JP2007203670A - Complex constituted by integrating epoxy resin-cured layer with structure component - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a complex which has an epoxy resin-cured layer excellent in adhesion to a different kind of material, particularly, a metal, and also excellent in flexibility (followability). <P>SOLUTION: A curable epoxy resin composition comprises: an ingredient (A) as a liquid epoxy resin at 25°C, which contains 30-100 mass% diglycidyl ether obtained from polyether glycol with a number-average molecular weight of 200-2,000, and another 0-70 mass% epoxy resin; an ingredient (B) as an acid anhydride and/or a phenolic curing agent; and an ingredient (C) as a curing accelerator. The curable epoxy resin composition is brought into contact with another component in an uncured state, and cured under the state of the contact with it, so that the epoxy resin-cured layer can be formed. The epoxy resin-cured layer and another component are integrated together to constitute the complex. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a composite structure having an epoxy resin cured layer having excellent adhesive strength and flexibility (followability) as a layer in a state of being integrated with another structural body constituent material. More specifically, excellent adhesive strength and flexibility formed by bringing a specific curable epoxy resin composition into contact with other constituent materials and curing the curable epoxy resin composition as it is ( The present invention relates to a composite in which an epoxy resin cured layer having followability and other structural body constituent materials are integrated.

  Epoxy resins are excellent in heat resistance, adhesion, water resistance, mechanical strength, electrical properties, etc., so they are used in various fields such as adhesives, paints, materials for civil engineering and construction, insulating materials for electrical and electronic parts, etc. in use. In recent years, applications have diversified, and there are many demands for composites such as lamination and multilayering of epoxy resins and other substances (materials). In this compounding, firstly, good adhesion between the epoxy resin cured layer and other constituent materials is required. In addition, since it is often used for joining different constituent materials in the composite, for example, even if there is a difference in thermal expansion coefficient between different constituent materials after joining, the epoxy resin cured layer Is required to have a flexibility to follow the expansion and contraction of other materials, that is, not to cause phase separation.

  Providing flexibility to epoxy resins has been actively studied until now. Among them, a method for improving flexibility by blending an elastomer such as carboxyl group-terminated butadiene / acrylonitrile copolymer (CTBN) or a thermoplastic elastomer into an epoxy resin, or diglycidyl ester of dimer acid, polypropylene glycol A method of adding a flexible epoxy resin having a flexible skeleton in the molecule such as glycidyl ether is known.

  However, the method of adding a thermoplastic elastomer having flexibility has technical difficulties because it is necessary to disperse the elastic body in an epoxy resin with an appropriate particle size and with good reproducibility. It is extremely difficult. In addition, the method of adding a flexible epoxy resin is simply to soften the cured product, and the cured product has insufficient mechanical properties, particularly adhesive properties. A physical layer is not obtained.

  On the other hand, polyurethanes and polyesters using polyether glycols such as polytetramethylene ether glycol as raw materials are widely used as industrially important materials because they have excellent elasticity and hydrolysis resistance. A method has been proposed in which diglycidyl ether obtained from this polyether glycol is used as a diluent for a bisphenol type epoxy resin in an amount of about 20% by mass in the epoxy resin to improve the flexibility of the epoxy cured product (Patent Literature). 1, Patent Document 2)

However, in these methods, diglycidyl ether obtained from polyether glycol is used as a flexibility imparting agent, and the main epoxy resin component is 30% by mass or more in the total epoxy resin component. There is no example in which a composite having a cured layer with excellent adhesion to metal and flexibility (followability) is obtained. In the case of an epoxy resin composition used as a flexibility imparting agent, an aliphatic amine or a heterocyclic amine is used as a curing agent, but the cured product has heat resistance and water resistance (low water absorption). Rate) is insufficient, and the performance is not satisfactory particularly when used for electrical and electronic materials.
Therefore, development of a method for obtaining a composite having an epoxy resin cured layer having excellent adhesion to various structural materials, excellent flexibility (followability), and excellent heat resistance and water resistance was awaited. It was.
Japanese Patent Laid-Open No. 49-111461 JP 51-88599 A

  The present invention integrates an epoxy resin cured layer excellent in adhesion to various structural materials, particularly metal materials, excellent in flexibility (follow-up property), heat resistance and water resistance, with various structural materials. It is an object of the present invention to provide a composite having the above-described state.

