JP2006022179A - Thermosetting resin composition and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition which is excellent in solvent solubility without using any solvent such as N, N-dimethylformaide and N-methylpyrrolidone, yields a varnish showing a high safety/workability, yields a cured product excellent in heat resistance, flame retardance, moisture resistance, dielectric property, etc. and is suitably used for a sealing material, an electrical/electronic material such as a laminate, a molding material, etc., and its cured product. <P>SOLUTION: The thermosetting resin composition contains (A) a phenolic aminomaleimide prepolymer resin obtained from (a1) a phenolic resin composition having a triazine ring and (a2) a maleimide compound and (B) an alkylene glycol alkyl ether. The cured product is obtained by curing the same. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is excellent in heat resistance, moisture resistance and dielectric properties (low dielectric constant, low dielectric loss tangent) of the cured product obtained, a resin composition for printed circuit boards, a resin composition for encapsulants for electronic components, resist ink, Environment-friendly thermosetting that can be used suitably for conductive pastes, paints, adhesives, composite materials, etc., and can obtain cured products with excellent flame resistance without using halogen-based flame retardants. The present invention relates to a resin composition and a cured product thereof.

  Conventionally, polyimide-based resins have been used in the field of high heat-resistant printed wiring boards that require severe heat resistance, moisture resistance, and dielectric properties (low dielectric constant, low dielectric loss tangent). However, since this polyimide resin is poor in solvent solubility, N, N-dimethylformamide, which is a chemical substance designated by the Chemical Substances Control Law, and a cured product because it has a boiling point of 200 ° C. or higher in order to use a solvent to form a varnish Since N-methylpyrrolidone or the like, which has a problem of residual solvent that lowers the physical properties of the resin, has to be used, the workability is extremely poor and the required properties such as moisture resistance and flame retardancy are adversely affected.

  On the other hand, epoxy resins are suitably used for semiconductor sealing materials, printed wiring boards, paints, casting materials, and the like because cured products having excellent heat resistance, adhesion, electrical insulation, and the like are obtained. However, it has become impossible to sufficiently cope with high demand levels such as heat resistance, moisture resistance, flame retardancy, low dielectric constant and low thermal expansion associated with technological innovation.

  In addition, in recent efforts to address environmental issues, there is a strong demand for the development of new halogen-free flame retardant methods by renewing flame retardant methods that use halogen-based flame retardants, which are feared to generate dioxins. ing.

  As a means for solving the above problem, a technical method has been proposed in which a bisimide compound and a diamine compound are prepolymerized in a specific solvent under specific conditions to increase the solvent solubility (see, for example, Patent Document 1). In order to improve the physical properties of the cured product to a usable level, it is modified with an epoxy resin and used as a curing agent such as dicyandiamide as a common curing agent for the bisimide compound and the epoxy resin. In general, when dicyandiamide is used as a curing agent for an epoxy resin, the above required characteristics are inferior to the cured product obtained by curing the epoxy resin with a phenolic novolac resin in terms of moisture resistance and dielectric properties of the resulting cured product. It is difficult to satisfy.

Japanese Patent Laid-Open No. 5-230242 (page 3-4)

  The present invention has been made in view of such circumstances, and has excellent solvent solubility without using a solvent such as N, N-dimethylformamide or N-methylpyrrolidone, and has good varnish safety and workability. The cured product obtained is excellent in heat resistance, flame retardancy, moisture resistance, dielectric properties, etc., and can be used suitably for electrical and electronic materials such as sealing materials and laminates, and molding materials. It aims at providing curable resin composition and its hardened | cured material.

  The inventors of the present invention diligently studied to solve the above problems, and as a result, a phenolic aminomaleimide prepolymer resin (A) obtained from a phenol resin composition having a triazine ring and a maleimide compound and an alkylene glycol alkyl ether (B And the thermosetting resin composition characterized in that it is excellent in solvent solubility and heat resistance, flame retardancy, moisture resistance, dielectric properties, etc. of the resulting cured product. Completed.

  That is, the present invention contains a phenolic aminomaleimide prepolymer resin (A) obtained from a phenol resin composition (a1) having a triazine ring and a maleimide compound (a2) and an alkylene glycol alkyl ether (B). The thermosetting resin composition characterized by this, and the hardened | cured material obtained using this are provided.

