JP4984385B2 - Epoxy resin composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an eco-friendly epoxy resin composition giving a cured material having excellent heat-resistance and moisture-resistance and exhibiting excellent flame-retardancy without using a halogen-based flame-retardant and suitable for a printed circuit board, an interlayer insulation material for a printed circuit board and a resin-coated copper foil, a sealing material for electronic parts, a resist ink, a conductive paste, a coating material, an adhesive material, a composite material, etc., and provide a cured material of the resin composition. <P>SOLUTION: The epoxy resin composition contains (A) an epoxy resin, (B) a phenolic resin having triazine ring and (C) a phosphorus compound having triazine ring, and the cured material is produced by curing the epoxy resin composition. <P>COPYRIGHT: (C)2006,JPO&amp;NCIPI

Description

  The present invention provides a cured product having excellent heat resistance and moisture resistance of the obtained cured product, and further capable of obtaining a cured product having excellent flame retardancy without using a halogen-based flame retardant. For printed circuit boards, printed circuit boards and resins Environmentally friendly epoxy that can be suitably used for interlayer insulation materials used in coated copper foils, sealing materials for electronic components, resist inks, conductive pastes, paints, adhesive materials, composite materials, etc. The present invention relates to a resin composition and a cured product thereof.

  Conventionally, epoxy resin compositions are suitable for use in semiconductor encapsulants, printed wiring boards, paints, casting materials, etc., because cured products with excellent heat resistance, adhesion, electrical insulation, etc. are obtained. ing. For example, in the semiconductor field, a sealing material using an epoxy resin composition is currently used in most semiconductor devices. In order to impart flame retardancy to this epoxy resin composition, halogen-based flame retardants such as brominated epoxy resins and antimony compounds such as antimony trioxide, antimony tetraoxide and antimony pentoxide are blended as flame retardant aids. ing. However, in recent environmental and safety initiatives, it is required to avoid the use of halogenated flame retardants that are likely to generate dioxins and antimony compounds that are suspected of causing carcinogenicity. There is an increasing demand for development of a resin composition that is easy to use and can be used to obtain a cured product that is excellent in flame retardancy.

  In addition, with recent technological innovation, there is a demand for an epoxy resin composition that has higher levels of heat resistance, moisture resistance, and flame retardancy. Under such circumstances, phosphorus and nitrogen are used as flame retardant components in order to obtain an epoxy resin composition excellent in heat resistance, moisture resistance, and flame retardancy without using the above-mentioned halogen flame retardant (free of halogen). Epoxy resins containing them have been developed. For example, a composition containing phosphorus obtained by reacting a phosphorus compound containing a triazine ring in the molecule with an epoxy resin and a nitrogen-modified epoxy resin is disclosed. (For example, refer to Patent Document 1). However, since the phosphorus and nitrogen-modified epoxy resin composition is modified with a phosphorus compound containing a triazine ring, an increase in molecular weight is inevitable, resulting in poor solvent solubility and glass fiber. Since the impregnation property is also poor, it could not be used for prepregs and laminates. Moreover, the cured product obtained using this phosphorus and nitrogen-modified epoxy resin composition is not sufficient in heat resistance and moisture resistance.

JP 2002-284850 A

  An object of the present invention is to obtain a cured product having excellent heat resistance and moisture resistance of the obtained cured product and excellent flame retardancy without using a halogen-based flame retardant. Environmentally friendly type that can be suitably used for interlayer insulation materials used for copper foils with resin, sealing materials for electronic components, resist inks, conductive pastes, paints, adhesive materials, composite materials, etc. An epoxy resin composition and a cured product thereof are provided.

  As a result of intensive studies to solve the above problems, the present inventor is an epoxy resin containing an epoxy resin, a curing agent and a flame retardant, and a phenol resin having a triazine ring as the curing agent and a triazine as the flame retardant. Cured products obtained using epoxy resin compositions each containing a ring-containing phosphorus compound are excellent in heat resistance, moisture resistance and flame retardancy, and the epoxy resin composition also has good solubility in solvents. The present invention has been completed by finding that it is easily impregnated into glass fibers and the like and is suitable for prepregs and laminates.