The present invention includes the following inventions.
[1] A curable epoxy resin composition containing the following component (A), component (B), and component (C) is brought into contact with another component material in an uncured state, and the uncured state is left in a contacted state. A composite formed by curing an epoxy resin composition, in which an epoxy resin cured layer and the other constituent materials are integrated.
Component (A): epoxy resin (B) liquid at 25 ° C. containing 30 to 100% by mass of diglycidyl ether obtained from polyether glycol having a number average molecular weight of 200 to 2000 and 0 to 70% by mass of other epoxy resins Component; acid anhydride and / or phenol-based curing agent (C) component; curing accelerator

[2] The diglycidyl ether obtained from the polyether glycol in the component (A) is a diglycidyl ether obtained from a polyether glycol having a number average molecular weight of 250 to 1500. Complex.

[3] The diglycidyl ether content in the component (A) is 40 to 90% by mass and the other epoxy resin content is 10 to 60% by mass, the item [1] or [2] The complex described in 1.

[4] The other epoxy resin in component (A) is one or more epoxy resins selected from epoxy resins having an aromatic ring and / or an alicyclic structure, [3] The composite according to any one of [1] to [3].

[5] The other epoxy resin in component (A) is one or more epoxy resins selected from bifunctional epoxy resins having an aromatic ring and / or an alicyclic structure, [1] Item 4. The complex according to any one of Items 4 to 4.

[6] Item [1] to [5], wherein the total chlorine content of diglycidyl ether obtained from polyether glycol in component (A) is 0.01 to 0.6% by mass. The complex according to any one of the above.

[7] The diglycidyl ether obtained from the polyether glycol in the component (A) is a diglycidyl ether of polytetramethylene ether glycol, any one of the items [1] to [6] The composite according to Item.

[8] The composite according to any one of [1] to [7], which is composed of electrical and electronic parts.

[9] Item [1] to [8], wherein the cured epoxy resin layer of the composite has a moisture absorption (water) ratio of 121 ° C., 100% RH, 24 hr of 0 to 2.0 mass%. The complex in any one of.

[10] A curable epoxy resin composition for producing a composite comprising the following (A) component, (B) component and (C) component, wherein the epoxy resin cured layer and other constituent materials are integrated. .
Component (A): epoxy resin (B) liquid at 25 ° C. containing 30 to 100% by mass of diglycidyl ether obtained from polyether glycol having a number average molecular weight of 200 to 2000 and 0 to 70% by mass of other epoxy resins Component; acid anhydride and / or phenol-based curing agent (C) component; curing accelerator

[11] The diglycidyl ether obtained from the polyether glycol in the component (A) is a diglycidyl ether obtained from a polyether glycol having a number average molecular weight of 250 to 1500. The curable epoxy resin composition described.

[12] Item [10] or [11], wherein the diglycidyl ether content in component (A) is 40 to 90% by mass and the other epoxy resin content is 10 to 60% by mass. The curable epoxy resin composition described in 1.

[13] The other epoxy resin in component (A) is one or more epoxy resins selected from epoxy resins having an aromatic ring and / or an alicyclic structure, The curable epoxy resin composition according to any one of items 12).

[14] The other epoxy resin in component (A) is one or more epoxy resins selected from bifunctional epoxy resins having an aromatic ring and / or an alicyclic structure, [10] Item 10. A curable epoxy resin composition according to any one of items [13].

[15] Item [10] to [14], wherein the total chlorine content of diglycidyl ether obtained from polyether glycol in component (A) is 0.01 to 0.6% by mass. The curable epoxy resin composition according to any one of the above.

[16] The diglycidyl ether obtained from the polyether glycol in the component (A) is a diglycidyl ether of polytetramethylene ether glycol, any one of the items [10] to [15] The curable epoxy resin composition according to Item.

  The cured epoxy resin layer in the composite of the present invention is a layer having excellent adhesion to different materials, particularly metals, and excellent flexibility (followability). The composite having the layer is excellent particularly in the case of a flexible printed wiring board, a fiber reinforced composite, a composite reinforced glass, a semiconductor encapsulating material, a vibration (automobile) component adhesive, and has high utility value.

