JP2000256635A - Substrate with adhesive layer using acrylic resin and adhesive film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide substrates with an adhesive layer stable in adhesive strength which are different in adhesive strength at both sides and have heat resistance, resistance to galvanic corrosion and moisture resistance necessary for mounting semiconductor chips large in the difference in coefficient of thermal expansion on various types of high density printed-wiring boards of glass epoxy substrates, flexible substrates and the like, and adhesive films. SOLUTION: A substrate with an adhesive layer using an acrylic resin is obtained by forming an adhesive layer comprising an acrylic resin composed of (A) 1-10 wt.% structural units derived from a (meth)acrylate monomer having an epoxy group, (B) 10-50 wt.% structural units derived from acrylonitrile, and (C) 40-89 wt.% structural units derived from another copolymerizable monomer and having a weight average molecular weight of 500,000-1,500,000 and a glass transition temperature of -50 to 0 deg.C; an epoxy resin; and an epoxy resin curing agent on a substrate having no same tendency in hydrophobicity or hydrophilicity as the acrylic resin. An adhesive film is obtained by removing the substrate from this substrate with an adhesive resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a substrate having an adhesive layer using an acrylic resin and an adhesive film.

[0002]

2. Description of the Related Art In recent years, with the development of electronic devices, the mounting density of electronic components has increased, and bare chip mounting of semiconductors on printed wiring boards, where low cost can be expected, has been promoted.

As a substrate for mounting a semiconductor chip, a ceramic substrate having a relatively small coefficient of thermal expansion in order to ensure connection reliability and a ceramic substrate having a relatively high thermal conductivity in order to easily radiate heat to the outside have been used in many cases. Was. A liquid adhesive represented by a silver paste is used for mounting a semiconductor chip on such a ceramic substrate.

A film adhesive is used for a flexible printed wiring board and the like, and a system mainly containing acrylonitrile butadiene rubber is often used.

[0005] Investigations on printed wiring board-related materials include an acrylic resin, an epoxy resin, a polyisocyanate, and an inorganic filler disclosed in JP-A-60-243180 as an improved solder heat resistance after moisture absorption. There is glue. Also, JP-A-61-13868.
There is an acrylic resin, an epoxy resin, and an adhesive containing a primary amine compound having a urethane bond in the molecule and having both ends terminated with a primary amine compound and an inorganic filler, which are disclosed in Japanese Patent Publication No. However, these deteriorate significantly when a moisture resistance test is performed under severe conditions such as a pressure cooker test (PCT) treatment.

When a silver paste adhesive is used for mounting a semiconductor chip on a ceramic substrate, the dispersion of the silver filler becomes uneven due to the sedimentation of the silver filler, and it is necessary to pay attention to the storage stability of the paste. Is L
There are problems such as inferiority to OC (Lead on Chip) and the like. In addition, as the film-like adhesive, a system containing acrylonitrile-butadiene rubber as a main component has been often used, but when treated at a high temperature for a long time, there are problems such as a large decrease in the adhesive strength and inferior electric corrosion resistance. there were. In particular, when a humidity resistance test is performed under severe conditions such as a PCT process used in reliability evaluation of semiconductor-related components, deterioration is large.

Further, Japanese Patent Application Laid-Open No. Sho 60-243181,
Japanese Patent Application Laid-Open No. 61-138680 also discloses P
Deterioration is large in a moisture resistance test under severe conditions such as CT processing.

As one means for solving the above-mentioned problems, it has been proposed to convert a composition of an acrylic resin, which is less deteriorated in a moisture resistance test under severe conditions such as a PCT treatment, into a monomer which is hardly hydrolyzed. However, when such an acrylic resin is processed / formed into a plate, a film, or a thin film, the acrylic resin component is affected by the environmental conditions and physical properties of a jig and a substrate material used for the processing / or formation. In some cases, the strength may decrease on the surface of a plate, a film, or a thin film, and as a result, there is a problem that the bonding strength is not stable.

