WO2003035744A1

WO2003035744A1 - Thermosetting resin composition

Info

Publication number: WO2003035744A1
Application number: PCT/JP2002/010909
Authority: WO
Inventors: Toru Fujiki; Toshiyuki Hasegawa; Hironobu Iyama; Toshiki Mori; Shigeki Naitoh
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2001-10-24
Filing date: 2002-10-22
Publication date: 2003-05-01

Abstract

A thermosetting resin composition comprising the following components (A), (B) and (C); a thermosetting film made from the composition; and laminates produced by thermosetting the film: (A) an ethylene/α,β-unsaturated carboxylic acid copolymer obtained by copolymerizing (a1) ethylene with (a2) an α,β-unsaturated carboxylic acid and/or an α,β-unsaturated carboxylic anhydride and (a3) a vinyl ester and/or an α,β-unsaturated carboxylic acid ester, (B) an epoxy-containing ethylene copolymer obtained by copolymerizing (b1) ethylene with (b2) a monomer represented by the general formula (1): (1) [wherein R is alkenyl having 2 to 18 carbon atoms; and X is carbonyl, phenylene, or methylene], and (C) an organic solvent and/or water.

Description

Description Thermosetting resin composition Technical field

The present invention relates to a thermosetting resin composition comprising ethylene ″ a,] 3-unsaturated carboxylic acid, an epoxy group-containing ethylene-based copolymer, and a solvent, a thermosetting film obtained from the composition, The present invention relates to a laminate obtained by thermosetting the film. Background art

In recent years, in the field of electric and electronic components, lighter, thinner and shorter have been promoted, and die bonding materials between semiconductor encapsulation materials, electronic component encapsulation materials (such as solar cells and electroluminescence lamps), and integrated circuit Z substrates Adhesives used for electrical and electronic components such as interlayer insulating layers between sheets and substrates are required to have low elastic modulus and thin film in addition to heat resistance when soldering. In addition, in order to simplify the manufacturing process of electric and electronic parts, it is required that the adhesive before curing be in a dry film form. On the other hand, a resin composition obtained by dry-blending an ethylene ', i3-unsaturated carboxylic acid copolymer containing a polar group and an ethylene copolymer containing an epoxy group, followed by extrusion molding. A film is disclosed in JP-A-64-142435. However, the resin composition film does not have sufficient adhesive strength, and the method described in the publication does not make it easy to obtain a thin film.

It is an object of the present invention to provide a thermosetting resin composition having excellent coatability and fluidity before thermosetting and capable of easily forming a thin film; To provide a thermosetting film having excellent adhesiveness and heat resistance and a low elastic modulus; and an electronic and electrical device in which a layer obtained by thermosetting the film and an adherend layer are in close contact with each other. An object of the present invention is to provide a laminate suitable for parts and the like. Disclosure of the invention The present invention

[1] A thermosetting resin composition containing the following components (A), (B) and (C): (A): (a ethylene,

(a ₂ ) a, | 3-unsaturated carboxylic acid and di- or di-, 0-unsaturated carboxylic anhydride and

(a ₃ ) bierester and / or di-unsaturated carboxylic acid ester

Ethylene and jS-unsaturated carboxylic acid copolymers obtained by polymerizing ethylene

(B): (b ethylene and

(b ₂ ) The following general formula (1)

(In the formula, R represents an alkenyl group having 2 to 18 carbon atoms, and X represents a carbonyl group, a phenylene group or a methylene group.)

Monomer represented by

Epoxy group-containing ethylene copolymer obtained by polymerizing

(C): an organic solvent and / or water.

