JP3465153B2 - Epoxy resin composition for laminated board - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to interlayer adhesion, heat resistance,
TECHNICAL FIELD The present invention relates to an epoxy resin composition for a laminate, which is used for a laminate, an adhesive or the like that requires stress relaxation and tracking resistance.

[0002]

2. Description of the Related Art Conventionally, epoxy resins have been widely used for laminates, adhesives, etc. because of their excellent electrical characteristics. However, they are hard and brittle and hardened by internal stress generated by cooling from high temperature. There is a drawback that the glass cloth is likely to be warped or the adhesiveness is deteriorated, and there is a drawback that delamination between the glass cloths is likely to occur due to an external impact, and improvement thereof is demanded. Acrylonitrile-butadiene rubber is mainly used as an elastomer in order to improve these drawbacks, but it has a drawback that heat resistance is lowered.

[0003]

DISCLOSURE OF THE INVENTION The present inventors have aimed to obtain a copper foil and a laminate excellent in interlayer adhesion, stress relaxation and tracking resistance while maintaining the heat resistance of conventional epoxy resins. As a result of various studies on useful epoxy resins, the above problems were solved by adding 2 to 25 parts by weight of a (meth) acrylic acid ester-based polymer component, which is an elastomer component, to the epoxy resin to obtain a predetermined epoxy equivalent. The present invention has been completed and the present invention has been completed, and an object of the present invention is to provide an epoxy resin composition for obtaining a copper foil and a laminate excellent in interlayer adhesion, stress relaxation, and tracking resistance. And

[0004]

SUMMARY OF THE INVENTION The gist of the present invention is to include a (meth) acrylic acid ester-based polymer.
The epoxy equivalent containing 2 to 25 parts by weight of a (meth) acrylic acid ester-based polymer reacted with a chain extender in the presence of a catalyst in a liquid epoxy resin (B) at a temperature of not higher than 23 is 23.
It is an epoxy resin composition for laminated boards, which contains 0-1200 g / eq of epoxy resin (A) as an essential component. That is, in the present invention, 2 to 25 parts by weight of a (meth) acrylic acid ester-based polymer component is contained and an epoxy equivalent of 230 to 1200 g / eq is used as the epoxy resin (A). Is in the range of 230 to 1200 g / eq, excellent performance in flowability, workability, adhesiveness, heat resistance and stress relaxation can be obtained.

The present invention will be described in detail below. The epoxy resin (A) according to the present invention is obtained by uniformly dispersing the (meth) acrylic acid ester-based polymer component in the epoxy resin (B) which is liquid at 100 ° C. or lower in advance, and then in the presence of a catalyst It is obtained by reacting with a lengthening agent to adjust to a predetermined epoxy equivalent. Thus, the epoxy resin used in the present invention in which the (meth) acrylic acid ester-based polymer component is uniformly contained and dispersed can be manufactured by a known method. For example, a (meth) acrylic acid ester-based polymer produced by various conventional polymerization methods such as an emulsion polymerization method, a suspension polymerization method, and a solution polymerization method and an epoxy resin which is liquid at a predetermined temperature are forced under shear force. After stirring, a method of removing water or a solvent, a method of heating and mixing powdery polymer fine particles in an epoxy resin, a method of copolymerizing an acrylic monomer in an epoxy resin, and the like can be mentioned. A method of adding the obtained water dispersion of the (meth) acrylic acid ester-based polymer to an epoxy resin which is liquid at 100 ° C. or lower, forcibly stirring it under a shearing force and then dehydrating is preferable, and industrially advantageous. .

The epoxy resin (B) which is liquid at 100 ° C. or lower used in the present invention is preferably a polyfunctional type having two or more epoxy groups in one molecule, such as bisphenol A, bisphenol F and tetra. Brombispheno
Diglycidyl ethers such as bisphenols such as A, polyethylene glycol, polypropylene glycol
Polyglycidyl ethers such as alcohols, polyglycidyl esters such as hexahydrophthalic acid and dimer acid, polyglycidyl amines such as diaminodiphenylmethane, and novolac type polyphenols such as phenol novolac and orthocresol-ren novolac. Diglycidyl ethers such as glycidyl ethers and hydrogenated bisphenol,
One or several kinds of alicyclic epoxy compounds such as 3,4-epoxycyclohexylmethyl-3,4 epoxycyclohexylcarboxylate may be mixed and used.