[0009] Further, the conventionally known adhesive film has almost the same adhesive strength on both sides, but is not suitable for the application of single-sided bonding performed in a part of semiconductor packaging. Was required. In the case of double-sided bonding, the optimum bonding strength cannot be selected due to the mechanical strength of each mating material. If one is mechanically strong and the other is fragile, it is necessary that the bonding strength be different on both sides. Was.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to mount a semiconductor chip having a large difference in thermal expansion coefficient on various high-density printed wiring boards such as a glass epoxy board and a flexible board with different adhesive strengths on both sides. An object of the present invention is to provide a substrate with an adhesive and an adhesive film having heat resistance, electrolytic corrosion resistance, and moisture resistance necessary for the above-mentioned method, and having stable adhesive strength.

[0011]

According to the present invention, there are provided (A) 1 to 10% by weight of a structural unit derived from a (meth) acrylate monomer having an epoxy group, (B) 10 to 50% by weight of a structural unit derived from acrylonitrile, (C) a weight average molecular weight of 40 to 89% by weight of a structural unit derived from another copolymerizable monomer is 500,000 to 1,500,000.
An acrylic resin having a glass transition temperature of −50 to 0 ° C., an adhesive layer made of an epoxy resin and an epoxy resin curing agent is formed on a base material whose hydrophobicity or hydrophilicity is not the same as the acrylic resin. To provide a substrate with an adhesive layer using an acrylic resin.

Further, the present invention provides an adhesive film obtained by removing a substrate from the above-mentioned substrate having an adhesive layer.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The acrylic resin used in the adhesive of the present invention comprises (A ') 1 to 10% by weight of an epoxy group-containing (meth) acrylate monomer, (B') 10 to 50% by weight of acrylonitrile and ( C ') It is obtained by solution polymerization of a solution comprising 40 to 89% by weight of another copolymerizable monomer.

As the (meth) acrylate monomer having an epoxy group (A ') used in the synthesis of the acrylic resin, compounds having a copolymerizable double bond such as glycidyl methacrylate and glycidyl acrylate are used.

Further, in order to improve insulation reliability during moisture absorption, a (meth) acrylate monomer having a total of 30 ppm or less of epoxy groups in total containing chlorine ions and hydrolyzable chloride ions, for example, NOF Corporation Blenmer GS can be preferably used.

(A ') The amount of the (meth) acrylate monomer having an epoxy group used is as defined in (A') and (B ').
And 1 to 10% by weight, preferably 3 to 7% by weight, based on the total amount of component (C '). If it is less than 1% by weight,
The required adhesive strength cannot be obtained. If it exceeds 10% by weight, the resin may gel.

(B) The amount of acrylonitrile used is based on the total amount of the components (A '), (B') and (C ').
It is 10 to 50% by weight, preferably 20 to 40% by weight. If it is less than 10% by weight, the required elastic modulus cannot be obtained.
If it exceeds 50% by weight, the elastic modulus becomes too high.

The (C ') other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and (meth) acrylic acid. Alkyl (meth) acrylates or cycloalkyl (meth) acrylates, such as 2-ethylhexyl acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate,
Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; aminomethyl (meth) acrylate; N-methylaminomethyl (meth) acrylate; ) Aminoalkyl (meth) acrylates such as N, N-diethylaminoethyl acrylate, styrene monomers such as methacrylic acid, acrylic acid, styrene, vinyltoluene, α-methylstyrene, vinyl chloride, vinylidene chloride,
Vinyl derivatives such as vinyl acetate and isopropenyl acetate, unsaturated dibasic acids such as maleic acid and fumaric acid, acid anhydrides thereof, monoesters such as monomethyl esters and monoethyl esters, or dimethyl esters and diethyl esters thereof Diesters.

When a (meth) acrylic acid having a carboxyl group or a hydroxyalkyl (meth) acrylate having a hydroxyl group is used, a crosslinking reaction proceeds, so that the adhesive strength may be reduced.