[2] The content of the structural unit derived from the monomer (a ₂ ) is 0.01 to 20 parts by weight based on 100 parts by weight of the component (A), and the content of the structural unit derived from the monomer (a ₃ ) is The thermosetting resin composition according to [1], wherein the content of the structural unit is 25 to 70 parts by weight,

[3] The thermosetting composition according to [1] or [2], wherein the content of the structural unit derived from the monomer (b ₂ ) is 1 to 30 parts by weight based on 100 parts by weight of the component (B). Resin composition,

[4] In addition to the monomer (bj and the monomer (b ₂ ), the component (B) may further comprise (b ₃ ) a monomer copolymerizable with ethylene, which does not react with the epoxy group. A thermosetting toughening resin composition according to any one of [1] to [3], which is a copolymer obtained by polymerizing

[5] The total content of the structural unit derived from the monomer () and the structural unit derived from the monomer) is 30 to 100 parts by weight of the total of the polymers of the components (A) and (B). 75 parts by weight of the thermosetting resin composition according to any one of [1] to [4],

[6] The thermosetting resin composition according to any one of [1] to [5], wherein the component (C) is an aromatic hydrocarbon,

[7] The thermosetting composition according to any one of [1] to [6], wherein the weight ratio of the component (A) to the component (B) is (A) / (B) = 20/80 to 60/40. Resin composition,

[8] The thermosetting adhesive according to any one of [1] to [7], wherein the total weight of the components (A) and (B) is 100 to 150 parts by weight based on 100 parts by weight of the component (C). Resin composition,

[9] A thermosetting film obtained by forming the thermosetting resin composition according to any one of [1] to [8] into a film, and removing a solvent in the composition. 10] The thermosetting film according to [9], wherein the molding is performed by applying the thermosetting resin composition onto a support substrate surface.

[11] A thermosetting film comprising applying the thermosetting resin composition according to any one of [1] to [8] by roll coating, and removing a solvent in the composition. Production method,

[1 2] A laminated body in which a layer obtained by thermosetting the thermosetting film according to [9] or [10] and an adherend layer are adhered and laminated, and

[13] The surface of the thermosetting film according to [9] or [10], which is formed by laminating one surface on the support substrate surface, and the surface opposite to the lamination surface with the support substrate is used as the adherend layer. Provided is a method for producing a laminate, comprising peeling a supporting substrate after laminating, and thermally curing the thermosetting film. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

Component (A) used in the present invention, _(ai) _{ethylene, (a 2) a,]} 3- unsaturated cull Bonn acid and / Matawahi monounsaturated carboxylic acid anhydrides,及Pi (a ₃₎ Bieruesute Ethylene. _Α , β-unsaturated carboxylic acid copolymers obtained by polymerizing R-Z or β-unsaturated ruponic acid esters.

As the _α , β-unsaturated carboxylic acid of the component (a ₂ ), for example, Monocarponic acids such as lylic acid, crotonic acid, monoalkyl fumarate, and monoalkyl malate; maleic acid, fumaric acid, itaconic acid, citraconic acid, 3,6-endo methylene 1,2,3,6-tetrahidonic acid And dicarboxylic acids such as drosis-phthalic acid. Further, the monounsaturated carboxylic acid anhydride of the component (a ₂ ) is an intramolecular or intermolecular anhydride of an α, β monounsaturated carboxylic acid.

As the component (ii), acrylic acid, methacrylic acid, and maleic anhydride are particularly preferable.

In (Alpha) component, structural units derived from the monomer (¾) (hereinafter, (a ₂₎ referred to as monomer units.) The content of, per 1 0 0 parts by weight of component (A) Usually, it is about 0.1 to 20 parts by weight, preferably about 0.1 to 15 parts by weight. It is preferable that the content of () the monomer unit be 0.01 part by weight or more, since the mechanical strength of the obtained adhesive tends to be improved. A) It is preferable because it tends to have excellent storage stability as a component.

[0 0 0 1]

As the unsaturated carboxylic acid ester in the monomer (a ₃ ), usually, an α,] 3-unsaturated carboxylic acid alkyl ester having about 3 to 8 carbon atoms is used. Specifically, for example, acrylic acid Acrylic esters such as methyl, ethyl acrylate, η-propyl acrylate, isopropyl acrylate, η-butyl acrylate, t-butyl acrylate, and isobutyl acrylate; methyl methacrylate, ethyl methacrylate, and n-methacrylate Methacrylates such as —propyl, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and isobutyl methacrylate;

As the biel ester in the monomer (a ₃ ), usually, a vinyl ester of sulfonic acid having about 1 to 20 carbon atoms is used. Specifically, vinyl acetate, butyl butyrate, butyl propionate, piperic acid Examples include burs, vinyl laurate, burs isononanoate, and bielsnosatic acid.