Monomers used for producing the (meth) acrylic acid ester-based polymer include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. , (Meta)
Examples of the acrylic acid esters such as isoamyl acrylate, 2-ethylhexyl (meth) acrylate, and decyl (meth) acrylate, the corresponding alkyl esters of (meth) acrylic acid, and monomers having a functional group include ( Carboxyl group-containing monomers such as (meth) acrylic acid, hydroxyl group-containing monomers such as hydroxypropyl acrylate and hydroxypropyl methacrylate, methyl group-containing monomers such as N-methyl acrylamide, dimethylol acrylamide, Alkoxymethyl-containing monomers such as N-butoxymethylacrylamide, glycidyl (meth) acrylates, monomers containing epoxy groups such as (meth) acrylglycidyl ether, acrylonitrile, methacrylonitrile, azobisisobutylnitrile, etc. Cyano group-containing monomer - further crosslinking monomer - as divinylbenzene, Arirumetakurire -
And ethylene glycol dimethacrylate and the like can be used.

As the emulsion polymerization of the monomer, a conventionally known method can be applied. For example, a method in which an emulsifier, water, a polymerization catalyst and a monomer are mixed together for polymerization, a method in which the monomer is added later, a pre-emulsion method in which the monomer is emulsified in advance, a decomposable or polymerizable surfactant is used. The soap free emulsion polymerization method used and the multi-stage polymerization method for forming a multi-layer structure can be used. As the catalyst used in the emulsion polymerization, for example, potassium persulfate, ammonium persulfate, hydrogen peroxide and the like generally used in the emulsion polymerization can be used. As the emulsifier, anionic or nonionic emulsifiers can be used. The polymerization is usually performed at a temperature of 30 to 90 ° C. and the reaction time is 2 to 10 hours.

An aqueous dispersion of a (meth) acrylic acid ester-based polymer obtained by emulsion polymerization is mixed under shearing force with an epoxy resin (B) which is liquid at 100 ° C. or lower, and then 80 to 200. A liquid epoxy resin in which the polymer is uniformly contained and dispersed can be produced by dehydration at a temperature of ° C under a reduced pressure of 200 torr or less, and the obtained epoxy resin and phenols and / or alcohol A desired epoxy equivalent can be obtained by a polyaddition reaction with a chain extender such as a carboxylic acid or a carboxy-containing compound. As the phenols, monovalent phenols such as nonylphenol and butylphenol, divalent and trivalent mononuclear phenols such as resorcin, hydroquinone, catechol and pyrogallol. , Biphenols, bisphenols, divalent phenols such as halogenated bisphenols, and novolak resins obtained by the condensation reaction of compounds having a phenolic hydroxyl group with aldehydes. Examples of the polyols include polyols, polyester polyols and polyether polyols, and examples of the carboxy compound include hydrogenated bisphenol.
It is possible to increase the addition product of hexahydrophthalic anhydride with A and the acidic polyesters. These can be used alone or as a mixture of several kinds. The catalyst used in the polyaddition reaction includes tertiary amines such as benzyldimethylamine, triethylamine and benzylamine, and 2
-Imidazols such as methylimidazole and 2-ethyl-4-methylimidazole, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, quaternary ammonium such as benzyltrimethylammonium chloride and tetraammonium chloride Examples thereof include compounds, phosphines such as triphenylphosphine and tributylphosphine, and phosphonium salts such as n-butyltriphenylphosphonium bromide. The catalyst is used in an amount of 10 ppm to 0.5% based on the polymer-containing epoxy resin, and is 60 to 200 ° C.
Preferably, the reaction is carried out at 120 to 180 ° C for 1 to 10 hours. Laminates produced using the epoxy resin composition of the present invention, it is preferable to contain a halide when the flame retardancy of the adhesive is required, tetrabromobisphenol A, tetrabromobisphenol -A A diglycidyl ether and the like can be used.