<A component>
The component (A) in the curable epoxy resin composition used for forming the epoxy resin cured layer of the composite of the present invention is 30 to 30 diglycidyl ether obtained from polyether glycol having a number average molecular weight of 200 to 2000. It is an epoxy resin that is liquid at 25 ° C. and contains 100% by mass and 0 to 70% by mass of other epoxy resins.

  The diglycidyl ether of polyether glycol in the component (A) is an epoxy resin obtained by reacting a polyether glycol having a number average molecular weight in the range of 200 to 2000, preferably 250 to 1500 with epichlorohydrin. When the number average molecular weight of the polyether glycol is less than 200, the flexibility of the epoxy resin cured layer is lowered, and when it exceeds 2000, the resulting diglycidyl ether becomes a solid and the handling property is deteriorated, which is not preferable.

  The production of diglycidyl ether of polyether glycol is carried out in the presence of an acid catalyst such as boron trifluoride ethyl ether and tin tetrachloride, or a phase transfer catalyst such as quaternary ammonium salts, quaternary phosphonium salts and crown ethers. Alternatively, the polyether glycol can be reacted with an alkaline compound such as epichlorohydrin and sodium hydroxide. Specifically, phase transfer of polytetramethylene ether glycol and epichlorohydrin to acidic catalysts such as sulfuric acid, boron trifluoride ethyl ether, tin tetrachloride, or quaternary ammonium salts, quaternary phosphonium salts, crown ethers, etc. By reacting in the presence of a catalyst to produce a chlorohydrin ether body, this chlorohydrin ether body is then reacted with a dehydrohalogenating agent such as sodium hydroxide to cyclize the polytetramethylene. Diglycidyl ether of ether glycol can be obtained.

  When the composite of the present invention is an electric / electronic component, the diglycidyl ether of polyether glycol used for the component (A) in the curable epoxy resin composition has a total chlorine content of 0.01 to 0.00. 6% by mass is preferred. If the total chlorine content exceeds 0.6% by mass, corrosion of a metal material such as aluminum occurs, which is not preferable for an electric / electronic material. Moreover, when it uses for the use for which a weather resistance is requested | required, since an epoxy resin hardened layer will color (deteriorate), it is unpreferable. The reduction to less than 0.01% by mass is not economical because the effect of reducing the total chlorine content cannot be expected any more and a special reduction process is required.

  The epoxy resin comprising polytetramethylene ether glycol diglycidyl ether having a low total chlorine content is 0.8 to 20 mol, preferably 1 to 10 mol, of epichlorohydrin with respect to 1 equivalent of the hydroxyl group of polytetramethylene ether glycol. In the presence of a phase transfer catalyst such as quaternary ammonium salts, quaternary phosphonium salts, crown ethers, etc., at a temperature of 20 to 100 ° C. for 0.5 to 10 hours. After producing the ether body, the chlorohydrin ether body is subjected to a ring-closing reaction with a dehydrohalogenating agent such as sodium hydroxide at a temperature of 20 to 100 ° C. for 0.1 to 10 hours to obtain an epoxy resin. be able to.

  In the component (A) of the curable epoxy resin composition used for producing the composite of the present invention, another epoxy resin is used in combination as long as the effect of the cured epoxy resin layer in the composite of the present invention is not impaired. can do. As an example of the other epoxy resin which can be used together, the following are mentioned, for example.

[1] Bifunctional epoxy resin; bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, bisphenol A-alkylene oxide adduct Diglycidyl ether, diglycidyl ether of alkylene oxide adduct of bisphenol F, bisphenol S type epoxy resin, tetramethylbisphenol A type epoxy resin, tetramethylbisphenol F type epoxy resin, thiodiphenol type epoxy resin, dihydroxy diphenyl ether type epoxy Resin, terpene diphenol type epoxy resin, biphenol type epoxy resin, tetramethylbiphenol type epoxy resin, hydroquinone type epoxy resin, Chill hydroquinone type epoxy resin, dibutyl hydroquinone type epoxy resins, resorcin type epoxy resin, methyl resorcin type epoxy resin, dihydroxynaphthalene type epoxy resin.