Further, a copolymerizable monomer having a bromo atom can be used. Examples of the copolymerizable monomer having a bromine atom include brominated styrene (trade name: frame cut 310-K, commercially available from Tosoh Corporation);
Flamecut 122K, a trade name of 2,2-bis (4-allyloxy-3,5-dibromophenyl) propane; Pyrogard FR-100, a trade name of tribromophenylallyl ether commercially available from Daiichi Kogyo Seiyaku; Trade name FR-1025 of pentabromobenzyl acrylate commercially available from East Co., Ltd.
M and other copolymerizable monomers having a bromine atom can be used. The number of copolymerizable double bonds in one molecule of a copolymerizable monomer having a bromine atom is preferably one, and if it is two or more, there is a possibility of gelling, so that the amount used is small and flame retardancy is low. Effect is reduced. The amount of the copolymerizable monomer having a bromine atom is preferably at least 10% by weight, more preferably 20 to 30% by weight, based on the total amount of the components (A '), (B') and (C '). Is done.

The method of polymerizing the acrylic resin used in the present invention is not particularly limited, but is preferably (A ')
It is obtained by subjecting a monomer solution composed of the components (B ′) and (C ′) to solution polymerization by a known radical polymerization method or the like. In this case, aromatic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, and chlorine solvents such as carbon tetrachloride can be used as the organic solvent. Further, upon polymerization, benzoyl peroxide, dicumyl peroxide, dibutyl peroxide, organic peroxides such as t-butylperoxybenzoate, azobisisobutyronitrile, azobisvaleronitrile and the like An azobis compound is used.

The monomer concentration at the start of the solution polymerization is preferably from 90 to 100% by weight, more preferably from 95 to 100% by weight. If the monomer concentration is less than 90% by weight, the molecular weight tends not to be increased. The reaction temperature is preferably from 80 to 90 ° C, more preferably from 82 to 88 ° C. If it is higher than 90 ° C., the molecular weight of the polymer tends to decrease, and if it is lower than 80 ° C., the reaction tends to stop.
The polymerization rate at the time of stopping the reaction is preferably 20 to 40%, more preferably 25 to 35%. If the polymerization rate is low, the yield tends to decrease, and if it is high, the molecular weight dispersity tends to increase. The target degree of dispersion is preferably 2.0-3.0, more preferably 2.
3 to 2.5. The polymerization initiator concentration is (A '),
It is preferably 0.01 to 0.1 part by weight, more preferably 0.02 to 0.1 part by weight, based on 100 parts by weight of the total amount of the components (B ') and (C'). If it exceeds 0.1 part by weight, the molecular weight of the polymer tends to be low, and if it is too small, it does not tend to react.

Composition of structural units (A), (B) and (C) derived from these monomers in a polymer obtained by polymerizing components (A '), (B') and (C ') Is substantially the same as the composition of the monomer composed of the components (A '), (B') and (C ') used in the polymerization.

The weight average molecular weight of the acrylic resin used in the present invention needs to be 500,000 or more in view of the balance of properties. If it is less than 500,000,
The strength and flexibility in sheet and film form are reduced, and tackiness is increased. The preferred weight average molecular weight is 500,
000 to 1,500,000, more preferably 7
It is between 00,000 and 1,000,000. The weight average molecular weight is measured by a gel permeation chromatography (GPC) using a calibration curve with standard polystyrene.

The acrylic resin used in the present invention must have a glass transition temperature of -50 ° C to 0 ° C.
If the temperature is lower than −50 ° C. or more than 0 ° C., it is not preferable from the balance between the elastic modulus and other properties. Preferred glass transition temperature is -50 to -5C, more preferably -40 to -10C.
It is.

The epoxy resin used in the present invention may be any resin as long as it cures and exhibits an adhesive action.
An epoxy resin having two or more functional groups and preferably having a molecular weight of less than 5000 is used. For example, bisphenol A type,
Liquid epoxy resins such as bisphenol F type, and polyfunctional epoxy resins such as phenol novolak type and cresol novolak type can be used, and the trade names of Yuka Shell Epoxy Co., Ltd. Epicoat 807, Epicoat 827, Epicoat 828, Dow Chemical Japan Company product name E. FIG. R. 330, D.I. E. FIG. R. 331; E. FIG.
R. 361, trade name YD128, Y of Toto Kasei Co., Ltd.
DF170, trade name EPPN-20 of Nippon Kayaku Co., Ltd.
1, EOCN1012, EOCN1025, and ESCN-001 and ESCN-195 of Sumitomo Chemical Co., Ltd. can be used.