  That is, the present invention provides an epoxy resin composition comprising an epoxy resin (A), a phenol resin (B) having a triazine ring, and a phosphorus compound (C) having a triazine ring.

  The present invention also provides a cured product obtained by curing the epoxy resin composition.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the epoxy resin composition which has a moldability and curability of a practical level, and can obtain the hardened | cured material which has the flame retardance, heat resistance, and moisture resistance further superior to the conventional material. . When this epoxy resin composition is used in the field of electronic materials such as a resin composition for printed circuit boards, a resin composition for electronic component encapsulants, resist ink, and conductive paste, It is extremely useful as a resin composition for high-speed computing. In addition, the obtained molded cured product satisfies the above-mentioned uses in moisture resistance, adhesion and the like, and further high demands on adhesives, composite materials, and the like, and can respond to fields requiring high reliability.

  As the epoxy resin (A) used in the present invention, various epoxy resins can be used and are not particularly limited. However, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type are exemplified. Epoxy resin, bisphenol AD type epoxy resin, resorcinol type epoxy resin, hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, xanthene type epoxy resin, etc. Bifunctional epoxy resins such as epoxy resins derived from various phenols; phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type Poxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol Polyfunctional epoxy resins such as epoxy resins derived from trivalent or higher phenols such as co-condensed novolac type epoxy resins, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resins, biphenyl modified novolak type epoxy resins, etc. Can be mentioned. Furthermore, an epoxy resin obtained by modifying these epoxy resins with an organic phosphorus compound can also be used as the epoxy resin (A). An epoxy resin (A) may be used independently and may use 2 or more types together.

  Among these, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin , Cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol Aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolak Epoxy resin, the heat resistance to use a biphenyl-modified novolak type epoxy resin, moisture resistance is preferable since flame retardancy is improved. Among them, in order to improve flame retardancy, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, xanthene type epoxy A bifunctional epoxy resin such as a resin or an epoxy resin modified with an organophosphorus compound is preferable. In order to improve heat resistance, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a triphenylmethane type epoxy resin, tetra It is particularly preferable to use a polyfunctional epoxy resin such as a phenylethane type epoxy resin or a naphthol novolac type epoxy resin.

  The phenol resin (B) used in the present invention only needs to have a triazine ring, and the production method thereof is not particularly limited. For example, the phenol resin (B) is preferably produced by the method described in JP-A No. 11-21419. be able to. Specifically, it can be obtained, for example, by subjecting a phenol (b1), a compound (b2) having an amino group-containing triazine ring, and an aldehyde (b3) to a condensation reaction. The reaction product obtained by this condensation reaction includes a phenol (b1) as a phenol resin (B) having a triazine ring, a condensation reaction product of a compound (b2) having an amino group-containing triazine ring and an aldehyde (b3). A condensate of phenols (b1) and aldehydes (b3), a condensate of compound (b2) having an amino group-containing triazine ring and aldehydes (b3), unreacted phenols (b1), unreacted A composition containing the compound (b2) having an amino group-containing triazine ring may be used.

  The phenols (b1) are not particularly limited, and examples thereof include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o- Isopropylphenol, m-propylphenol, p-propylphenol, p-sec-butylphenol, p-tert-butylphenol, p-cyclohexylphenol, p-chlorophenol, o-bromophenol, m-bromophenol, p-bromophenol, etc. Phenols, naphthols such as α-naphthol and β-naphthol, monohydric phenols such as xylenols such as 2,4-xylenol, 2,5-xylenol and 2,6-xylenol; resorcin, catechol, hydroquinone, 2,2- Bis (4′-hydroxyphenyl) propane, 1,1′-bis (dihydroxyphenyl) methane, 1,1′-bis (dihydroxynaphthyl) methane, tetramethylbiphenol, biphenol, hexamethylbiphenol, 1,2-dihydroxynaphthalene 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, Examples thereof include dihydric phenols such as naphthalenediols such as 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene; trihydric phenols such as trishydroxyphenylmethane. Especially phenol, o-cresol, m-cresol, naphthols, 2,2-bis (4′-hydroxyphenyl) propane, 2,6-xylenol, resorcin, hydroquinone, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene and 2,7-dihydroxynaphthalene are preferable from the economical point and the phenol resin (B) is easy to produce, and phenol is more preferable. The phenols (b1) are not limited to one type in use, and two or more types can be used in combination.