[2] Multifunctional epoxy resin: phenol novolak epoxy resin, cresol novolac epoxy resin, bisphenol A novolac epoxy resin, dicyclopentadiene phenol epoxy resin, terpene phenol epoxy resin, phenol aralkyl epoxy resin, biphenyl aralkyl Type epoxy resin, naphthol novolak type epoxy resin, polyhydric phenol resin obtained by condensation reaction with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde, glyoxal, heavy petroleum oil or pitches and formaldehyde polymer and phenols An epoxy resin produced from various phenolic compounds such as modified phenolic resins obtained by polycondensation of aldehydes in the presence of an acid catalyst and epihalohydrin.

[3] Other epoxy resins; epoxy resins produced from various amine compounds such as diaminodiphenylmethane, aminophenol and xylenediamine and epihalohydrin, various carboxylic acids such as methylhexahydroxyphthalic acid and dimer acid, and epihalohydrin An epoxy resin produced from the above, a diluent for epoxy resin such as glycidyl ether of aliphatic alcohol, and an alicyclic epoxy resin represented by 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate. Bisphenol A type epoxy resin, bisphenol A-alkylene oxide adduct diglycidyl ether, bisphenol F type epoxy resin, bisphenol F alkylene oxide adduct diglycidyl ether, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, tetramethyl Bisphenol A type epoxy resin, tetramethylbisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin.
Among these epoxy resins, an epoxy resin that is liquid at 25 ° C. is preferable in terms of handleability.

  The ratio of the polyether glycol paper diglycidyl ether and other epoxy resin used in the component (A) in the curable epoxy resin composition used for the production of the composite of the present invention is 30 to 30 It is the ratio of other epoxy resins 0-70 mass% with respect to 100 mass%, Preferably they are 40-90 mass% of diglycidyl ethers of polyether glycol, and 60-10 mass% of other epoxy resins. When the other epoxy resin exceeds 70% by mass, the flexibility (following property) of the cured epoxy resin layer constituting the laminate is lowered, and the adhesiveness is also lowered, so that the laminate (composite) layer is reduced. It is not preferable because peeling occurs.

  The viscosity of the epoxy resin of component (A) in the curable epoxy resin composition used for producing the composite of the present invention is such that the E-type viscosity at 25 ° C. is 10 to 100,000 mPa.s. It is preferable that it is s. The viscosity is 100,000 mPa.s. When it is higher than s, the component (A) is in a semi-solid state or a solid state, and the handleability is deteriorated.

<B component>
As the curing agent for the B component epoxy resin in the curable epoxy resin composition used for producing the composite of the present invention, the following acid anhydrides and / or phenolic curing agents are used.

Acid anhydride curing agent Aromatic acid anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride , Cycloaliphatic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride and trialkyltetrahydrophthalic anhydride

Phenolic hardeners Catechol, resorcin, hydroquinone, bisphenol F, bisphenol A, bisphenol S, biphenol, and the like dihydric phenols, phenol novolacs, cresol novolacs, bisphenol Polyphenols such as Ru-A novolak compounds, trishydroxyphenylmethanes, aralkylpolyphenols, dicyclopentadiene polyphenols, etc. These curing agents for epoxy resins may be used alone. It is also possible to use more than one species in combination. Of these, alicyclic acid anhydrides and polyhydric phenols are particularly desirable in terms of improving the heat resistance and moisture resistance of the cured layer.

  When an amine curing agent is used as the curing agent corresponding to the component (B) in the curable epoxy resin composition, the epoxy resin cured layer is applied when high heat of 150 ° C. or higher is applied to the resulting composite. Is significantly colored (deteriorated), the tensile elongation rate is significantly reduced, and it becomes hard due to thermal deterioration, against expansion and contraction of other constituent materials with heat, and deformation of the composite due to external stress This is not preferable because the function as a composite is impaired.