Further, a phenoxy resin compatible with the epoxy resin can be used. Examples of the phenoxy resin include Phenototo Y, a trade name of Toto Kasei Co., Ltd.
P-40, Phenotote YP-50, Phenotote YP
-60 can be used.

The epoxy resin is preferably added in an amount of 40 to 250 parts by weight, more preferably 50 to 100 parts by weight, based on 100 parts by weight of the acrylic resin.

Examples of the epoxy resin curing agent used in the present invention include amine, polyamide, acid anhydride, polysulfide, boron trifluoride, and bisphenol A, bisphenol A, which is a compound having two or more phenolic hydroxyl groups in one molecule. F, bisphenol S and the like can be used. In particular, it is preferable to use a phenol novolak resin, a bisphenol novolak resin, or a cresol novolak resin, which is excellent in electric corrosion resistance when absorbing moisture.
FENOLITE L, a trade name of Dainippon Ink and Chemicals, Inc.
F2882, phenolite LF2822, phenolite TD-2090, phenolite TD-2149, phenolite VH4150, and phenolite VH4170 can be preferably used. Epoxy resin curing agent is acrylic resin,
It is preferable to mix 10 to 20 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin and the epoxy resin curing agent.

It is preferable to use a curing accelerator together with the epoxy resin curing agent. As the curing accelerator, various imidazole compounds can be used. For example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-
Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazolium trimellitate, etc. can be used, and the trade name of Shikoku Chemicals Co., Ltd. 2E4M
Z, 2PZ-CN, 2PZ-CNS can be used. The epoxy resin curing accelerator is used in an amount of 0.1 to 100 parts by weight of the total amount of the acrylic resin, the epoxy resin and the epoxy resin curing agent.
It is preferable to add 0.5 parts by weight.

A coupling agent may be added to the adhesive to improve the bonding at the interface. As the coupling agent, a silane coupling agent is preferable. As a silane coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
γ-ureidopropyltriethoxysilane, N-β-aminoethyl-γ-aminopropyltrimethoxysilane and the like can be used. It is preferable to add 0.5 to 3 parts by weight of the coupling agent to 100 parts by weight of the total amount of the acrylic resin, the epoxy resin, and the epoxy resin curing agent.

Further, the handling and heat conductivity of the adhesive and the adhesive film are improved, the flame retardancy is imparted, the melt viscosity is adjusted,
For the purpose of imparting thixotropic properties and improving surface hardness, an inorganic filler can be added. The amount of the epoxy resin curing agent is from 5 to 100 parts by weight of the total amount of the acrylic resin, the epoxy resin and the epoxy resin curing agent from the viewpoint of the effect.
It is preferable to mix 40 parts by weight.

As the inorganic filler, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina powder, crystalline silica, amorphous silica, aluminum nitride powder, Boron nitride powder, aluminum borate whiskers and the like can be used.

In order to improve the thermal conductivity, alumina,
It is preferable to use aluminum nitride, boron nitride, crystalline silica, amorphous silica, or the like.

For imparting flame retardancy, aluminum hydroxide, magnesium hydroxide, antimony trioxide, diantimony pentoxide and the like are preferable.

For adjusting the melt viscosity and imparting thixotropic properties, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina powder, crystalline silica, amorphous Silica and the like are preferred.

Further, an ion scavenger can be used to prevent adsorption of ionic impurities. As the ion scavenger, for example, a triazine thiol compound or a bisphenol-based reducing agent known as a copper damage inhibitor for preventing copper from being ionized and eluted can be used. It is preferable to add 0.1 to 1 part by weight of the ion scavenger to 100 parts by weight of the total amount of the acrylic resin, the epoxy resin, and the epoxy resin curing agent.

