JP2003020379A - Insulation resin composition for electronic part, and adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material which is excellent in adherence to a constituent base material for electronic parts, causes little deformation of an adhesive layer in thermal adhesion, is flexible before and after curing, and is excellent in handleability during processing. SOLUTION: This insulating resin composition for electronic parts is characterized in that it contains an epoxy resin (a), a curing agent (b) and a core-shell crosslinked rubber (c) having a mean particle diameter of 1 μm or smaller, wherein the content of the core-shell crosslinked rubber (c) is 60-95 wt.% based on the total resin content.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an insulating resin composition used for assembling electronic parts.

[0002]

2. Description of the Related Art As an insulating resin composition for electronic parts, an epoxy resin composition comprising an epoxy resin and a curing agent has been conventionally used.

[0003]

With the recent miniaturization and weight reduction of electronic parts such as chip resistors, chip capacitors, and chip inductors, they have excellent adhesiveness to the base material that constitutes the electronic parts, and they adhere at the time of heat bonding. There is a demand for a material that is small in shape deformation of the layer, has flexibility before and after curing, and is excellent in handling during the process.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that an insulating resin composition for electronic parts which simultaneously satisfies the above-mentioned properties can be obtained, and the present invention completed. That is, the present invention contains (1) an epoxy resin (a), a curing agent (b), and a core-shell structure crosslinked rubber (c) having an average particle size of 1 μm or less,
The content of the core-shell structure crosslinked rubber (c) is 60% by weight or more and 95% by weight or less based on the total amount of the resin, and the insulating resin composition for electronic parts, (2) the core-shell structure crosslinked rubber (c) The core layer is a crosslinked polybutadiene, and the shell layer is an alkyl acrylate-alkyl methacrylate copolymer (1), the insulating resin composition for electronic parts, (3) the core of the core-shell structure crosslinked rubber (c) The layer is crosslinked polybutadiene and the shell layer is an alkyl methacrylate-styrene copolymer. (1) Insulating resin composition for electronic parts, (4) Core shell structure Crosslinked rubber (c) Core layer is crosslinked acrylic The insulating resin composition for electronic parts according to claim 1, wherein the insulating layer is an acid alkyl copolymer and the shell layer is an alkyl acrylate copolymer.
A sheet of the insulating resin composition for electronic parts according to any one of (1) to (4), (6) the sheet has a thickness of 5 μm or more and 50 μm or less, and is heated at 150 ° C. and 1 MPa,
A sheet of the insulating resin composition for electronic parts according to (5), wherein the amount of resin deformation of the side portion when pressed is 100 μm or less.
(7) A cured product of the insulating resin composition for electronic parts or the sheet according to any one of (1) to (6).

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The insulating resin composition for electronic parts of the present invention contains an epoxy resin (a), a curing agent (b), and a core-shell structured crosslinked rubber (c) having an average particle diameter of 1 μm or less.

Epoxy resin (a) used in the present invention
May be any compound as long as it has two or more epoxy groups in the molecule, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, phenol. Examples include novolac type epoxy resin, cresol novolac type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, epoxy resin obtained by glycidylating halogenated phenols, epoxidized polybutadiene, and particularly bisphenol A type epoxy resin, Bisphenol F type epoxy resin,
Phenol novolac type epoxy resin and cresol novolac type epoxy resin are preferable, and two or more of them can be used in combination.