  Since the thermosetting resin composition of the present invention is excellent in solvent solubility, N, N-dimethylformamide, which is a chemical substance designated by the Chemical Substances Control Law, and a solvent residue in the cured product because the boiling point is 200 ° C. or higher. Since there is no need to use a problematic solvent such as N-methylpyrrolidone, the safety of the varnish and the physical properties after curing are excellent. In addition, it has a practical level of moldability and curability, and can impart heat resistance, moisture resistance, dielectric properties, and flame retardancy superior to those of general phenol resin compositions and epoxy resin compositions to the cured product. . In particular, migration that is likely to occur when dicyandiamide is used as a curing agent for an epoxy resin has a deterrent effect because the cured product obtained using the thermosetting resin composition of the present invention has excellent moisture resistance. Therefore, when the thermosetting resin composition of the present invention is used in the field of electronic materials such as a resin composition for printed circuit boards, a resin composition for encapsulants for electronic parts, resist inks, conductive pastes, etc. It is extremely useful as a resin composition that is compatible with high-frequency, high-frequency compatibility, and high-speed computation. In addition, the obtained molded cured product satisfies the requirements for the above-mentioned uses in terms of heat resistance, adhesion, and the like, and can also cope with fields requiring high reliability.

Hereinafter, the present invention will be described in detail.
The phenol resin composition (a1) having a triazine ring used in the present invention is not particularly limited as a production method thereof. For example, a phenol (x1), a compound (x2) having a triazine ring, and an aldehyde (X3) can be obtained by condensation reaction, and in addition to the condensation product of phenols (x1), a compound (x2) having a triazine ring and aldehydes (x3), phenols (x1) and Condensates with aldehydes (x3), compounds (x2) having triazine rings and aldehydes (x3), unreacted phenols (x1), compounds having unreacted triazine rings (x3), etc. It may be a mixture containing

  As the phenol resin composition (a1) having a triazine ring, phenols (x1) and a compound (x2) having a triazine ring can be obtained from suppressing generation of volatile components during molding and obtaining a uniform cured product. The resin composition preferably contains a condensate with aldehydes (x3), does not contain unreacted aldehydes, and does not contain a methylol group.

  The content of monofunctional phenols remaining in the phenol resin composition (a1) having a triazine ring is preferably 3% by weight or less in the phenol resin composition (a1). By making monofunctional phenols into 3 weight% or less, there exists an effect that the heat resistance of the hardened | cured material obtained and moisture resistance improve. The monofunctional phenol here means a compound containing only one phenolic hydroxyl group capable of reacting with an epoxy group in one molecule.

  The phenols (x1) 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; and 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, 2,7-dihydroxynaphthalene and the like are preferable from the viewpoints of economy and ease of production. In addition, these phenols are not limited to one type, and two or more types can be used in combination.

  The compound (x2) having a triazine ring is not particularly limited, but the following general formula (1)

（式中、Ｒ_１、Ｒ_２、Ｒ_３は、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であることが好ましい。

(In the formula, R ₁ , R ₂ and R ₃ are amino group, alkyl group, phenyl group, hydroxy group, hydroxyalkyl group, alkoxy group, alkylcarbonyloxy group, alkyloxycarbonyl group, acid group, vinyl group, cyano group. Represents either a group or a halogen atom)
It is preferable that it is a compound represented by these.

Specific examples of the compound represented by the general formula (1) include melamine, guanamine derivatives such as acetoguanamine and benzoguanamine, cyanuric acid, cyanuric acid such as methyl cyanurate, ethyl cyanurate, acetyl cyanurate, and cyanuric chloride. Examples include acid derivatives. Among these, guanamine derivatives such as melamine, acetoguanamine, and benzoguanamine in which any two or three of R ₁ , R ₂ , and R ₃ are amino groups are more preferable. In particular, melamine is preferably used from the viewpoint of excellent moldability and curability of the resulting thermosetting resin composition.

  The use of the compound (x2) having a triazine ring is not limited to one type, and two or more types can be used in combination.

  The aldehyde (x3) 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, the thermosetting resin composition from which formaldehyde is obtained is preferable from the viewpoint of excellent fluidity and curability and heat resistance of the cured product.