<C component>
As the curing accelerator for the component (C) in the curable epoxy resin composition used for producing the composite of the present invention, the following general curing (acceleration) agents for epoxy resins are used.
Imidazole compounds such as 2-methylimidazole, 2-ethyl-4imidazole and 2-phenylimidazole and salts thereof, BF ₃ complex compounds of amines, Bronsted acid salts such as aliphatic sulfonium salts and aromatic sulfonium salts, dicyandiamides Organic acid hydrazides such as adipic acid dihydrazide and phthalic acid dihydrazide, organic phosphine compounds such as polymercaptans and triphenylphosphine, and the like. These curing accelerators may be used alone or in combination of two or more.

<Arbitrary ingredients>
In the curable epoxy resin composition for forming the epoxy resin cured layer in the composite of the present invention, the following components may be added and blended as necessary.
(1) Powdery reinforcing agents and fillers such as metal oxides such as aluminum oxide and magnesium oxide, silicon compounds such as fine powder silica, fused silica and crystalline silica, fillers such as glass beads, and aluminum hydroxide Metal hydroxide, gold, silver, copper, aluminum and other metals, carbon, rubber, kaolin, mica, quartz powder, graphite, molybdenum disulfide, etc.
These blends are suitably 0.1-1500 parts by mass with respect to 100 parts by mass of the curable epoxy resin composition of the present invention.

(2) Colorants or pigments such as titanium dioxide, molybdenum red, bitumen, ultramarine blue, cadmium yellow, cadmium red, and organic dyes.
(3) Flame retardants such as antimony trioxide, bromine compounds and phosphorus compounds.
These substances are blended in an amount of 0.01 to 30 parts by mass with respect to 100 parts by mass of the curable epoxy resin composition for forming the epoxy resin cured layer constituting the composite of the present invention.

(4) Furthermore, various curable monomers, oligomers and synthetic resins can be blended for the purpose of improving the properties of the epoxy resin cured layer. For example, diluent for epoxy resin such as aliphatic monoepoxy, thermosetting resin such as acrylic resin, phenol resin, silicone resin, thermoplastic resin such as polyethylene resin, polypropylene resin, vinyl chloride resin, nylon resin, acrylic resin, etc. One type or a combination of two or more types can be mentioned. The compounding ratio of these compounds and resins is 50% by mass with respect to 100 parts by mass of the curable epoxy resin composition in an amount that does not impair the original properties of the epoxy resin hard layer in the composite of the present invention. Part or less.

<Epoxy resin cured layer>
The epoxy resin hardened layer forming the composite of the present invention can be disposed as a heat-resistant and seismic isolation adhesive layer for automobiles. Since the adhesive layer for automobiles is often used in a portion that receives strong vibration, the constituent substrate is easily peeled off by external stress such as vibration or impact. Even when the constituent substrate is deformed by external stress, the cured epoxy resin layer in the composite of the present invention is preferable because it absorbs (relaxes) stress and prevents peeling between constituent substrates. .

About the softness | flexibility of the epoxy resin hardened layer used for the composite_body | complex of this invention, ShoreA hardness 90 or less and ShoreD hardness 80 or less are preferable. If the Shore hardness is higher than this, the flexibility of the cured epoxy resin layer is lowered, and the followability to other constituent materials is lowered, which is not preferable.
The cured epoxy resin layer in the composite of the present invention is required to have excellent adhesion to other constituent materials. If the epoxy resin hardened layer is flexible if the adhesiveness is poor, due to the lack of adhesive strength against the difference in thermal expansion and shrinkage between other components and deformation of the composite due to external stress Since peeling will occur, it is not preferable.

  As for the hygroscopicity of the cured epoxy resin layer used in the composite of the present invention, the hygroscopicity at 121 ° C., 100% RH, 24 hr is preferably 0 to 2.0 mass%. When the moisture absorption rate exceeds 2% by mass, it is not preferable when used for electrical and electronic applications because reliability is lowered due to deterioration of insulation properties due to water and corrosion of metal materials such as copper and aluminum.

<Other components>
Other constituent materials used in the composite of the present invention include metals such as copper, aluminum, iron, stainless steel, gold, silver, polyethylene resin, polypropylene resin, ABS resin, vinyl chloride resin, nylon resin, polystyrene resin, Synthetic resins such as acrylic resins, PET, polycarbonate, thermoplastic resins such as thermoplastic elastomers, epoxy resins, melamine resins, polyester resins, silicone resins, phenolic resins, etc., natural rubber, synthetic rubber, glass, Fibers such as ceramics, carbon, carbon fiber, and glass fiber are preferably used.