Examples of the curing agent (b) used in the present invention include phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol trimellitic acid anhydride, Aromatic carboxylic acid anhydrides such as biphenyl tetracarboxylic acid anhydrides, Aliphatic carboxylic acid anhydrides such as azelaic acid, sebacic acid, dodecanedioic acid, tetrahydrophthalic acid anhydride, hexahydrophthalic acid anhydride, nadic acid anhydride Compounds, alicyclic carboxylic acid anhydrides such as het acid anhydride, hymic acid anhydride, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 1,5- Diaminonaphthalene, m-xylylene diene Aromatic amines such as down, ethylenediamine, diethylenediamine, isophoronediamine, bis (4-amino-3-methyl dicyclohexyl) methane, aliphatic amines such as polyether diamines,
Dicyandiamide, guanidines such as 1- (o-tolyl) biguanide, amine adduct of epoxy resin, bisphenol A, bisphenol F, bisphenol S,
4,4'-biphenylphenol, tetramethylbisphenol A, dimethylbisphenol A, tetramethylbisphenol F, dimethylbisphenol F, tetramethylbisphenol S, dimethylbisphenol S,
Tetramethyl-4,4'-biphenol, dimethyl-
4,4′-biphenylphenol, 1- (4-hydroxyphenyl) -2- [4- (1,1-bis- (4-hydroxyphenyl) ethyl) phenyl] propane, 2,
2'-methylene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidene-bis (3-
Methyl-6-tert-butylphenol), trishydroxyphenylmethane, resorcinol, hydroquinone, pyrogallol, phenols having a diisopropylidene skeleton, phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene, phenol Novolak resins made from various phenols such as modified polybutadiene, phenol, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, bisphenol F, bisphenol S, and naphthols, xylylene skeleton-containing phenol novolac resins, dicyclopentadiene Skeleton-containing phenol novola / methylimidazole isocyanuric acid 2: 3 adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl Sulfonyl-3,5-dihydroxy methyl imidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2
Various imidazoles such as phenyl-3,5-dicyanoethoxymethylimidazole, and imidazoles and polyhydric acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid and oxalic acid. Examples thereof include salts with carboxylic acids, dihydrazides, Lewis acids, Bronsted acid salts, polymercaptons, isocyanates and blocked isocyanates.

[0008] Among these curing agents, which curing agent is used is appropriately selected depending on the properties required for the adhesive, but is preferably amine adduct of epoxy resin or dihydrazide.

The amount of these curing agents (b) used is usually 0.3 to 2.0, preferably 0.4 to 1.6, more preferably the equivalent ratio of the curing agent to the epoxy groups of the epoxy resin (a). It is used in the range of 0.5 to 1.3. Two or more kinds of the above curing agents can be mixed and used. Also,
You may mix | blend a hardening accelerator as needed. Any curing accelerator may be used as long as it accelerates the curing of the epoxy resin, and examples thereof include imidazoles, organic phosphorus compounds, tertiary amines and quaternary ammonium salts.

The crosslinked rubber (c) having a core-shell structure used in the present invention has a two-layer or three-layer structure, the core layer is a crosslinked rubber having rubber elasticity, and the core layer is coated with a crosslinked polymer having no rubber elasticity. Any structure may be used as long as it has the above structure. Examples of the core layer include cross-linked polybutadiene, cross-linked alkyl acrylate copolymer, cross-linked polyisoprene, and the like, and the shell layer includes alkyl acrylate-alkyl methacrylate copolymer, alkyl methacrylate-styrene copolymer, alkyl acrylate. Examples thereof include copolymers. Among these, a preferred combination of the core layer and the shell layer is a combination in which the core layer is a crosslinked polybutadiene and the shell layer is an alkyl acrylate-alkyl methacrylate copolymer or an alkyl methacrylate-styrene copolymer, the core layer Is a crosslinked alkyl acrylate copolymer and the shell layer is an alkyl acrylate copolymer. The average particle diameter of the core-shell structure crosslinked rubber is preferably 1 μm or less. If the average particle size is larger than 1 μm, the shape deformation of the adhesive layer tends to increase during heat bonding. Further, if the particle size is too small, the particles are likely to aggregate, so that the average particle size is preferably 0.1 μm or more.

The addition amount of the core-shell structured crosslinked rubber in the insulating resin composition for electronic parts of the present invention is 60% by weight or more and 95% by weight or less, preferably 80% by weight, based on the total amount of the resin content in the insulating resin composition. % To 90% by weight.
When the amount is less than 60% by weight, the shape of the adhesive layer is changed during heat bonding, and when the amount is more than 95% by weight, the adhesion reliability is deteriorated.