An adhesive layer comprising the above-mentioned acrylic resin, epoxy resin and epoxy resin curing agent is formed on a substrate having the same hydrophobicity or hydrophilicity as the above-mentioned acrylic resin to form a substrate having an adhesive layer. I do. When the substrate is removed from the substrate with the adhesive layer, an adhesive film is obtained.

The concentration of chloride ion and hydrolyzable chloride ion in the adhesive film is preferably 30 ppm or less in total as measured by ion chromatography.

The method for measuring the chloride ion and the hydrolyzable chloride ion of the adhesive film is as follows.
g, add 10 ml of ultrapure water, and add PCT (120 ° C./2 at
m / 20 hours). Take 1 g of this extract and measure the chloride ion concentration by ion chromatography. The ion chromatograph is measured using ICS-A23 manufactured by Yokogawa Analytical Systems Co., Ltd.

The formation of the adhesive layer on the substrate is preferably performed by
Each component of the adhesive is dissolved or dispersed in a solvent to form a varnish having an adhesive concentration of preferably 10 to 80% by weight, more preferably 20 to 70% by weight, and is applied on a substrate and heated to remove the solvent. It is done by doing. The varnishing solvent is relatively low boiling point methyl ethyl ketone, acetone,
Methyl isobutyl ketone, toluene, butyl cellosolve, 2-ethoxyethanol, methanol, ethanol and the like can be used. In the production of the varnish, it is preferable to disperse the varnish using a grinder, a three-roll mill, a bead mill, or the like in consideration of dispersion of the inorganic filler.

The thickness of the adhesive layer varies depending on the mixing ratio of each monomer of the acrylic resin and the mixing ratio of the acrylic resin, the epoxy resin and the curing agent for the epoxy resin. Preferably, there is. In order to improve the adhesive strength, it is preferable to make the thickness as thin as possible. For application and other thin film formation methods,
There are various methods and devices, which are determined as appropriate.

As the base material, a base material whose hydrophobicity or hydrophilicity is not the same as that of the acrylic resin in the adhesive is used. When the contact angle of the water of the acrylic resin is a and the contact angle of the water of the substrate is b, preferably, a / b <3 /
4 or a / b> 4/3, more preferably a / b <2/3
Or a / b> 3/2, more preferably a / b <1/2
Alternatively, a substrate having a relationship of a / b> 2/1 is used.

The contact angle of water of the acrylic resin is usually 60 to 9
Since it is 0 °, as such a substrate, a substrate of a polymer film material or an inorganic material coated with a water-breaking component or a hydrophobic component such as fluorine-coated polyimide, slide glass, fluorine-coated polypropylene or fluorine-coated polypropylene ethylene terephthalate is used. It is preferably used. Further, a substrate obtained by hydrophobizing the surface of the above-mentioned substrate or another substrate and having a water contact angle within the above range can be used as the substrate. The thickness of the substrate is 1 to 800
μm is preferred.

The adhesive film of the present invention can be obtained by removing the substrate from the substrate with an adhesive layer of the present invention. The adhesive film obtained by removing the base material from the base material with the adhesive layer using a base material that is not the same as the acrylic resin in hydrophobicity or hydrophilicity has the same hydrophobicity or hydrophilicity as the acrylic resin. As compared with an adhesive film obtained by removing the base material from the base material with the adhesive layer using the base material having the tendency, the adhesive strength on the base material surface is reduced, and an adhesive film having different adhesive strengths on both surfaces can be obtained. Further, heat resistance, electric corrosion resistance, and moisture resistance are superior to conventional adhesive films.

The acrylic resin used in the present invention has a low modulus of elasticity at around room temperature. By increasing the mixing ratio of the acrylic resin in the adhesive or the adhesive film, the difference in the coefficient of thermal expansion between the semiconductor chip and the printed wiring board is increased. Cracks can be suppressed by the effect of relaxing the stress generated in the heating / cooling process at the time of the temperature cycle test due to the above. Also,
The acrylic resin of the present invention has excellent reactivity with an epoxy resin, and thus exhibits excellent performance in a moisture resistance test typified by a PCT treatment because the cured adhesive is chemically and physically stable. In addition, the use of a high molecular weight acrylic resin solves problems of workability such as a decrease in strength, a decrease in flexibility, and an increase in tackiness of a conventional adhesive film.