As the monomer (a ₃ ), among them, biel acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate are preferred. The content of the structural unit derived from the monomer (a ₃ ) in the component (A) (hereinafter referred to as () monomer unit) in the component (A) is usually based on 100 parts by weight of the component (A). , 25 to 70 parts by weight, preferably about 25 to 65 parts by weight. When the amount of the monomer unit is at least 25 parts by weight, the solubility of the component (C) is excellent when the component (C) is an organic solvent, and when the amount is at most 70 parts by weight, a high pressure radical method or the like is used. (A) It is preferable because the component tends to be easily produced.

The component (A) may be any of a block copolymer, a graft copolymer, a random copolymer, and an alternating copolymer. The component (B) in the present invention comprises () ethylene and (b ₂ ) the following general formula (1)

Is an epoxy group-containing ethylene copolymer obtained by polymerizing a monomer represented by the formula:

Specific examples of the component (b ₂ ) include unsaturated glycidyl ethers such as aryl glycidyl ether, 2-methylaryl glycidyl ether and styrene-p-glycidyl ether; glycidyl phthalate, glycidyl methacrylate, and glycidyl ester itaconic acid. And unsaturated glycidyl esters.

The content of the structural unit derived from the monomer (b ₂ ) in the component (B) (hereinafter referred to as “(b ₂ ) monomer unit”) is usually based on 100 parts by weight of the component (B). , 1 to 30 parts by weight. (B ₂ ) When the amount of the monomer unit is 1 part by weight or more, the mechanical strength of the obtained adhesive tends to be improved, and when the amount is 30 parts by weight or less, storage as the component (B) is preferred. It is preferable because it tends to have excellent stability.

The component (B) is obtained by adding a monomer (bj) and a monomer (b ₂ ) to a monomer (b ₃ ) which is not reactive with an epoxy group and which can be copolymerized with ethylene, if necessary. Or a copolymer obtained by polymerizing these.

As the monomer (b ₃ ), for example, the monomer () can be used. _Α -olefins containing about 3 to 20 carbon atoms, including propylene, and vinyl compounds such as vinyl chloride, styrene, acrylonitrile, methacrylotrile, acrylamide, and methacrylamide. Of these, propylene, biel acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, and methyl methacrylate are preferred.

The content of the structural unit derived from the monomer (b ₃ ) in the component (B) (hereinafter, referred to as (b ₃ ) monomer unit) is as follows, based on 100 parts by weight of the component (B). Usually, it is about 0 to 70 parts by weight, preferably about 25 to 60 parts by weight. (B ₃₎ Then containing monomer units, (B) component is an organic solvent (C) good since it tends to dissolve the ingredients preferred, is not more than 70 parts by weight, the high-pressure radical method, (B) It is preferable because the component tends to be easily produced.

The component (B) in the present invention may be any of a block copolymer, a graft copolymer, a random copolymer, and an alternating copolymer. For example, propylene-ethylene described in Japanese Patent No. 2632980. the block copolymer (b ₂₎ a copolymer component grafted, Japanese Patent No. 2600248 JP ethylene one epoxy group-containing monomer copolymer Nihi, obtained by grafting the β monounsaturated carboxylic acid ester Copolymers and the like.

In the thermosetting resin composition of the present invention, the monomer) and the monomer () are ethylene, and the content of the structural unit derived from ethylene is 100% in total of the components (A) and (B). The total amount of the components (A) and (B) is preferably about 30 to 75 parts by weight with respect to parts by weight.

The weight ratio of the component (A) and the component (B) in the thermosetting resin composition is usually (A) / (B) = 20Z80 to 60/40.