<Composite>
A preferred example of the composite of the present invention is a flexible printed wiring board. In the case of flexible printed wiring boards, not only the metal-to-metal and metal-to-synthetic resins are strongly bonded by the adhesive layer, but even if thermal expansion or external stress is applied to the wiring board, It is important that the adhesive layer flexibly follows deformation and does not impair the function as a flexible printed wiring board, but the cured epoxy resin layer forming the composite of the present invention satisfies the above conditions. It is preferable to satisfy it sufficiently.

  Examples of the composite of the present invention include composites with carbon fibers and glass fibers. By coating the surface of carbon fiber or glass fiber and arranging an epoxy resin hardened layer to form an adhesion layer between carbon fiber and glass fiber, not only the strength of the fiber is increased, but also the conventional fiber reinforced composite This is preferable because the fiber-reinforced composite can be toughened by improving the “brittleness”.

Examples of the composite of the present invention include composite glass such as tempered glass and crime prevention glass formed by bonding glass and glass or glass and synthetic resin.
Moreover, the epoxy resin hardened layer in the composite of the present invention can be disposed as a surface protective layer of a laminate that seals the surface of the electric / electronic component. The disposed epoxy resin hardened layer adheres closely to the surface of the electrical / electronic component, flexibly follows the base material, and does not generate cracks due to external impact applied to the electrical / electronic component. This has the effect of preventing disconnection of the circuit of the electronic component and detachment of the component.

A diglycidyl ether of polytetramethylene ether glycol used in Examples and Comparative Examples was prepared as follows.
<Production example>
162.5 g of polytetramethylene ether glycol (Mitsubishi Chemical Corporation, trade name: PTMG # 650) having a number average molecular weight of 650 previously heated to 45 ° C. in a 1 L glass flask equipped with a stirrer, dropping funnel and thermometer The borohydride ethyl ether 1.046g was prepared and it heated to 80 degreeC. Epichlorohydrin (50.9 g) (1.1 equivalent per hydroxyl group equivalent of diol) was added dropwise over 1 hour so as not to exceed 85 ° C. The mixture was aged for 1 hour while maintaining at 80 to 85 ° C, and then cooled to 45 ° C. 170.5 g of 48.5 mass% sodium hydroxide aqueous solution was added, and it heated at 70 degreeC, and stirred vigorously for 4 hours. After cooling to 60 ° C., 208.75 g of methyl isobutyl ketone was added and dissolved, and 150 g of water was added and washed with water to separate the aqueous phase to remove the generated salt. After repeating this washing with water three times, the organic layer was separated, heated to 150 ° C. at normal pressure to distill off methyl isobutyl ketone, and then desolvated at 150 ° C. for 30 minutes under reduced pressure to remove colorlessness. 200 g of transparent polytetramethylene ether glycol diglycidyl ether was obtained. The analytical value of this product was an epoxy equivalent of 437 g / equivalent, and a viscosity at 25 ° C. of 193 mPa.s. s.

<Measurement method of total chlorine content>
The total chlorine is measured by dissolving 0.1 g of a sample in a mixed solvent of 12.5 ml of toluene / 12.5 ml of dimethyl cellosolve, adding 4 ml of biphenyl sodium, stirring for 2 minutes at room temperature, and then adding 0.01N silver nitrate. It can be determined by titrating with a solution. As a result of measurement by this analytical method, the total chlorine content of the polytetramethylene ether glycol epoxy compound obtained in Production Example 1 was 2.0 mass%.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the part in an example means a mass part.

Example 1
Diglycidyl ether of polytetramethylene ether glycol obtained in Production Example 1 (epoxy equivalent: 437 g / equivalent, viscosity at 25 ° C .; 193 mPa.s), Epicoat 828 (trade name of Japan Epoxy Resin Co., Ltd .; bisphenol as epoxy resin) 40 parts of A-type epoxy resin, epoxy equivalent; 186 g / equivalent), 36 parts of PSM-4261 (product name of Gunei Chemical Co., Ltd .; phenol novolac resin, hydroxyl equivalent: 103 g / equivalent) as a phenol curing agent uniformly at a temperature of 95 ° C. Then, TPP (triphenylphosphine) was added and mixed as a curing accelerator to obtain an epoxy resin composition. This composition was degassed under reduced pressure, poured into a mold, and cured in an oven at 100 ° C. for 3 hours and then at 140 ° C. for 3 hours to obtain a cured product. The physical property values of this epoxy cured product are shown in Tables 1 and 2.