  The compound (b2) may be any compound having an amino group-containing triazine ring. For example, the compound represented by the following general formula (1)

（式中、Ｒ_１、Ｒ_２は、同一でも異なっていても良く、それぞれアミノ基、アルキル基、フェニル基、ヒドロキシ基、ヒドロキシアルキル基、アルコキシ基、アルキルカルボニルオキシ基、アルキルオキシカルボニル基、酸基、ビニル基、シアノ基、ハロゲン原子のいずれかを表す）
で表わされる化合物を好ましく使用することができる。

(In the formula, R ₁ and R ₂ may be the same or different, and amino group, alkyl group, phenyl group, hydroxy group, hydroxyalkyl group, alkoxy group, alkylcarbonyloxy group, alkyloxycarbonyl group, acid, respectively. Group, vinyl group, cyano group, or halogen atom)
The compound represented by can be preferably used.

Specific examples of the compound represented by the general formula (1) include melamine; guanamine derivatives such as acetoguanamine and benzoguanamine; cyanuric acid derivatives such as cyanuric acid, methyl cyanurate, ethyl cyanurate, acetyl cyanurate, and cyanuric chloride. Etc. Among these, melamine or guanamine derivatives such as acetoguanamine and benzoguanamine, in which any one or two of R ₁ and R ₂ are amino groups, are more preferable.

  The use of the compound (b2) having a triazine ring is not limited to one type, and two or more types can be used in combination.

  The aldehyde (c3) is not particularly limited as long as it is a compound having one or more aldehyde groups in one molecule. Examples thereof include formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde and the like. Among these, formaldehyde is preferable from the viewpoint of excellent fluidity and curability of the resulting epoxy resin composition and heat resistance of the cured product.

  As a composition containing a condensation reaction product of a phenol (b1), a compound (b2) having an amino group-containing triazine ring and an aldehyde (b3), which can be preferably used as the phenol resin (B), volatilization during molding Condensation product of phenols (b1), a compound (b2) having an amino group-containing triazine ring and aldehydes (b3) from the point that it is possible to obtain a uniform cured product by suppressing generation of fractions, It is preferable that the resin composition does not contain unreacted aldehydes and does not contain a methylol group. Specifically, this resin composition is a step of adjusting the pH of the system to 5 to 10 with a mixture of the phenols (b1), the compound (b2) having an amino group-containing triazine ring and the aldehydes (b3). (I), comprising a step (ii) of reacting the mixture under conditions where aldehydes (x3) are not volatilized and a step (iii) of removing reaction water in the system, and the step (i) as a first stage reaction, Step (ii) and step (iii) are carried out sequentially, then step (ii) and step (iii) are carried out sequentially as a second stage reaction at a temperature higher than that of the first stage reaction, and step ( By carrying out ii) and step (iii) at a temperature higher than that of the second stage reaction, it can be obtained by a method of converting dimethylene ether bonds in the molecule into methylene bonds. Here, the second-stage reaction and the third-stage reaction may be repeated as necessary. The reaction is carried out so that the molar ratio of the phenol (b1) and the compound (b2) having an amino group-containing triazine ring to the aldehyde (b3) is 1: 0.2 to 0.9. preferable. Contains a condensate of the phenols (b1), the compound (b2) having an amino group-containing triazine ring and the aldehydes (b3), the condensate does not contain unreacted aldehydes, and contains a methylol group Examples of commercially available resin compositions that do not include PHENOLITE LA-7054 (manufactured by Dainippon Ink & Chemicals, Inc.) and PHENOLITE LA-1356 (manufactured by Dainippon Ink & Chemicals, Inc.).