The insulating resin composition for electronic parts of the present invention comprises:
Other additives can be added as needed. For example, plasticizers such as natural waxes, synthetic waxes and metal salts of long chain aliphatic acids, release agents such as acid amides, esters and paraffins, stress relaxation agents such as nitrile rubber and butadiene rubber, trioxide. Inorganic flame retardants such as antimony, antimony pentoxide, tin oxide, tin hydroxide, molybdenum oxide, zinc borate, barium metaborate, red phosphorus, aluminum hydroxide, magnesium hydroxide, calcium aluminate, tetrabromobisphenol A, tetrabromoanhydrous Brominated flame retardants such as phthalic acid, hexabromobenzene, brominated phenol novolac, silane coupling agents, titanate coupling agents, aluminum coupling agents, and other coupling agents, fused silica, crystalline silica, low α Wire silica, glass flakes, glass beads, glass balloons, talc Alumina, calcium silicate, aluminum hydroxide, calcium carbonate, barium sulfate, magnesia, silicon nitride, boron nitride, ferrite, rare earth cobalt, gold, silver, nickel, copper, lead, iron powder, iron oxide, iron sand, etc. Inorganic fillers such as powder, graphite, carbon, rouge, yellow lead or conductive particles, colorants such as dyes and pigments, carbon fibers, glass fibers, boron fibers, silicon carbide fibers, alumina fibers, silica-alumina fibers Inorganic fibers such as, aramid fibers, polyester fibers, cellulose fibers, organic fibers such as carbon fibers, oxidation stabilizers, light stabilizers, moisture resistance improvers, thixotropic agents, diluents, defoamers, and various other types. The resin, tackifier, antistatic agent, lubricant, ultraviolet absorber and the like can also be added.

Since the insulating resin composition for electronic parts of the present invention uniformly mixes each component, it is preferable to use a varnish by adding a solvent. Any solvent may be used as long as it dissolves the epoxy resin, but in particular, methyl ethyl ketone, toluene, xylene, ethyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, cyclohexanone, propylene glycol diacetate, Ethylene glycol monomethyl ether and the like are preferable because they have excellent solubility in the epoxy resin. The blending amount of these solvents is not particularly limited as long as the resin dissolves and the core-shell structured crosslinked rubber can be mixed, but is 30 to 30 parts by weight based on 100 parts by weight of the total amount of the epoxy resin, the curing agent and the core-shell structured crosslinked rubber. 200 parts by weight is preferred. In order to uniformly disperse the crosslinked rubber having a core-shell structure, it is effective to use a ladle machine, a homogenizer, a triple roll, or the like.

The sheet of the insulating resin composition for electronic parts according to the present invention has a sheet thickness of 5 μm or more and 100 μm or less, and a side resin deformation amount of 100 μm or less when heated and pressed at 150 ° C. and 1 MPa. Are preferred.
The amount of resin deformation in this case means that a sheet punched into a circle with a diameter of 5 mm is sandwiched between two glass plates,
It is the amount of deformation of the diameter when heated and pressed at 0 ° C. and 1 MPa for 1 hour to cure. The sheet of the present invention is formed on a film serving as a support. As a forming method, it is preferable to apply a varnish of the insulating resin composition for electronic parts onto a film and dry the solvent, but it is not limited to this. The sheet thickness after drying depends on the application, but is practically 5
It is preferable that the thickness is 100 μm or more. The film serving as a support needs to have heat resistance to withstand the drying process. Polyethylene terephthalate (PET) film and the like can be mentioned as a material which satisfies this requirement and is inexpensive. In order to improve the releasability of the adhesive sheet, the surface of the support film is preferably subjected to a release treatment.

The insulating resin composition for electronic parts of the present invention may be cured under any conditions, but the temperature is preferably 120 to 250 ° C. If the temperature is lower than 120 ° C, curing of the resin will be insufficient, and if the temperature is higher than 250 ° C, the resin will be thermally decomposed, which is not preferable.