The method for producing the component (A) or (B) in the present invention includes, for example, a predetermined amount of a monomer (monomer (a ₂ ) and monomer (a ₂ ); b ₂ ); a monomer (b ₂ ) and a monomer (b ₃ ) etc., in the presence of a predetermined amount of ethylene and a radical generator, at about 500 to 4000 atm, about 100 to 300 ° C. Of copolymerization in the presence or absence of a suitable solvent or chain transfer agent; Monomer (a J, monomer (a ₂ ) and monomer (a ₂ ); monomer (b and monomer (b ₂ ); monomer (bj, monomer (b ₂ ) and A method of mixing a monomer (b ₃ ) or the like with a radical generator and subjecting it to melt graft copolymerization in an extruder.

For example, a method for producing a copolymer of ethylene and an epoxy group-containing monomer described in Japanese Patent Publication No. 58-55964, propylene-ethylene described in Japanese Patent No. A method for producing a copolymer in which the component (b ₂ ) is grafted onto a block copolymer, and α, β- is added to the ethylene-epoxy group-containing monomer copolymer described in Japanese Patent No. 260002/48. Examples of the method include a method for producing a copolymer in which an unsaturated carboxylic acid ester is darafted.

In addition, the component (II) and the component (II) are commercially available, and such commercially available products can be used in the present invention. Commercially available (Α) components include, for example, “Bondane (registered trademark)” series (manufactured by Sumika AtoFina), “Seporjon Μ” series (manufactured by Sumitomo Seika Co., Ltd.), and “Let's Pearl Τ Τ” series. (Manufactured by Nippon Polyolefin (橾)), the PRIMA CO RJ series (manufactured by Dow Chemical 1), and the like, and the commercially available (B) component is “Pond First (registered trademark)” series. (Manufactured by Sumitomo Chemical Co., Ltd.), the "Seporjon G" series (manufactured by Sumitomo Seika Co., Ltd.), and the "Let's Pearl RA" series (manufactured by Nippon Polyolefin Co., Ltd.).

The molecular weight of each of the component (A) and the component (B) in the present invention is usually such that the thermosetting resin composition of the present invention can be uniformly dissolved and has a viscosity that allows coating. Molecular weight.

Examples of the organic solvent that can be used as the component (C) include aromatic hydrocarbons such as toluene, esters such as ethyl acetate and butyl acetate, and ketones such as acetone, methyl ethyl ethyl ketone, and methyl isobutynole ketone. Alcohols such as methanol, methanol, butanol, polyethylene glycol, partially saponified polybutyl alcohol, fully saponified polyvinyl alcohol, chlorinated hydrocarbons such as methylene chloride, hexane, heptane, petroleum ether, etc. And aliphatic hydrocarbons. The component (C) may be a mixture of two or more of water and an organic solvent, or a mixture of two or more of an organic solvent.

When the component (C) is an organic solvent, an aromatic hydrocarbon is preferably used.

When water is used as the component (C), the thermosetting resin composition of the present invention is used to disperse the components (A) and (B) and to improve the storage stability of the thermosetting resin composition. It preferably contains an emulsifying and dispersing agent such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol, and polyethylene glycol. Components containing the modified dispersant in the component (A) or the component (B) are commercially available, and such commercially available products, for example, “Seporjon M” series, “Seporjon G” series (Sumitomo) (Manufactured by Seika Co., Ltd.) can also be used. The thermosetting resin composition of the present invention is a liquid composition containing the components (A), (B) and (C). Examples of the production method include a method in which the components (A) and (B) are dissolved or dispersed in the component (C), and then mixed, and the components (A) and (B) are collectively converted into the component (C). A method of dissolving or dispersing, an aqueous emulsion of component (A), a method of separately preparing an aqueous emulsion of component (B), and mixing, a method of dissolving or dispersing in the emulsion of component (A) and the component (C). Examples thereof include a method of mixing the component (B) and a method of mixing the emulsion (B) and the component (A) dissolved or dispersed in the component (C).

The thermosetting resin composition of the present invention includes inorganic fillers, pigments, antioxidants, processing stabilizers, weathering agents, heat stabilizers, light stabilizers, nucleating agents, lubricants, as long as the effects of the present invention are not impaired. It may contain additives such as a release agent, a flame retardant, and an antistatic agent.