In the epoxy resin composition of the present invention, a curing agent other than the phenol resin (B) having a triazine ring may be used in combination as long as the effects of the invention are not impaired. Curing agents other than the phenol resin (B) having a triazine ring are not particularly limited, and examples thereof include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, and linolenic acid. Polyamide resin synthesized with ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, pheno Ruaralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl-modified phenol aralkyl resin, phenol trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolak resin, biphenyl Examples thereof include polyphenol compounds such as modified phenol resins and aminotriazine-modified phenol resins, and modified products thereof, imidazoles, BF ₃ -amine complexes, and guanidine derivatives. Moreover, these hardening | curing agents may be used independently and may mix 2 or more types.

  The amount of the curing agent containing the phenol resin (B) is such that the active hydrogen group in the curing agent is equivalent to 1 equivalent of the epoxy group of the epoxy resin (A) from the viewpoint that the curing is sufficient and the cured physical properties are good. A range of 0.5 to 1.5 equivalents is preferred.

  The phosphorus compound (C) used in the present invention only needs to have a triazine ring, and the production method and the like are not limited. For example, it can be obtained by reacting a compound (c1) having an amino group-containing triazine ring, an aldehyde (c2) and an organophosphorus compound (c3). Specifically, for example, JP-A-54-3081 (Japanese Examined Patent Publication No. 59-6318), the compound (c1) having an amino group-containing triazine ring is reacted with an aldehyde (c2) in the presence of an alkaline catalyst to form a methylol, and an alcohol is reacted with an alcohol under an acidic catalyst. It can obtain preferably by making it react with an organophosphorus compound (c3) after carrying out dehydration condensation.

  As said compound (c1) which has an amino group containing triazine ring, the compound (b2) which has an amino group containing triazine ring used for preparation of the phenol resin (B) which has a triazine ring can be used, for example. Here, (c1) may be the same as (b2), or may be different.

  As said aldehydes (c2), the aldehydes (b3) used for preparation of the phenol resin (B) which has a triazine ring can be used, for example. Here, (c2) may be the same as (b3) or may be different.

  Examples of the organic phosphorus compound (c3) include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide, 6-methyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene. -10-oxide etc. are mentioned. Among these compounds, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 oxide is preferable from the viewpoint of good flame retardancy.

  As the phosphorus compound (C) having a triazine ring, specifically, 2,4,6-tris (O, P-biphenyl 2, 2′-diylphosphonomethylamino)-represented by the following structural formula (2): 1,3,5-triazine, 2,4-bis (O, P-biphenyl 2,2′-diylphosphonomethylamino) -6-amino-1,3,5- represented by the following structural formula (3) Triazine, 2- (O, P-biphenyl 2,2′-diylphosphonomethylamino) -4,6-diamino-1,3,5-triazine represented by the following structural formula (4), 2,4-bis (O, P-biphenyl 2,2′-diylphosphonomethylamino) -6-phenyl-1,3,5-triazine, represented by the following structural formula (6) Amino-4- (O, P-biphenyl 2,2′-diylpho Phosphono-methyl) -6-phenyl-1,3,5-triazine. Among these compounds, 2,4-bis (O, P-biphenyl 2,2′-diylphosphonomethylamino) -6-phenyl-1,3 is preferable because the solvent solubility of the epoxy resin composition is good. 5-Triazine, 2-amino-4- (O, P-biphenyl 2,2′-diylphosphonomethylamino) -6-phenyl-1,3,5-triazine is preferred.

  Although the usage-amount of the phosphorus compound (C) which has the said triazine ring is not specifically limited, Phosphorus content is 0.5 to 7.0 weight with respect to the resin part in the epoxy resin composition of this invention. It is preferable to use it so that it may become%, and it is especially preferable to use it so that it may become 1.0 to 4.0 weight%.

  The use ratio of the phenol resin (B) having the triazine ring and the phosphorus compound (C) having the triazine ring is 0.1 [(B) / (C)] in terms of a weight ratio in consideration of the synergistic effect of nitrogen and phosphorus. It is preferable that the ratio of the content of nitrogen and phosphorus in the epoxy resin composition [(nitrogen content) / (phosphorus content)] is 0.2 to 1 in weight ratio.

  A curing accelerator (D) can be further added to the epoxy resin composition of the present invention. The curing accelerator (D) is not particularly limited, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. Two or more types can be used in combination.