[0016]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. In Examples and Comparative Examples,% and parts are by weight unless otherwise specified. Example 1 RE-310S (liquid bisphenol A epoxy resin,
Nippon Kayaku Co., Ltd., epoxy equivalent 182g / eq) 5
0 parts, YD-012 (solid bisphenol A epoxy resin, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 670 g / e
q) 50 parts, Amicure MY-H (epoxy resin amine adduct, manufactured by Ajinomoto Co., Inc.) 20 parts, Paraloid E
XL-2602 (core shell structure crosslinked rubber, manufactured by Kureha Chemical Industry Co., Ltd., core layer: crosslinked polybutadiene, shell layer: alkyl acrylate-alkyl methacrylate copolymer, average particle diameter 200 nm) 600 parts, propylene glycol diacetate 800 parts Was weighed, pre-mixed with a planetary mixer, and then kneaded with three rolls to obtain a varnish. This varnish was applied to PET film # 3811 (manufactured by Lintec Co., Ltd., release treated product) and the thickness after drying was 2
It was applied so as to have a thickness of 5 μm and dried at 140 ° C. for 3 minutes to obtain a sheet of an insulating resin composition for electronic parts. The obtained sheet had flexibility before and after curing.
The obtained sheet was punched into a circular shape with a diameter of 5 mm, sandwiched between two glass plates, heated at 150 ° C. and 1 MPa for 1 hour, and pressed to cure, so that the deformation amount of the diameter was 50 μm.
It was m. Further, the peeling strength of the adhered glass in the vertical direction was as good as 5 MPa.

Example 2 RE-310S (liquid bisphenol A epoxy resin,
Nippon Kayaku Co., Ltd., epoxy equivalent 182g / eq) 5
0 parts, YD-012 (solid bisphenol A epoxy resin, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 670 g / e
q) 50 parts, Amicure MY-H (epoxy resin amine adduct, manufactured by Ajinomoto Co., Inc.) 20 parts, Paraloid E
XL-2655 (core shell structure crosslinked rubber, manufactured by Kureha Chemical Industry Co., Ltd., core layer: crosslinked polybutadiene, shell layer: alkyl methacrylate-styrene copolymer, average particle diameter 200 nm) 600 parts, propylene glycol diacetate 800 parts are weighed. Then, after premixing with a planetary mixer, it was further kneaded with a three-roll mill to obtain a varnish.
This varnish was applied to PET film # 3811 (manufactured by Lintec Co., Ltd., release treated product) so that the thickness after drying was 25 μm, and dried at 140 ° C. for 3 minutes to obtain a sheet of an insulating resin composition for electronic parts. Obtained. The obtained sheet had flexibility before and after curing. The obtained sheet was punched into a circle having a diameter of 5 mm, sandwiched between two glass plates, and heated at 150 ° C. and 1 MPa for 1 hour to be pressed and cured, and the amount of deformation of the diameter was 50 μm. Further, the peeling strength of the adhered glass in the vertical direction was as good as 5 MPa.

Example 3 RE-310S (Liquid bisphenol A epoxy resin,
Nippon Kayaku Co., Ltd., epoxy equivalent 182g / eq) 5
0 parts, YD-012 (solid bisphenol A epoxy resin, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 670 g / e
q) 50 parts, Amicure VDH (1,3-bis (hydrazinocarboethyl) -5-isopropylhydantoin,
Ajinomoto Co., Ltd.) 20 parts, Zeon F351 (core-shell structure crosslinked rubber, manufactured by Nippon Zeon Co., Ltd., core layer: crosslinked alkyl acrylate copolymer, shell layer: alkyl acrylate copolymer, average particle diameter 300 nm) 600 parts, 800 parts of propylene glycol diacetate was weighed, premixed with a planetary mixer, and then kneaded with three rolls to obtain a varnish. Use this varnish with PET film # 3
811 (manufactured by Lintec Co., Ltd., release treated product) was applied so that the thickness after drying would be 25 μm, and dried at 140 ° C. for 3 minutes to obtain a sheet of an insulating resin composition for electronic parts.
The obtained sheet had flexibility before and after curing. The obtained sheet was punched into a circle with a diameter of 5 mm and sandwiched between two glass plates at 150 ° C and 1MP.
The amount of deformation of the diameter when it was heated and pressurized at a for 1 hour to cure was 70 μm. Further, the peeling strength of the adhered glass in the vertical direction was as good as 4 MPa.