The total weight of the components (A) and (B) in the thermosetting resin composition of the present invention is usually 10 to 150 parts by weight based on 100 parts by weight of the component (C). When the total of the components (A) and (B) is at least 10 parts by weight, the coatability of the thermosetting resin composition of the present invention on the support substrate tends to be excellent, and the components (A) and (B) When the total amount of the components is 150 parts by weight or less, the viscosity of the composition comprising the components (A), (B) and (C) decreases, and the coating properties of the composition on the supporting substrate tend to be excellent. Because it is Good. After the thermosetting resin composition of the present invention is formed into a film, the solvent in the composition is removed to obtain the thermosetting film of the present invention.

The molding can be usually performed by coating the thermosetting resin composition of the present invention on the surface of the supporting substrate. The removal of the solvent from the thermosetting resin composition of the present invention formed into a film is a so-called drying treatment, which can be specifically performed by a standing treatment at normal temperature, a heating treatment, a blowing treatment, or the like. . Further, the formation into a film and the removal of the solvent may be performed continuously. Here, the removal of the solvent means that the solvent (component (C)) contained in the thermosetting resin composition of the present invention is substantially completely removed.

The support substrate in the present invention is a film-like substrate through which the thermosetting resin composition of the present invention does not penetrate, and examples thereof include a polyolefin-based film, release paper, and release polyethylene terephthalate (PET) film. No.

Examples of the method of applying the thermosetting resin composition to the supporting substrate include, for example, a rohner coating using a rohno recorder such as a reverse throw coater, a gravure coater, a microknow coater, a kiss coater, a Meyer coater, and an air knife coater. Examples of the method include coating by blade coating using a blade coater or the like. Examples of the solvent removing method include a method of drying by leaving the coating as it is, and a method of drying in a heated blast oven. Among them, it is preferable to produce a thermosetting film by roll coating using a roll coater because the thickness of the film from a thin film to a thick film can be easily controlled.

The thickness of the thermosetting film is not particularly limited. Usually, when the thickness is about 3 μηι or more, the adhesiveness tends to be excellent, preferably about 3 to 100 μm, and particularly preferably about 3 to 100 μm. It is about 50 μπι.

The coating thickness of the thermosetting resin composition of the present invention, and the thickness of the thermosetting film of the present invention from the weight ratio of the total of (（) and (Β) components in the thermosetting resin composition of the present invention. Approximate value (For example, when the coating thickness is 50 μππι and the weight ratio is 50%, the thickness of the heat-cured green film is expected to be 25 μm), and the estimated value and the actual The desired thickness of the thermosetting film can be obtained by appropriately adjusting the coating thickness of the thermosetting resin composition based on the thickness of the obtained thermosetting film. The laminate in the present invention is a laminate in which a layer obtained by thermosetting the thermosetting film of the present invention and an adherend layer are laminated in close contact with each other. It can be obtained by laminating with a body layer and then thermosetting.

The adherend in the present invention is a material that can be bonded to the thermosetting film of the present invention by thermosetting, unlike the above-mentioned support substrate, and the adherend layer is the adherend. It is layered. Specific examples of the adherend include cellulosic polymer materials, metals such as gold, silver, copper, iron, tin, and lead; inorganic substances such as ceramics; and polar resins. The polar resin is a resin containing a polar group in the resin, and specifically, a melamine resin, an acrylic resin, a urethane resin, a urethane resin, a (meth) acrylic resin, Styrene acrylonitrile-based copolymer, polycarbonate-based resin, phenol resin, alkyd resin, epoxy resin and the like may be mentioned, and these may be a mixed material of two or more kinds or a composite material.

As a method for producing a laminate, for example, after the thermosetting film of the present invention is peeled from the supporting substrate, the laminate is laminated with the adherend layer, usually heated at about 80 to 150 ° C., and pressed. A method in which a layer formed by thermosetting the thermosetting film is brought into close contact with the adherend layer by applying a pressure of, for example, about 1 to 6 MPa with a machine; one side of the thermosetting film of the present invention is used as a supporting substrate. A method in which the surface opposite to the support substrate is laminated with the adherend layer in the state of being laminated, and the support substrate is peeled off after heating and pressing in the same manner; one side of the thermosetting film of the present invention A method in which the surface opposite to the supporting substrate is laminated with the adherend layer in a state in which the supporting substrate is laminated, and the supporting substrate is peeled off, followed by heating and pressing similarly; Laminated with the adherend layer with one side of the thermosetting film laminated with the supporting substrate After the base material is peeled off, another adherend layer is laminated on the surface from which the supporting base material has been peeled off, followed by heating and pressing in the same manner. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

The following (A) and (B) components were used. The MFR (melt flow rate) is a value measured under the conditions of 190 ° C and a load of 2160 g according to JIS-K7210.