  In addition, the epoxy resin composition of the present invention includes, as necessary, an inorganic filler, a thermosetting and thermoplastic resin used as a modifier, a flame retardant, a pigment, a silane coupling agent, a release agent, and the like. The various compounding agents can be added.

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and magnesium hydroxide. In order to increase the blending amount of the inorganic filler, it is common to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The desired range varies depending on the application and desired properties, but for example, when used in semiconductor encapsulant applications, it is preferably higher in view of the coefficient of linear expansion and flame retardancy. It is preferably 65% by weight or more, particularly preferably 85% by weight or more. Moreover, when using for uses, such as an electrically conductive paste and an electrically conductive film, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various thermosetting and thermoplastic resins can be used as the modifier. For example, phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyethersulfone resin, polyphenylene ether resin. And polyphenylene sulfide resin, polyester resin, polystyrene resin, polyethylene terephthalate resin and the like.

  Various flame retardants can be used as the flame retardant, and examples thereof include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specific examples thereof include halogen compounds such as tetrabromobisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, tri Phosphate esters such as phenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, polyphosphorus Ammonium acid, polyphosphoric acid amide, red phosphorus, guanidine phosphate, dialkylhydroxymethylphospho Phosphorus atom-containing compounds such as condensed phosphoric acid ester compounds such as chromatography bets, nitrogen atom-containing compound such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, inorganic flame retardant compounds such as calcium borate may be exemplified. Among these, it is added that the halogen compound does not meet the development requirements of a new flame retardant method friendly to the global environment that does not use halogen-containing flame retardants and antimony compounds.

  The use of the epoxy resin composition of the present invention is not particularly limited, and for example, for printed circuit boards, electronic component sealing materials, resist inks, interlayer insulating materials, conductive pastes, resin injections. It can be preferably used for mold materials, adhesive materials, composite materials, insulating paints and the like. Among these, from the point which is excellent in the dielectric property of the hardened | cured material obtained, it can be used more suitably for printed circuit boards, electronic component sealing materials, resist inks, and conductive pastes. It can be suitably used as an adhesive material, and can be suitably used as a composite material because of its high functionality.

  As the printed circuit board, it can be suitably used particularly for prepregs, copper-clad laminates, and interlayer insulation materials for build-up printed circuit boards.

  In order to make the epoxy resin composition of the present invention into a resin composition for a prepreg for a printed circuit board, it is preferably made into a resin composition for a prepreg by varnishing with an organic solvent. Examples of the organic solvent include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, and the like. Non-alcoholic polar solvents and the like have a boiling point of 160 ° C. or lower, and can be used as a mixed solvent of two or more as appropriate. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The weight ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 60% by weight.

  In order to obtain a resin composition for a copper-clad laminate from the epoxy resin composition of the present invention, it is the same as the method for preparing the resin composition for prepreg, and the obtained prepreg is disclosed in, for example, JP-A-7-41543. A copper-clad laminate can be obtained by laminating as described, stacking copper foils as appropriate, and thermocompression bonding at 170-250 ° C. for 10 minutes to 3 hours under a pressure of 1-10 MPa.

  Although it does not specifically limit as a method of obtaining the interlayer insulation material for buildup boards from the epoxy resin composition of the present invention, for example, Japanese Patent Publication No. 4-6116, Unexamined-Japanese-Patent No. 7-304931, Unexamined-Japanese-Patent No. 8-64960, Various methods described in JP-A-9-71762, JP-A-9-298369 and the like can be employed. More specifically, the resin composition appropriately blended with rubber, filler, and the like is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  As a sealing material for the electronic component, it can be suitably used for a tape-shaped sealing material for a semiconductor chip, a potting type liquid sealing agent, an underfill resin, and a semiconductor interlayer insulating film.

  In order to adjust the epoxy resin composition of the present invention for a semiconductor sealing material, the epoxy resin (A), the phenol resin (B) having a triazine ring, the phosphorus compound (C) having a triazine ring, as required After pre-mixing the curing accelerator (D), other coupling agents, mold release agents, and other inorganic fillers, etc., blended in a uniform manner using an extruder, kneader, roll, etc. The method of mixing thoroughly until it becomes is mentioned. When used as a tape-like sealant, the resin composition obtained by the above-described method is heated to produce a semi-cured sheet, which is used as a sealant tape, and then this sealant tape is applied to a semiconductor chip. And a method of softening by heating to 100 to 150 ° C. and completely curing at 170 to 250 ° C. can be mentioned.

