be (C) component. Further, in Example 29, DETA and PACM are used by being mixed in advance. Detailed preparation amounts follow Tables 1 to 3, and all numerical values are expressed in parts by mass.

Comparative Example 9 is a two-component acrylic resin that reacts by contact of an organic peroxide and a metal complex. In order to prepare Comparative Example 9, the following components were further prepared.
・ Isobornyl acrylate (light acrylate IB-XA manufactured by Kyoeisha Chemical Co., Ltd.)
・ 2-Hydroxyethyl acrylate (light ester HOA manufactured by Kyoeisha Chemical Co., Ltd.)
2-hydroxyethyl methacrylate acid phosphate (JPA-514, manufactured by Johoku Chemical Industry Co., Ltd.)
・ Ethylenediaminetetraacetic acid disodium dihydrogen dihydrate (Chillest 3B, manufactured by Kirest Co., Ltd.)
-Cumene hydroperoxide (Park Mill H-80, NOF Corporation)
-Copper naphthenate (Naphtex copper manufactured by Nippon Chemical Industry Co., Ltd.)
・ 1-Acetyl-2-phenylhydrazine (reagent)
-Fumed silica surface-treated with octylsilane (Aerosil R805 manufactured by Nippon Aerosil Co., Ltd.)

The comparative example 9 is as follows, A agent and B agent are mix | blended, respectively, and A agent and B agent are mixed and used by mass ratio 1: 1. All numerical values are expressed in parts by mass.
[Comparative Example 9]
A agent UV-3000B 100 mass parts BPE-80N 10 mass parts IB-XA 70 mass parts HOA 25 mass parts JPA-514 1 mass part 3B 0.1 mass part H-80 2 mass parts R805 2 mass parts B agent UV- 3000B 100 parts by mass BPE-80N 10 parts by mass IB-XA 70 parts by mass HOA 25 parts by mass Naphtex copper 0.10 parts by mass 1-acetyl-2-phenylhydrazine 3.0 parts by mass R805 2 parts by mass

[Curability check]
The A agent and the B agent are weighed according to Tables 1 to 3, and mixed with a defoaming stirrer. (Hereinafter referred to as a mixed solution) Immediately after mixing, 2 g is weighed in a cup and left in an atmosphere at 25 ° C. The surface of the composition is touched with a polytetrafluoroethylene rod, and “curability” is confirmed according to the following evaluation criteria. For the compositions in Table 1, the curability after 24 hours at 25 ° C. is confirmed, and for the compositions in Table 2, the curability after 30 minutes, 1 hour, 12 hours and 24 hours is confirmed. In consideration of workability, the curability is preferably “◯” or “Δ”.
Evaluation criteria ○: No tack △: There is tack but does not adhere to the rod ×: There is tack and adheres to the rod

[Confirmation of thermal change]
Confirmation is made on a cured product that has become “O” after 24 hours due to the curability of the curability confirmation. A cylindrical cured product having a thickness of 5 mm and a diameter of 20 mm was prepared and allowed to stand in an 80 ° C. atmosphere for 100 hours. After taking out, the shape of the hardened | cured material when it returns to room temperature on the following evaluation criteria is confirmed again, and it is set as "thermal changeability." However, in the case of “x” after 24 hours, a cured product cannot be prepared, so “thermal change” is described as “−”.
Evaluation criteria ○: The same shape as the thickness and diameter before being put into the 80 ° C atmosphere.
X: Different from the shape before the cured product is dissolved and put into an 80 ° C. atmosphere.

In Examples 1 to 16, a urethane-modified acrylic oligomer and / or an epoxy-modified acrylic oligomer are verified as the component (A). On the other hand, in Comparative Examples 1 and 2, an oligomer other than the component (A) is used, but does not cure after 24 hours. Further, when only the monomer other than the component (B) is used as in Comparative Example 3, the curability is exhibited after 24 hours but the heat changeability is not exhibited.

When Examples 18 to 21 and Comparative Examples 4 and 5 are compared, if the ratio of the component (A) to the component (B) is 8: 2 to 5: 5, the curability after 24 hours is exhibited. Further, when Examples 18 to 21 and Comparative Example 6 are compared, the combination of only the component (A) and the component (C) does not exhibit curability after 24 hours. When Examples 18 to 21 and Comparative Examples 7 and 8 are compared, if the component (C) does not have a specific structure, the curability after 24 hours is not expressed.

From Examples 22 to 26, the component (A) may be a urethane-modified acrylic oligomer and / or an epoxy-modified acrylic oligomer. When Examples 23 and 27 to 30 and Comparative Example 10 are compared, when component (C) is used, curability develops 1 hour after mixing.