(A) Ingredient

A-1: (Yes) Bondaine AX8390J, manufactured by Sumika Atofina

Ethylene-ethyl acrylate-maleic anhydride copolymer,

Ethyl acrylate unit content 30% by weight,

Maleic anhydride unit content 2% by weight, MFR = 7 gZl 0 min A-2: "Seporjon M220 E" manufactured by Sumitomo Seika Co., Ltd.

An aqueous emulsion containing an ethylene-ethyl acrylate-maleic anhydride copolymer, a solid content of 40% by weight,

'Total content of ethyl acrylate and maleic anhydride units in the copolymer is 20% by weight,

(B) Ingredient

B-1: "Bond First 7M" manufactured by Sumitomo Chemical Co., Ltd.

Ethylene-methyl acrylate-glycidyl methacrylate copolymer, glycidyl methacrylate unit content 6 weight ⁰

Atariru methyl unit content 30 wt ^{_{0/0, MFR = 9 g}} / l O min B- 2: rectification I arsenide Ltd. Sumitomo "Seporujon G 1 18J,

Contains ethylene-daldicidyl methacrylate copolymer

Water-based emulsion, solid content 40% by weight,

Daricidyl methacrylate unit content in copolymer 16% by weight

(1) Preparation of (A) component-containing solution

<(A-1) Preparation of solution>

(A-1) Transfer 20 parts by weight of the components and 80 parts by weight of toluene into a flask, Stir and dissolve for 1 hour while keeping the temperature at 20kg. A toluene solution containing the (A-1) component (/ ₀ ) was obtained.

(2) Preparation of (B) component-containing solution

Preparation of solution (B-1)>

20 parts by weight of the component (B) and 80 parts by weight of toluene are placed in a flask, and dissolved by stirring for 1 hour while keeping the temperature at 80 ° C. A toluene solution containing 20% by weight of the component (B) (B-1) I got

(Examples 1 to 4)

(3) Production example 1 of thermosetting resin composition

The solution of (A-1) and (B-1) obtained by the above (1) and (2) is stirred and mixed at room temperature for 10 minutes at the mixing ratio (parts by weight) shown in Table 1. As a result, a thermosetting resin composition was obtained. Table 1 also shows the weight ratio (%) of each of the components (A) to (C) in the obtained composition.

(Examples 5 to 8)

(4) Production example 2 of thermosetting resin composition

The aqueous emulsion solution of (A-2) and (B-2) was stirred and mixed at room temperature for 10 minutes at the mixing ratio (parts by weight) shown in Table 2 to obtain a thermosetting resin. A composition was obtained. Table 2 also shows the weight ratio (%) of each of the components (A) to (C) in the obtained composition.

(5) Production example of thermosetting film (before bonding)

(I): The thermosetting resin composition obtained by the above (3) and (4) was released from a PET film (“FF-50” manufactured by Unitika Ltd.) using a bar coater. 4 ^ m 8 μπι and 20 μm laminated on the release PET film surface by coating on the release surface of PET film and film thickness and drying for 3 minutes at 80 ° C open A thermosetting film having a thickness of m was subjected to a heat test using a solder.

(6) Example of thermosetting film (before bonding) (II) The thermosetting resin composition obtained by the above (3) and (4) was applied to a polyethylene terephthalate (PET) film (DI AFO IL T600E50 W07, manufactured by Mitsubishi Chemical Corporation) using a Meyer bar coater, 50 m) and dried in an oven at 80 ° C. for 3 minutes to obtain a thermosetting film laminated on the PET film. By adjusting the amount of the thermosetting resin composition used, three types of thermosetting films having a thickness of 4 μπι, 8 and 20 tm were obtained. The thermosetting film having a thickness of 20 μm was subjected to a peel test.