  Further, when used as a potting type liquid sealant, the resin composition obtained by the above-mentioned method is dissolved in a solvent as necessary, and then applied onto a semiconductor chip or an electronic component and directly cured. That's fine.

  The method of using the epoxy resin composition of the present invention as an underfill resin is not particularly limited. However, the epoxy resin composition of the present invention is semi-cured on a substrate or a semiconductor element in advance, and then heated to form a semiconductor element. For example, a compression flow method in which the substrate is brought into close contact and completely cured can be used.

  When the epoxy resin composition of the present invention is used as a semiconductor interlayer insulating material, for example, the method described in JP-A-6-85091 can be employed. When used as an interlayer insulating film, it will be in direct contact with the semiconductor, so it is required that the linear expansion coefficient of the insulating material be close to the linear expansion coefficient of the semiconductor so that cracks due to the difference in linear expansion coefficient do not occur in a high temperature environment. The In addition, in order to deal with the problem of signal delay due to miniaturization, multilayering, and high density of semiconductors, there is a demand for technology for reducing the capacity of insulating materials, and this problem can be solved by reducing the dielectric of insulating materials. be able to. The resin composition is preferable because it has characteristics satisfying these requirements.

  When the epoxy resin composition of the present invention is used as a resist ink, for example, according to the method described in JP-A No. 5-186567, a resist ink composition is prepared and then printed on a printed circuit board by a screen printing method. The method of making it a resist ink hardened | cured material after apply | coating to is mentioned.

  When using the epoxy resin composition of the present invention as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition, and the composition for anisotropic conductive film is used. And a paste resin composition for circuit connection which is liquid at room temperature as disclosed in JP-A-62-240183, JP-A-62-276215, JP-A-62-176139, etc. And an anisotropic conductive adhesive.

  When the epoxy resin composition of the present invention is used as a resin composition for an adhesive, for example, (A), a phenol resin (B) having a triazine ring, a phosphorus compound (C) having a triazine ring, and a curing accelerator. (D) Can be obtained by uniformly mixing other curing agents, resins, curing accelerators, solvents, additives, and the like blended as necessary using a mixing mixer or the like at room temperature or under heating. After applying to various base materials, the base materials can be adhered by allowing them to stand at room temperature or under heating.

  In order to obtain a composite material from the epoxy resin composition of the present invention, a varnish was formed using an organic solvent in order to adjust the viscosity according to the application, the varnish was impregnated into a reinforcing substrate, and heated to obtain a prepreg. Thereafter, it is possible to include a method in which the direction of the fiber is changed little by little, the layers are laminated so as to have pseudo-isotropic properties, and then cured and cured by heating. Examples of the organic solvent include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and dimethylformamide. Examples thereof include non-alcoholic polar solvents such as solvents having a boiling point of 160 ° C. or lower, and can be appropriately used as a mixed solvent of two or more. The heating temperature is determined in consideration of the type of solvent used, and is preferably 50 to 150 ° C. The type of the reinforcing substrate is not particularly limited, and examples thereof include carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The ratio of the resin component and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin component in the prepreg is adjusted to 20 to 60% by weight.

  The cured product of the present invention is obtained by molding and curing the above-described epoxy resin composition of the present invention, and can be used as a laminate, a cast product, an adhesive, a coating film, a film and the like. The curing method is not particularly limited. For example, the epoxy resin (A), the phenol resin (B) having a triazine ring, the phosphorus compound (C) having a triazine ring, and a curing accelerator (D) are necessary. The method of thermally curing at room temperature or 80-200 degreeC can be mentioned, after mixing uniformly the other hardening | curing agent mix | blended according to various, various compounding agents, etc. Moreover, it is preferable to employ | adopt suitably the hardening method according to the use to which the epoxy resin composition prepared according to the above-mentioned various uses.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In the following, “parts” and “%” are based on weight unless otherwise specified.