The content of the (meth) acrylic acid ester polymer in the epoxy resin of the present invention is preferably 2 to 25 parts by weight. If the amount is 2 parts by weight or less, the intended copper foil and the laminate having excellent interlayer adhesion, stress relaxation and tracking resistance cannot be obtained, and if the amount is 25 parts by weight or more, the melt viscosity of the resin increases. . When the polymer is contained and dispersed, the particle diameter is preferably 2 μm or less, and more preferably 0.5 μm or less so that the polymer can be uniformly and stably present as a dispersed phase in the epoxy resin. When the glass transition temperature of the polymer is room temperature or higher,
Since the properties of the laminate as the object of the present invention are not improved, the temperature is preferably room temperature or lower, preferably 0 ° C. or lower. Therefore, it is necessary to consider the kind and combination of the above-mentioned monomers in the production of the polymer.

The epoxy resin composition (A) of the present invention is generally used by blending a curing agent for the purpose of curing, but the curing agent is not particularly limited, and the curing agent generally used. For example, aliphatic amines, aromatic amines, acid anhydrides, imidazoles, hydrazides, dicyandiamides, phenolic hydroxyl group-containing compounds and the like can be used. Examples of the aliphatic amines include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, N, N-dimethylpropylenediamine, N, N
-Diethyl propylene diamine etc. are mentioned. As aromatic amines, m-xylylenediamine, m-phenylenediamine, p-phenylenediamine, bis (4-
Aminophenyl) methane, bis (4-aminophenyl)
Examples thereof include sulfone. In addition, as the amine curing agent, an addition product of the monoepoxy compound with the amines,
An addition product of a bisphenol A and / or bisphenol F type epoxy resin, an addition product of an alicyclic epoxy resin, an addition polycondensation product of a dimer acid and the like can also be used. Examples of the acid anhydride include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, succinic anhydride and the like. As the imidazole, 2-methylimidazole
And 2-ethyl-4-methylimidazole and the like. Further, phenolic hydroxyl group-containing compounds (epoxy resin curing agents containing phenolic hydroxyl groups at both ends, such as TH-4000 and TH-4100 manufactured by Tohto Kasei Co., Ltd., phenolic compounds).
Lunovolac resin and cresol-runovolac resin) can be used.

In addition to the above-mentioned components, various additives and fillers can be appropriately added to the composition of the present invention, if necessary. The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
In addition, "part" represents a part by weight unless otherwise specified.

[0013]

[Examples and Comparative Examples]

Reference Example 1 As a monomer component, methacrylic acid 6 parts and butadiene 6
7 parts, 25 parts of acrylonitrile and 2 parts of divinylbenzene, 250 parts of water, 1 part of sodium dodecylbenzenesulfonate, 0.45 part of tertiary dodecyl mercaptan, 0.27 part of potassium persulfate, cyanoethylated Diethanolamine 0.15 parts and potassium hydroxide 0.1 parts were added, and the mixture was heated in an autoclave at 20 ° C. by a conventional method.
Was copolymerized. When the conversion of polymerization reached 70% or more, 0.2 part of hydroxyamine sulfate was added to stop the polymerization, and the unreacted monomer remaining was removed by steam distillation to disperse the polymer in water. Got the body 300 g of YD-128 (Epoxy equivalent 187 g / eq, 25 ° C. viscosity 12800 mps manufactured by Toto Kasei Co., Ltd.) as an epoxy resin (B) in a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas supply device. Then, 300 g of the aqueous dispersion of the polymer obtained above was added, and the mixture was gradually heated to dehydration and heated to 150 ° C. Next 100 torr
After sufficiently dehydrating under reduced pressure, the mixture was filtered through a 100-mesh wire net to obtain a white liquid epoxy resin in which the polymer was uniformly contained and dispersed. The epoxy equivalent of this product is 226 g /
eq, viscosity at 25 ° C. was 50 ps, polymer content was 16.6%, polymer particle size was 0.3 ± 0.1 μ, and glass transition temperature was −30 ° C.