(7) Laminate production example and solder heat resistance test

The thermosetting film side of the two-layer film consisting of the release PET film Z thermosetting film obtained in (5) above was placed on the printed wiring board (Single-sided copper-clad laminate R made by Matsushita Electric Works, Ltd.) -Laminated on the wiring pattern side of 1705 (FR4 printed wiring board)), using a laminator (“Fast Laminator VA-700J” manufactured by Taisei Laminator Co., Ltd.), upper and lower roll temperature 110 ° C, line pressure 14.5 k gZcm, thermocompression bonding at a speed of 0.5 m / min, followed by thermocompression at 100 ° C, 3MPa for 10 minutes using a hot press, and 180 ° C, 3MPa using a hot press. After heat curing for 60 minutes under the condition of a, the release PET film on the surface of the laminate was peeled off to obtain a laminate in which the printed wiring board and the thermosetting film obtained by thermosetting were in close contact with each other. .

The obtained laminate was subjected to 260 using SOLDERAB ILITY TES TER E ST-11 made by Tabai Espec. C was immersed in a solder bath for 10 seconds. After repeating this immersion six times, the surface appearance was visually observed. The results are shown in Tables 1 and 2. The determination of the solder heat test was based on the following criteria.

〇: There is no abnormality (peeling, swelling) in the thermosetting film appearance,

No solder

X: The thermosetting film has abnormal appearance (peeling, swelling),

Or those with solder holes

(8) Laminate production example and peel test

The thermosetting film side of the two-layer film (8 OmmX 10 Omm) made of the PET film thermosetting film obtained in (6) above was used as the adherend with resin-coated copper. Laminate the foil and use a heat seal tester (“Heat Seal Tester TP-701-B”, manufactured by Tester Sangyo Co., Ltd.) with a part (25 mm x 80 mm) from the upper and lower bars at 180 ° C and 0. The two-layer film was laminated and adhered to the adherend (copper foil with resin) in a width of 25 mm by heat sealing at a pressure of (gauge pressure) for 60 minutes. After the obtained laminate was prepared for 1 hour under the conditions of a temperature of 23 ° C and a relative humidity of 50%, a 10 mm wide x 10 Omm length (adhesive length 25 mm) test piece was cut from the laminate. At a temperature of 23 ° C and a relative humidity of 50%, the peeling speed was 100 mm / sec and the peeling angle was 180. A peel test was performed.

The same test was performed using slide glass ("Microslide Glass S9213", surface polished surface, manufactured by MATSUNAMI Co., Ltd.) as the adherend instead of resin-coated copper foil.

When a peeling test was performed on the thermosetting resin composition composed of (A-2) and (B-2), peeling occurred at the interface between the thermosetting film and the PET film as the supporting substrate, Since the peel strength between the adherend Z thermosetting resin layers cannot be obtained, the peel strength between the adherend Z thermosetting films is at least 12.3 N / 10 mm or more obtained in Example 2. It shows very good adhesion. Example

1 2 3 4 Mixed A—1 (parts by weight) 20 30 40 50 Ratio B-1 (parts by weight) 80 70 60 50 Thermosetting (A) component (% by weight) 4 6 8 10 Resin (B) component (weight) %) 16 14 12 10 Composition (C) Ingredient (Toruyun, wt%) 80 80 80 80 Peeling Copper foil with resin (N / lOmm) 3.9 6.5 4.0 4.8

Glass (NZlOmm) 9.1 12.3 11.0 11.4 Solder heat test 〇〇〇〇 Table 2

(8) Comparative example (mixing of A-1 / B_1 by melt-kneading)