Reference Example 1 (Preparation of comparative control phosphorus and nitrogen-modified epoxy resin composition)
2,4-bis {[6H-dibenzo- <c, e> (1,2) -oxaphosphorin-6-yl] -methylamino} -6-phenyl-1,3,5-triazine, 100 g, bisphenol A Type epoxy resin (Epicoat 828 manufactured by Japan Epoxy Resin Co., Ltd.) 380 g, dicyandiamide 19 g and benzyldimethylamine 0.9 g were charged and heated at 150 ° C. for 1 hour to prepare phosphorus and nitrogen-modified epoxy resin composition.

Example 1
The epoxy resin composition of the present invention is prepared using the epoxy resin (A), the phenol resin (B) having a triazine ring, the phosphorus compound (C) having a triazine ring and the curing accelerator (D) in the formulation shown in Table 1. Prepared. Varnish was prepared by the method shown below using this epoxy resin composition. A laminate was prepared using the obtained varnish under the following conditions.

[Adjustment of varnish]
A solvent was mixed with the epoxy resin composition of the present invention, and finally the non-volatile content (NV) of the composition was adjusted to 55% to prepare a varnish.

[Laminate production conditions]
Base material: Nitto Boseki Co., Ltd. glass cloth “WEA7628H258” 180 μm
Number of plies: 8
Prepregation conditions: 160 ° C / 2 minutes
Copper foil: “GTS-MP” 35 μm manufactured by Furukawa-Sakit Foil Co., Ltd.
Curing conditions: 170 ° C., 2.9 MPa, 1 hour
Thickness after molding: 1.6mm Resin content: 40%

  Observation of the molded state of the laminate and the physical properties tests (glass transition temperature, peel strength, delamination strength, moisture absorption rate, moisture resistance solder resistance, combustion test) were performed. The test conditions for each evaluation item are shown below. The results are shown in Table 1.

Molding state: After removing the copper foil by etching, visually inspect the appearance, and there is no defect, crease, and mising, and the one that is uniformly molded is marked with ◯, and there is a defect, crease, and mising. Or what was not shape | molded uniformly was set as x.
Glass transition temperature: Measured by DMA method after removing copper foil by etching. Temperature rising speed 3 ° C / min.
Peel strength: measured by a method based on JIS-K6481.
Interlaminar peel strength: Measured by a method based on JIS-K6481.
Moisture absorption: Using a pressure cooker tester, a test piece (25 mm × 50 mm) was held for 1 to 3 hours under the conditions of 121 ° C., 2.1 atm and 100% RH, and the weight change before and after the test piece was measured.
Moisture resistance / solder resistance: Using a pressure cooker tester, hold a test piece (25 mm × 50 mm) for 2 to 6 hours under the conditions of 121 ° C., 2.1 atm and 100% RH, and then solder the test piece to 260 ° C. It was immersed in a bath for 30 seconds, and the state change before and after that was observed.
○: No change in appearance, Δ: 5 or less bulges with a diameter of 5 mm or less, X: Generation of bulge larger than 5 mm in diameter, or 6 or more bulges with a diameter of 5 mm or less.
Combustion test: Conforms to UL-94 vertical test.

Examples 1-6, Comparative Examples 1-3
Except for using the epoxy resin (A), the phenol resin (B) having a triazine ring, the phosphorus compound (C) having a triazine ring (C) and a curing accelerator (D) and a solvent in the formulations shown in Tables 1 and 2. A varnish was prepared in the same manner as in 1. Using these varnishes, a laminate was prepared in the same manner as in Example 1, and the molded state was observed and the physical properties were tested. These results are shown in Tables 1 and 2.

Example 7 and Comparative Example 4
Ten pieces of kraft paper cut into 10 cm pieces are stacked to a thickness of 2 mm. The compositions of Example 7 and Reference Example 1 are placed in the center of kraft paper and sandwiched between mirror plates, 170 ° C., 2 ° C. It was press-molded under curing conditions of 9 MPa for 1 hour to obtain a cured product having a thickness of 2 mm. Using this cured product, the molded state was observed and the physical properties were tested. These results are shown in Table 3.