Regarding Examples 22 to 26 and Comparative Examples 9 and 10, hardness measurement and tensile shear bond strength measurement are performed. The results are summarized in Table 4.

[Hardness measurement]
Each mixture is filled in a container so that the thickness becomes 6 mm, and left in an atmosphere at 25 ° C. for 24 hours. While keeping the pressure surface of the A-type durometer (hardness meter) parallel to the sheet-like cured product, the pressure surface and the sample are brought into intimate contact with each other without being accompanied by an impact with a force of 10N. The maximum value is read at the time of measurement, and the maximum value is “hardness (no unit)”, which is an index of the softness of the cured product itself. Detailed conditions conform to JIS K 6253. When uncured or not fully cured, it is described as “not measurable”. The hardness is preferably 70 or less in consideration of followability.

[Measurement of tensile shear bond strength]
The adherend is Zylon (registered trademark) 540Z (manufactured by Asahi Kasei Chemicals Corporation), which is a modified polyphenylene ether resin, and has a width of 25 mm, a length of 100 mm, and a thickness of 2 mm. Two adherends are bonded to each mixture with an adhesive area of 25 mm × 10 mm and left at 25 ° C. for 24 hours to prepare a test piece. Using a universal testing machine, the test piece is pulled at a tensile speed of 50 mm / s, and the strength at the maximum load is defined as “shear adhesive strength 1 (MPa)”, which is used as an index of the adhesive force to the adherend. Details follow JIS K 6850. When the test piece is handled, the mixture is uncured and cannot be measured. Further, when the adherend uses SPCC-SD, the shear bond strength is 2 (MPa). The shear bond strength is preferably 2.0 MPa or more.

When the hardness of Examples 22-26 and Comparative Examples 9 and 10 are compared, Examples 22-26 and Comparative Example 9 exhibit sufficient hardness, but Comparative Example 10 cannot be measured because the cured product is too soft. . On the other hand, with a shear bond strength of 1 using a modified polyphenylene ether resin as an adherend, Comparative Example 9 is insufficiently cured at the adherend interface, and adhesiveness is manifested when the test piece is handled. I found that there was no. In Comparative Example 10, the cured product is too soft and the shear bond strength is very low.

[Reference 1-9]
Prepare references 1-9. (A) component, (B) component, other monomers, (D) component and other components are weighed and put into a stirring vessel, and stirred for 30 minutes to give agent A. B agent shall be (C) component. Detailed addition amounts are in accordance with Table 5, and all numerical values are expressed in parts by mass.

[Heat resistance test]
The tensile shear bond strength was measured in accordance with the above-described method, after being left for 168 hours at the initial stage and in an atmosphere of 100 ° C. (hereinafter referred to as after being left at high temperature) and “shear bond strength 1 (MPa)” and “shear bond strength”. "2 (MPa)" is measured. Further, the “change rate (%)” of the shear bond strength at the initial stage and after standing at high temperature is calculated. The results are summarized in Table 6.

Comparing References 1 to 3, Reference 6, and References 8 and 9 that do not contain component (D) and epoxy resin with References 4, 5, and 7 that contain component (D) and epoxy resin, component (D) and epoxy resin The rate of change is lower at a shear bond strength of 1 and the heat resistance is improved.

Engineering plastics such as modified polyphenylene ether resins are widely used in place of metals because of their good dimensional accuracy. At that time, an adhesive for adhering the material is required, and the present invention can be widely used for adhering the material because it exhibits a good adhesive force and is cured at 25 ° C. for a short time.

Claims (7)

Two-component curing comprising the components (A) to (C), and the ratio of the total parts by mass of the (meth) acrylic monomer containing the components (A) and (B) is 8: 2 to 5: 5. Resin composition.
(A) component: urethane-modified acrylic oligomer and / or epoxy-modified acrylic oligomer (B) component: acrylic monomer having three or more acrylic groups in the molecule (C) component: primary amino group not containing an ether group in the molecule 2 or more aliphatic polyamines that are liquid at 25 ° C The two-component curable resin composition according to claim 1, which does not include a latent curing agent and / or a latent curing accelerator. The two-component curable resin composition according to claim 1, wherein the component (C) includes an aliphatic polyamine having an alicyclic structure. The two-component curable resin composition according to any one of claims 1 to 3, comprising a compound having an epoxy group and an acrylic group in the molecule as the component (D). The composition containing the composition containing the component (A) and the component (B) is the first component, and the composition containing the component (C) is the second component. Liquid curable resin composition. The two-component curable composition according to claim 4, wherein the composition containing the component (A), the component (B) and the component (D) is the first component, and the composition containing the component (C) is the second component. Resin composition. A two-part adhesive for engineering plastics, comprising the two-part curable resin composition according to claim 1.