After dry blending 50 parts by weight of A-1 copolymer 50 parts by weight of B_1 copolymer, a small patch-type eder ("Laboplast Mill R-10" manufactured by Toyo Seiki Seisaku-sho, Ltd.) 0)) to set the barrel temperature to 100. Under the conditions of C, the mixture was preliminarily kneaded at 10 rpm for 7 minutes, and then kneaded at 50 rpm for 5 minutes. Immediately after the start of the main kneading, a significant increase in the temperature of the tree due to shearing heat was observed, and an increase in the kneading torque due to the progress of the curing reaction was confirmed. The obtained A-1 / B-1 resin yarn composition was already a cured product and could not be filled in an extruder to form a thin film. Industrial applicability

The thermosetting resin composition of the present invention is excellent in coatability, operability, and fluidity on a supporting substrate, and is adhered in a thin film by coating the composition and removing the component (C). A thermosetting film having excellent properties can be easily obtained. Further, when an adherend is laminated on the thermosetting film and thermally cured, the film layer in the obtained laminate has excellent heat resistance and low elastic modulus.

Since the laminate has such excellent characteristics, for example, a semiconductor encapsulating material, an encapsulating material for electronic components such as solar cells and EL (electroluminescence) lamps, and a die between an integrated circuit and a substrate. Interlayer insulating layer between bonder sheet and board, printed wiring It can be used as a solder resist for boards and paints for baking automotive parts.

Claims

The scope of the claims

1. A thermosetting resin composition containing the following components (A), (B) and (C).

(A): (a diethylene,

(a ₂ ) a,] 3-unsaturated carboxylic acid and / or monounsaturated carboxylic anhydride and

(a ₃ ) Vinyl ester and / or j, 3-unsaturated carponic acid ester

Ethylene mono-unsaturated carboxylic acid copolymer obtained by polymerizing

(B): (b _t ) ethylene and

(b ₂ ) The following general formula (1)

Monomer represented by

Epoxy group-containing ethylene copolymer obtained by polymerizing

(C): an organic solvent and water or water.

2. The content of the structural unit derived from the monomer (¾) is 0.01 to 20 parts by weight based on 100 parts by weight of the component (A), and the structural unit derived from the monomer (¾) is contained. The thermosetting resin composition according to claim 1, wherein the content of is from 25 to 70 parts by weight.

3. (B) of the component 1 00 parts by weight, thermal curing according to the first or second term claims the content of the structural unit is from 1 to 30 parts by weight derived from a monomer (b ₂₎ Resin composition

4. (B) component, in addition to the monomer (bj and monomer (b _2), further (b ₃₎ not to react with E epoxy group, ethylene monomers copolymerizable with The thermosetting resin composition according to any one of claims 1 to 3, which is a copolymer obtained by polymerizing a thermosetting resin.

5. The sum of the content of the structural unit derived from the monomer () and the content of the structural unit derived from the monomer () is 100 parts by weight of the total of the polymers of the components (A) and (B). The thermosetting resin composition according to any one of claims 1 to 4, which is 30 to 75 parts by weight.

6. The thermosetting resin composition according to any one of claims 1 to 5, wherein the component (C) is an aromatic hydrocarbon.

7. The method according to any one of claims 1 to 6, wherein the weight ratio between the component (A) and the component (B) is (A) / (B) = 20 to 80/40/40. The thermosetting resin composition according to the above.

8. The thermosetting composition according to any one of claims 1 to 7, wherein the total weight of the components (A) and (B) is 100 to 150 parts by weight based on 100 parts by weight of the component (C). Resin composition.

9. A thermosetting film obtained by forming the thermosetting resin composition according to any one of claims 1 to 8 into a film, and removing a solvent in the composition.

10. The thermosetting film according to claim 9, wherein molding is performed by applying the thermosetting resin composition onto a supporting base material surface.

11. A thermosetting film comprising applying the thermosetting resin composition according to any one of claims 1 to 8 by roll coating, and then removing a solvent in the composition. Manufacturing method.

12. A laminate comprising a layer obtained by thermosetting the thermosetting film according to claim 9 or 10 and an adherend layer laminated in close contact with each other.

13. The surface of the thermosetting film according to claim 9 or 10, wherein one surface is laminated on the supporting substrate surface, the surface opposite to the laminating surface with the supporting substrate is used as the adherend layer. A method for producing a laminate, comprising: after laminating, peeling off a supporting substrate and thermally curing the thermosetting film.