Further, the epoxy resin contained in the acrylic resin used in the present invention partially reacts with the epoxy resin,
Since the whole is crosslinked and gelled including unreacted epoxy groups, fluidity is suppressed, and workability is not impaired even when a large number of epoxy groups and the like are contained. Further, since a large number of unreacted epoxy resins are present in the gel, even when the whole is gelled, the decrease in the adhesiveness is reduced.

When the adhesive is dried, the epoxy group and the epoxy resin contained in the acrylic resin react together. However, the acrylic resin containing an epoxy group used in the present invention has a large molecular weight and an epoxy resin in one molecular chain. Even if the reaction progresses a little because it contains a group, it gels. Usually, a state in which heat generation of 10 to 40% of the total curing calorific value when measured by differential scanning calorimetry (DSC) is completed, that is, A or B
Gelation occurs in the first half of the stage. For this reason, the gel is formed in a state containing a large amount of unreacted components such as an epoxy resin, so that the melt viscosity is greatly increased as compared with the case where the gel is not formed, and the workability is not impaired. Furthermore,
Since the adhesive can be formed into a film while containing a large amount of unreacted components such as an epoxy resin, there is an advantage that the life (effective use period) of the adhesive film is increased.

In the conventional epoxy resin-based adhesive, gelation occurs for the first time in the C-stage state from the latter half of the B-stage, and the unreacted components at this stage have a small amount of unreacted components. Since less unreacted components ooze out, the adhesiveness decreases. Further, although it is not clear about the reactivity of the epoxy group contained in the acrylic resin and the epoxy group of the epoxy resin, it is sufficient that the epoxy group contained in the acrylic resin has at least the same degree of reactivity, and only the epoxy group contained in the acrylic resin is selectively used. You do not need to react to

The A, B, and C stages in this case are as follows:
The A stage indicates the degree of curing of the adhesive, and the A stage is in a state of almost uncured and not gelled, and a state in which the calorific value of curing using DSC is 0% to 20% of the total curing calorific value. . The B stage is a state in which curing and gelation have progressed slightly, and a state in which the heat generation of curing is 20 to 60% of the total heat generation of curing. The C stage is in a state where the curing has progressed considerably and is in a gel state, and a state in which the heating value of the curing has been 60 to 100% of the total curing heating value.

Regarding the determination of gelation, the adhesive was immersed in a highly permeable solvent such as tetrahydrofuran (THF) and allowed to stand at 25 ° C. for 20 hours, after which the adhesive was swollen without being completely dissolved. Those were judged to be gelled.

[0052]

The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified. [Production Method of Acrylic Resins A to C] The compound (I) shown in Table 1 was placed in a reactor equipped with a mixer and a cooler.
Heat to 85 ° C., add the blend (II) shown in Table 1, keep the temperature for 4 to 8 hours, and obtain a polymer reacted at a conversion of 20 to 30%. After cooling, methanol is added to precipitate the polymer, and the supernatant is removed. The methanol remaining in the polymer is dried, followed by the addition of methyl ethyl ketone to a solids content of 15%.

The weight average molecular weights of the polymers A to C were measured by the following method. [Method for measuring weight average molecular weight] The weight average molecular weight is measured by gel permeation chromatography (GPC) using a calibration curve with standard polystyrene. <GPC conditions> Equipment used: Hitachi 635 type HPLC [manufactured by Hitachi, Ltd.] Column: Gelpack R-440, R450, R400
M [trade name, manufactured by Hitachi Chemical Co., Ltd.] Eluent: tetrahydrofuran Measurement temperature: 40 ° C. Flow rate: 2.0 ml / min Detector: differential refractometer The measurement results are shown in Table 1. The glass transition temperature is a calculated value. (Reference data: An introduction to synthetic resins for paint: written by Kyozo Kitaoka)