Example 1 Stirrer, nitrogen gas supply device, condenser, thermometer,
In a four-necked separable flask installed in a polymerization tester equipped with a heating / cooling device, 635.0 g of the polymer-containing dispersed liquid epoxy resin obtained in Reference Example 1 and tetrabromobisphenol A 365. 0 g was charged, and the mixture was gradually heated to 120 ° C. and continuously stirred so as to be uniform, 0.18 g of triphenylphosphine was added as a catalyst, and the mixture was further stirred to keep the temperature at 120 ° C. to make the whole uniform. After this, heat gradually and raise the temperature to 170 ℃, 170 ℃ ±
Reacted at 1 ° C for 4 hours, the epoxy equivalent was 681 g / eq,
A milky white solid epoxy resin a containing a bromine content of 21.5% by weight and a polymer component content of 12.4% was obtained.

Example 2 As in Example 1, 480.0 g of the polymer-containing dispersed epoxy resin obtained in Reference Example 1, 365.0 g of tetrabromobisphenol A and YD-128 (Toto Kasei Co., Ltd.) Made Bisfer A type epoxy resin epoxy equivalent 187g
/ Eq) of 155.0 g was added and 0.18 g of the catalyst used in Example 1 was added and reacted at 170 ° C. ± 1 ° C. for 4 hours.
A milky white solid epoxy resin b containing an epoxy equivalent of 620.g / eq, a bromine content of 21.5% and a polymer component content of 8% was obtained. Example 3 Similar to Example 1, 480.0 g of the polymer-containing dispersed epoxy resin obtained in Reference Example 1 and 365.0 g of tetrabromobisphenol A, YDF-170 (Bispheno-produced by Tohto Kasei Co., Ltd.) LE F type epoxy resin Epoxy equivalent 170
155.0 g of (g / eq) was charged and 0.18 g of the catalyst used in Example 1 was added and reacted at 170 ° C. ± 1 ° C. for 4 hours to obtain an epoxy equivalent of 590 g / eq and a bromine content of 21.5%.
A milky-white solid epoxy resin c containing 8% of a polymer component was obtained at room temperature.

Example 4 495.0 g of the polymer-containing dispersed epoxy resin obtained in Reference Example 1 and YDB-400 (manufactured by Tohto Kasei Co., Ltd., brominated epoxy resin, epoxy equivalent 400 g) as in Example 1.
/ Eq, softening point 69 ° C., bromine content 49.0%) 430.
0 g and 75.0 g of ortho-cresol novolac resin D-5 (manufactured by Tohto Kasei Co., Ltd.) were charged, 0.18 g of the catalyst used in Example 1 was added, and the mixture was reacted at 170 ° C. ± 1 ° C. for 4 hours to obtain an epoxy resin. Equivalent 377 g / eq, bromine content 21.1
% And a polymer component content of 8% to obtain a milky white solid epoxy resin d at room temperature.

Comparative Example 1 Stirrer, nitrogen gas supply device, condenser, thermometer,
In a 4-neck separable flask installed in a polymerization tester equipped with a heating / cooling device, 555 g of YD-128, 365 g of tetrabromobisphenol A and CTBN-1 were placed.
80 g of 300X13 (liquid polybutadiene-acrylonitrile copolymer liquid rubber manufactured by Goodrich, USA) was charged, and 0.18 g of the catalyst used in Example 1 was added to 170 ° C.
React for 4 hours at ± 1 ° C, epoxy equivalent 633g / eq,
A light yellow solid epoxy resin e containing 21.5% of bromine and 8% of rubber component was obtained. Comparative Example 2 As in Comparative Example 1, 603 g of YD-128, 365 g of tetrabromobisphenol A and 32 g of bisphenol A were charged, and 0.18 g of the catalyst used in Example 1 was charged.
Was added and reacted at 170 ° C. ± 1 ° C. for 4 hours to obtain a colorless and transparent solid epoxy resin f having an epoxy equivalent of 623 g / eq and a bromine content of 21.5%. Comparative Example 3 YDB-500 (manufactured by Tohto Kasei Co., Ltd., brominated epoxy resin, epoxy equivalent 515 g / eq, softening point 75 ° C., bromine content 21.4%). Epoxy resin g. The characteristics of the epoxy resin obtained in the examples as a copper-clad laminate are shown below together with comparative examples. The conditions for producing the laminated plate are as follows.