Example 4 RE-310S (liquid bisphenol A epoxy resin,
Nippon Kayaku Co., Ltd., epoxy equivalent 182g / eq) 5
0 parts, YD-012 (solid bisphenol A epoxy resin, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 670 g / e
q) 50 parts, Amicure MY-H (epoxy resin amine adduct, manufactured by Ajinomoto Co., Inc.) 20 parts, SG-200
0 (fine powder of talc, manufactured by Nippon Talc Co., Ltd.) 200 parts,
Paraloid EXL-2655 (core shell structure crosslinked rubber, manufactured by Kureha Chemical Industry Co., Ltd., core layer: crosslinked polybutadiene, shell layer: alkyl methacrylate-styrene copolymer, average particle size 200 nm) 600 parts, propylene glycol diacetate 800 parts After weighing and premixing with a planetary mixer, the mixture was further kneaded with three rolls to obtain a varnish. Use this varnish with PET film # 3811
(Rintec Co., Ltd., release treated product) was applied so that the thickness after drying would be 25 μm, and dried at 140 ° C. for 3 minutes to obtain a sheet of an insulating resin composition for electronic parts. The obtained sheet had flexibility before and after curing. The obtained sheet was punched into a circular shape with a diameter of 5 mm, and sandwiched between two glass plates.
The amount of diameter deformation when heated and pressed for 3 hours to cure is 3
It was 0 μm. Further, the peeling strength of the adhered glass in the vertical direction was as good as 5 MPa.

[0020]

The insulating resin composition for electronic parts of the present invention comprises:
It has excellent adhesiveness to the base material that constitutes the electronic component, the shape deformation of the adhesive layer is small at the time of heat bonding, and it has flexibility before and after curing, which makes it excellent in handling during the process.
Therefore, the sheet of the present invention is extremely useful as an insulating sheet for electronic parts.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) (C08L 51/04 C08L 63:00 A 63:00) F Term (Reference) 4F071 AA12 AA12X AA13 AA13X AA33 AA41 AA42 AA77 AC09 AC11 AC12 AC13 AC19 AD02 AE02 AF39 AH12 BB02 BC01 4J002 BN121 BN141 CC033 CC043 CC053 CC063 CC273 CD022 CD051 CD062 CD102 CD112 CD122 CD132 CD182 CD203 CE003 EJ016 FE160 FD 176 016 010 176 010 216 176 010 010 216 010 006 006 010 010 006 006 010 006 006 FE 610 006 006 FE 610 FE 006 FE 006 FE 006 FE 006 FE 006 FE 006 FE 006 006 FD130 FD140 FD143 FD146 FD160 GQ01 4J040 DL141 EB052 EC062 EC072 EC092 EC122 EC152 EC172 EC262 EF152 HB35 HB47 HC01 HC16 HC24 HD16 JA03 JA09 KA16 LA06 LA09 NA19 5G305 AA07 AB34 AB36 BA09 BA18 CA15 CA47

Claims (7)

[Claims] 1. An epoxy resin (a), a curing agent (b), and a core-shell structure cross-linked rubber (c) having an average particle size of 1 μm or less, wherein the content of the core-shell structure cross-linked rubber (c) is the total resin content. To 60% by weight or more and 95% by weight or less of the insulating resin composition for electronic parts. 2. The insulating resin composition for electronic parts according to claim 1, wherein the core layer of the crosslinked rubber (c) having a core-shell structure is a crosslinked polybutadiene, and the shell layer is an alkyl acrylate-alkyl methacrylate copolymer. 3. The insulating resin composition for electronic parts according to claim 1, wherein the core layer of the crosslinked rubber (c) having a core-shell structure is a crosslinked polybutadiene, and the shell layer is an alkyl methacrylate-styrene copolymer. 4. The insulating resin composition for electronic parts according to claim 1, wherein the core layer of the crosslinked rubber (c) having a core-shell structure is a crosslinked alkyl acrylate copolymer and the shell layer is an alkyl acrylate copolymer. . 5. A sheet of the insulating resin composition for electronic parts according to claim 1. 6. The insulation for electronic parts according to claim 5, wherein the thickness of the sheet is 5 μm or more and 100 μm or less, and the amount of resin deformation of the side portion when heated and pressed at 150 ° C. and 1 MPa is 100 μm or less. A sheet of resin composition. 7. A cured product of the insulating resin composition for electronic parts or a sheet according to claim 1.