Examples 2 to 4, Example 7 and Comparative Examples 1 to 3
Except changing an epoxy resin and an acid anhydride hardening | curing agent as shown in Table 1 and Table 2, operation similar to Example 1 was performed, the epoxy resin composition was obtained, and hardened | cured material was obtained. The physical properties of the epoxy cured product are shown in Table 1.

Example 5
60 parts of diglycidyl ether obtained in Production Example 1 (epoxy equivalent; 437 g / equivalent, viscosity at 25 ° C .; 193 mPa.s), Epicoat 828 as epoxy resin (trade name of Japan Epoxy Resin Co., Ltd .; bisphenol A type epoxy resin, epoxy Equivalent; 186 g / equivalent) 40 parts, MH-700 as an acid anhydride curing agent (trade name of Shin Nippon Rika Co., Ltd .; methylhexahydrophthalic anhydride, acid anhydride equivalent; 164 g / equivalent) 58 parts at a temperature of 50 ° C. Then, Hishicolin PX-4MP (Nippon Kagaku Co., Ltd. trade name; quaternary phosphonium salt) was added and mixed as a curing accelerator to obtain an epoxy epoxy resin composition. This composition was degassed under reduced pressure, poured into a mold, and cured in an oven at 100 ° C. for 3 hours and then at 140 ° C. for 3 hours to obtain a cured product. The physical property values of this epoxy cured product are shown in Tables 1 and 2.

Examples 5-6
Except changing an epoxy resin and an acid anhydride hardening | curing agent as shown in Table 1 and Table 2, operation similar to Example 5 was performed, the epoxy resin composition was obtained, and hardened | cured material was obtained. The physical properties of the epoxy cured product are shown in Table 1.

Comparative Example 3
Diglycidyl ether of polytetramethylene ether glycol obtained in Production Example 1 (epoxy equivalent: 437 g / equivalent, viscosity at 25 ° C .; 193 mPa.s), Epicoat 828 (trade name of Japan Epoxy Resin Co., Ltd .; bisphenol as epoxy resin) 40 parts A type epoxy resin, epoxy equivalent; 186 g / equivalent), and MXDA (Mitsubishi Gas Chemical Company; metaxylylenediamine, active hydrogen equivalent; 34 g / equivalent) as amine curing agent 28 parts uniformly at a temperature of 50 ° C. The resulting mixture was mixed to obtain an epoxy epoxy resin composition. This composition was degassed under reduced pressure, poured into a mold, and cured in an oven at 100 ° C. for 3 hours and then at 140 ° C. for 3 hours to obtain a cured product. The physical property values of this epoxy cured product are shown in Table 2.

Comparative Examples 4 and 5
In the same manner as in Comparative Example 3, an epoxy resin composition was obtained with the formulation shown in Table 2, and a cured product was obtained. The physical property values of this epoxy cured product are shown in Table 2.

<Heat resistance deterioration test (color difference measurement)>
The epoxy cured products obtained by the methods described in Examples 5 to 7 and Comparative Examples 3 to 5 are measured for color difference (YI) values using a color difference meter, and are shown in Table 2. On the other hand, the obtained epoxy cured product is left in an oven at 180 ° C. for 7 hours, taken out from the oven after 7 hours, the epoxy cured product is cooled to room temperature, and the color difference ( YI) values were measured. (Values are shown in Table 2)

<Tensile test>
The epoxy cured product obtained by the method described in Examples 5 to 7 and Comparative Examples 3 to 5 was molded into a test piece for tensile test (JIS-K6251 No. 2 dumbbell), and a tensile test was performed based on the test method. The values performed are shown in Table 2. On the other hand, the molded test piece for tensile test was left in an oven at 180 ° C. for 72 hours, taken out of the oven after 72 hours, and the cured epoxy product was cooled to room temperature, and then a tensile test was performed in the same manner. Is shown in Table 2.