[0054]

[Table 1] Examples 1 to 3 and Comparative Examples 1 to 3 The materials (* ¹ to
* ⁵ ) was added to obtain a varnish of the adhesive composition. The obtained varnish was applied on various substrates shown in Table 2 and was heated at 140 ° C. for 5 minutes.
After heating and drying for a period of time, a coating film in a B-stage state having a film thickness of 80 μm was formed to prepare an adhesive film. * ¹ : Bisphenol A type epoxy resin (using Epicoat 828 manufactured by Yuka Shell Epoxy) * ² : Cresol novolak type epoxy resin (using ESCN001 manufactured by Sumitomo Chemical Co., Ltd.) * ³ : Phenol novolak resin (Dainippon Ink) * ⁴ : Phenoxy resin (uses Phenotote YP-50 manufactured by Toto Kasei Co., Ltd.) * ⁵ : 1-cyanoethyl-2-phenylimidazole (Curesol 2PZ- manufactured by Shikoku Chemicals Co., Ltd.) After evaluating the contact angle measurement of water between the obtained adhesive film and the substrate used, 42 alloys were adhered to each other using the adhesive film, and the average adhesive strength of the film (average peel strength) was examined. Was. Table 2 shows the results. <Evaluation conditions for measuring the contact angle of water on the adhesive film and the substrate used> Equipment used: contact angle measuring device (FACE manufactured by Kyowa Interface Science)
CONTACT ANGLE METER CA-D) Liquid: ion-exchanged water Liquid amount (once): 0.3 ml Number of measurements (n): 5 Measurement environment Temperature: 28 ° C., Humidity: 40% RH <Evaluation conditions for adhesive strength> Equipment used : Peel measuring device (peel strength tester manufactured by Vesta Sangyo Co., Ltd.) Tensile speed: 50 mm / 50 mm Strength measurement area: (L) 20 × (W) 10 mm ² Adhesion partner material: 42 alloy Number of measurements (n): 5 Measurement environment Temperature: 28 ° C, humidity: 40% RH

[0055]

[Table 2]

[0056]

The substrate with an adhesive and the adhesive film using the acrylic resin of the present invention have excellent adhesive properties with different adhesive strengths on both sides and stable adhesive strength.
Excellent resistance to electric corrosion, moisture and heat.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Yoshihiro Nomura 14 Goi South Coast, Ichihara City, Chiba Prefecture Hitachi Chemical Co., Ltd. Goi Factory F-term (reference) 4J004 AA10 AA13 AB04 BA02 DA02 DA03 DB02 FA05 4J040 DB041 DB071 DB081 DC031 DC071 DE011 DE021 DF011 DF041 DF051 DF061 DF062 DF082 DG001 DG011 DG021 EC232 HA116 HA156 HA206 HA306 HA316 HD32 HD35 HD37 JA09 JB02 KA16 KA17 KA30 LA01 LA08 MA04 MA10 MB03 MB09 4J04 A03P02 A03P02 A03P02 A02P02A AL34P AL36P AM02Q BA29P BA30P BA31P BC04P CA05 DA01 DA25 JA03

Claims (3)

[Claims] (1) 1 to 10% by weight of a structural unit derived from a (meth) acrylate monomer having an epoxy group,
(B) Structural unit 10 to 50 derived from acrylonitrile
% By weight and 40 to 89% by weight of structural units derived from (C) another copolymerizable monomer have a weight average molecular weight of 50%.
An adhesive layer composed of an acrylic resin, an epoxy resin, and an epoxy resin curing agent having a glass transition temperature of -50 to 0 ° C and a hydrophobicity or hydrophilicity equal to that of the acrylic resin is used. A substrate with an adhesive layer using an acrylic resin formed on a substrate that is not inclined. 2. The adhesive according to claim 1, wherein the contact angle a of the water of the acrylic resin and the contact angle b of the water of the base material have a relationship of a / b <3/4 or a / b> 4/3. Substrate with layer. 3. An adhesive film obtained by removing a substrate from the substrate with an adhesive layer according to claim 1.