Laminated plate preparation conditions Each resin was dissolved in methyl ethyl ketone, and a curing agent dicyandiamide (DICY manufactured by Nippon Carbide Industry Co., Ltd.) and 2-ethyl-4-methylimidazole (Shikoku Kasei Co., Ltd.) were prepared.
Methyl cellosolve solution of 2E4MZ manufactured by Co., Ltd. was mixed in the following mixing ratio, and glass cloth (WE-18K manufactured by Nittobo Co., Ltd.) was mixed.
It was impregnated with 105B22) and dried at 150 ° C. for 6 minutes to be B-staged. B-staged prepreg 8 ply with Mitsui Mining & Smelting Co., Ltd. copper foil 3EC (35μ)
Were laminated, and a double-sided copper clad laminate having a resin content of about 42% was prepared under the curing conditions of 170 ° C. × 2 hr and 20 kg / cm ² . Table 1 shows the properties of each epoxy resin and the properties of the obtained double-sided copper-clad laminate.

[0019]

[Table 1]

* 1 Tg was measured by a DuPont Viscoelasticity Spectrometer DMA982 at a temperature rising rate of 2 ° C./min and indicated by E'and tan δ values. * 2 For soldering heat resistance, the test piece subjected to forced moisture absorption of * 3 was immersed in a solder bath at 260 ° C for 90 seconds, and visually checked for blisters. * 3 Water absorption is after removing the copper foil by etching
It was dried at 50 ° C. for 24 hours, measured by forced moisture absorption at 120 ° C. × 100% humidity × 2 hours. * 4 According to IEC-112, electrodes were placed at intervals of 4 mm on the surface of the sample obtained by etching away the copper foil of the copper clad laminate, and a 0.1% NH4Cl aqueous solution was dropped while applying a predetermined voltage, and a current of 1 A or more. The maximum voltage that does not flow was measured.

[0021]

EFFECTS OF THE INVENTION A copper foil and a laminate having excellent interlayer adhesion, heat resistance, stress relaxation characteristics and tracking resistance are obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takara Hosono 3-17-14 Higashikasai, Edogawa-ku, Tokyo Toto Kasei Co., Ltd. (56) Reference JP-A-6-172490 (JP, A) JP HEI 2-80483 (JP, A) JP-A-6-329955 (JP, A) JP-A-6-116366 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08G 59 / 00-59/72 B32B 27/38 C08L 63/00-63/10

Claims (6)

(57) [Claims] 1. An epoxy resin (B) containing a (meth) acrylic acid ester polymer and liquid at 100 ° C. or lower.
An epoxy resin (A) having an epoxy equivalent of 230 to 1200 g / eq and containing 2 to 25 parts by weight of a (meth) acrylic acid ester-based polymer by adding and reacting a chain extender and a catalyst as an essential component An epoxy resin composition for a laminate, characterized by containing. 2. The epoxy resin composition for a laminate according to claim 1, wherein the epoxy resin (B) is a bisphenol type epoxy resin and / or a halogenated bisphenol type epoxy resin. 3. The epoxy resin (B) is hydrogenated bisphenol.
The epoxy resin composition for laminated boards according to claim 1, which is a diglycidyl ether and / or an alicyclic diglycidyl ether. 4. The chain extender is bisphenol and / or
The epoxy resin composition for laminated boards according to claim 1, which is a halogenated bisphenol. 5. The epoxy resin composition for laminates according to claim 1, wherein the chain extender is a condensation reaction product of a compound having a phenolic hydroxyl group and an aldehyde. 6. The epoxy resin composition for a laminate according to claim 1, wherein the (meth) acrylic acid ester-based polymer is a fine particle crosslinked polymer having a particle diameter of 2 μm or less, and has a glass transition temperature of room temperature or less.