In addition, each raw material and abbreviation in Tables 1-3 are as follows.
“N-770”: phenol novolac type epoxy resin (manufactured by Dainippon Ink and Chemicals, trade name [EPICLON N-770], epoxy equivalent 188 g / eq.)
"N-690": Cresol novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name [EPICLON N-690], epoxy equivalent 215 g / eq.)
“HP-7200H”: dicyclopentadiene type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name [EPICLON HP-7200H], epoxy equivalent 275 g / eq.)
“LA-7054”: Melamine-phenol co-condensed novolac type phenol resin (Dainippon Ink Chemical Co., Ltd., trade name [PHENOLITE LA-7054], hydroxyl group equivalent 125 g / eq.)
"LA-1356": Melamine-phenol co-condensed novolak type phenol resin (Dainippon Ink Chemical Co., Ltd., trade name [PHENOLITE LA-1356], hydroxyl group equivalent 146 g / eq.)
"TD-2090": Novolac type phenol resin (Dainippon Ink Chemical Co., Ltd., trade name [PHENOLITE TD-2090], hydroxyl group equivalent 105 g / eq.)
“2E4MZ”: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name [CURESOL 2E4MZ]).
"MEK": Methyl ethyl ketone "DMF": Dimethylformamide "828": Bisphenol A type epoxy resin (manufactured by Japan Epoxy Resins, trade name [Epicoat 828], epoxy equivalent 188 g / eq.)
“DICY”: Dicyandiamide “BDMA”: Benzyldimethylamine

Claims (17)

An epoxy resin composition comprising an epoxy resin (A), a phenol resin (B) having a triazine ring, and a phosphorus compound (C) having a triazine ring. The phenol resin (B) is a resin composition containing a condensate obtained by reacting a phenol (b1), a compound (b2) having an amino group-containing triazine ring and an aldehyde (b3), The epoxy resin composition according to claim 1, which is a resin composition containing no unreacted aldehydes and no methylol group in the condensate. The epoxy resin composition according to claim 2, wherein the compound (b2) having an amino group-containing triazine ring is one or more compounds selected from the group consisting of melamine, acetoguanamine and benzoguanamine. The epoxy resin composition according to claim 1, wherein the content of the phenol resin (B) is such that the amount of active hydrogen groups is 0.5 to 1.5 equivalents relative to 1 equivalent of epoxy groups in the epoxy resin composition. object. The epoxy resin composition according to claim 1, wherein the phosphorus compound (C) is obtained by reacting a compound (c1) having an amino group-containing triazine ring, an aldehyde (c2), and an organic phosphorus compound (c3). object. The compound (c1) having an amino group-containing triazine ring is one or more compounds selected from the group consisting of melamine, acetoguanamine and benzoguanamine, and the organophosphorus compound (c3) is 9,10-dihydro-9-oxa- The epoxy resin composition according to claim 4, which is 10-phosphaphenanthrene-10-oxide. The use ratio [(B) / (C)] of the phenol resin (B) and the phosphorus compound (C) is 0.1 to 1 by weight, and the content of nitrogen and phosphorus in the epoxy resin composition The epoxy resin composition according to claim 6, wherein the ratio [(nitrogen content) / (phosphorus content)] is 0.2 to 1 in weight ratio. Furthermore, the epoxy resin composition of any one of Claims 1-7 containing a hardening accelerator. The epoxy resin composition according to any one of claims 1 to 7, wherein the epoxy resin (A) is a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, or a dicyclopentadiene type epoxy resin. It is a resin composition for printed circuit boards, The epoxy resin composition of any one of Claims 1-7. The epoxy resin composition according to claim 1, which is a resin composition for a sealing material for electronic parts. It is a resin composition for resist inks, The epoxy resin composition of any one of Claims 1-7. It is a resin composition for electrically conductive pastes, The epoxy resin composition of any one of Claims 1-7. It is a resin composition for interlayer insulation materials, The epoxy resin composition of any one of Claims 1-7. It is a resin composition for adhesive materials, The epoxy resin composition of any one of Claims 1-7. It is a resin composition for composite materials, The epoxy resin composition of any one of Claims 1-7. A cured product obtained by curing the epoxy resin composition according to claim 1.