As is clear from the data in Tables 1 and 2, the cured epoxy resin layer forming the composite of the present invention is not only excellent in adhesive strength with dissimilar constituent materials such as copper and aluminum, but also rich in flexibility. Since the layer has a low moisture absorption rate and excellent heat resistance, the composite having the cured epoxy resin layer is required to have a wide range of heat resistance, adhesiveness, water resistance, mechanical strength, electrical properties, and the like. Useful as a structural material in the field.

Claims (16)

The curable epoxy resin composition containing the following component (A), component (B) and component (C) is brought into contact with other constituent materials in an uncured state, and the uncured epoxy resin composition in a contacted state. A composite formed by curing an object, in which an epoxy resin cured layer and the other constituent materials are integrated.
Component (A): Epoxy resin (B) which is liquid at 25 ° C. containing 30 to 100% by mass of diglycidyl ether obtained from polyether glycol having a number average molecular weight of 200 to 2000 and 0 to 70% by mass of other epoxy resins Component; acid anhydride and / or phenol-based curing agent (C) component; curing accelerator The complex according to claim 1, wherein the diglycidyl ether obtained from the polyether glycol in the component (A) is a diglycidyl ether obtained from a polyether glycol having a number average molecular weight of 250 to 1500. The composite according to claim 1 or 2, comprising 40 to 90% by mass of diglycidyl ether in component (A) and 10 to 60% by mass of another epoxy resin. The other epoxy resin in the component (A) is one or more epoxy resins selected from epoxy resins having an aromatic ring and / or an alicyclic structure. The composite according to Item. The other epoxy resin in the component (A) is at least one epoxy resin selected from bifunctional epoxy resins having an aromatic ring and / or an alicyclic structure. The complex according to any one of the above. The total chlorine content of the diglycidyl ether obtained from the polyether glycol in the component (A) is 0.01 to 0.6% by mass, according to any one of claims 1 to 5. Complex. The complex according to any one of claims 1 to 6, wherein the diglycidyl ether obtained from the polyether glycol in component (A) is a diglycidyl ether of polytetramethylene ether glycol.   The composite body according to any one of claims 1 to 7, wherein the composite body comprises an electrical / electronic component.   9. The moisture absorption (water) rate of 121 ° C., 100% RH, 24 hr of the cured epoxy resin layer used in the composite is 0 to 2.0% by mass, according to claim 1. Complex. A curable epoxy resin composition for producing a composite comprising the following (A) component, (B) component and (C) component, wherein an epoxy resin cured layer and other constituent materials are integrated.
Component (A): epoxy resin (B) liquid at 25 ° C. containing 30 to 100% by mass of diglycidyl ether obtained from polyether glycol having a number average molecular weight of 200 to 2000 and 0 to 70% by mass of other epoxy resins Component; acid anhydride and / or phenol-based curing agent (C) component; curing accelerator 11. The curability according to claim 10, wherein the diglycidyl ether obtained from the polyether glycol in the component (A) is a diglycidyl ether obtained from a polyether glycol having a number average molecular weight of 250 to 1500. Epoxy resin composition. The curable epoxy resin composition according to claim 10 or 11, wherein diglycidyl ether in component (A) is contained in an amount of 40 to 90% by mass and another epoxy resin in an amount of 10 to 60% by mass. The other epoxy resin in the component (A) is at least one epoxy resin selected from epoxy resins having an aromatic ring and / or an alicyclic structure. The curable epoxy resin composition according to Item. The other epoxy resin in component (A) is one or more epoxy resins selected from bifunctional epoxy resins having an aromatic ring and / or an alicyclic structure. The curable epoxy resin composition according to any one of the above. The total chlorine content of diglycidyl ether obtained from the polyether glycol in the component (A) is 0.01 to 0.6% by mass, according to any one of claims 10 to 14. Curable epoxy resin composition. The curable epoxy according to any one of claims 10 to 15, wherein the diglycidyl ether obtained from the polyether glycol in the component (A) is a diglycidyl ether of polytetramethylene ether glycol. Resin composition.