  Below, the method for obtaining the phenol resin composition (a1) which has a triazine ring used by this invention is demonstrated. First, the phenols (x1), the compound (x2) having a triazine ring and the aldehydes (x3) are reacted in the absence of a catalyst or in the presence of a catalyst. At this time, the pH of the system is not particularly limited, but is preferably in the range of pH 3.0 to 9.0. In addition, the reaction order of each raw material is not particularly limited, and the compound having a triazine ring is reversed even if the compound (x2) having a triazine ring is added after the phenols (x1) and aldehydes (x3) are first reacted. Phenols (x1) may be added after reacting (x2) and aldehydes (x3), or all raw materials may be added and reacted at the same time. At this time, the molar ratio of the aldehydes (x3) to the phenols (x1) is not particularly limited, but is preferably aldehydes (x3) / phenols (x1) = 0.1 to 1.1. More preferably, the ratio is 0.2 to 0.8.

  The molar ratio of the compound (x2) having a triazine ring to the phenols (x1) is appropriate in that the reaction system is uniform and the reaction product is uniform, and the crosslinking density of the resulting cured product is appropriate. In view of excellent physical properties of the cured product, the compound having a triazine ring (x2) / phenols (x1) is preferably 0.05 to 1.50, and particularly preferably the ratio is 0.10 to 0.00. 50.

  When a catalyst is used, the type of catalyst is not particularly limited. Examples of the basic catalyst include hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide and barium hydroxide. And oxides thereof, ammonia, primary to tertiary amines, hexamethylenetetramine, sodium carbonate, and the like. Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and sulfonic acid, oxalic acid, and acetic acid. Examples thereof include divalent metal salts such as organic acids, Lewis acids, and zinc acetate.

  When the thermosetting resin composition of the present invention is used as a resin for electrical and electronic materials, it is not preferable that an inorganic substance such as a metal remains as a catalyst residue. An organic acid is preferably used as the catalyst, but a non-catalytic system is more preferable.

  Further, from the viewpoint of reaction control, the reaction may be performed in the presence of various solvents. If necessary, the impurities such as salts may be removed by neutralization and washing with water, but this is not necessary when no amine is used in the catalyst or the catalyst.

  After completion of the reaction, unreacted aldehydes (x3), phenols (x1), solvent and the like are removed according to a conventional method such as atmospheric distillation or vacuum distillation. At this time, in order to obtain a resin composition substantially free of methylol groups, it is preferable to perform a heat treatment at 120 ° C. or higher. Further, if the temperature is 120 ° C. or higher, the methylol group can be extinguished by taking a sufficient time, but it is preferable to perform heat treatment at a higher temperature, preferably 150 ° C. or higher, for efficient elimination. At this time, it is preferable to distill together with heating according to a conventional method for obtaining a novolac resin at a high temperature. At this time, as described above, the monofunctional phenols are preferably 3% by weight or less.

  As the phenol resin composition (a1) having a triazine ring, plural kinds of compositions obtained in the same manner using different raw materials may be mixed and subjected to the following reaction.

The maleimide compound (a2) used in the present invention is not particularly limited, and examples thereof include bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-4,4′-. Phenyl group-substituted bismaleimides such as [3,3′-dimethyl-diphenylmethane] bismaleimide and N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N ′-(4 , 4-diphenylmethane) bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, N, N′-m-phenylenebismaleimide, N, N′-p-phenylenebismaleimide, N, N′-m-toluylene bismaleimide, N, N′-4,4′-biphenylene bismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismale N, N′-4,4′-diphenyl ether bismaleimide, N, N′-3,3′-diphenylsulfone bismaleimide, N, N′-4,4′-diphenylsulfone bismaleimide, 2,2- Bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-tert-butyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [3-s-butyl- 4- (4-maleimidophenoxy) phenyl] propane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] decane, 1,1-bis [2-methyl-4- (4-maleimidophenoxy) -5 -T-Butylphenyl] -2-methylpropane, 4,4'-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2- (1,1-dimethylethyl) benzene 4,4′-methylene-bis [1- (4-maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4′-methylene-bis [1- (4-maleimide) Phenoxy) -2,6-di-s-butylbenzene], 4,4′-cyclohexylidene-bis [1- (4-maleimidophenoxy) -2-cyclohexylbenzene], 4,4′-methylene-bis [ 1- (maleimidophenoxy) -2-nonylbenzene], 4,4 ′-(1-methylethylidene) -bis [1- (maleimidophenoxy) -2,6-bis (1,1-dimethylethyl) benzene], 4,4 ′-(2-ethylhexylidene) -bis [1- (maleimidophenoxy) -benzene], 4,4 ′-(1-methylheptylidene) -bis [1- (maleimidophenoxy) -benzene 4,4′-cyclohexylidene-bis [1- (maleimidophenoxy) -3-methylbenzene], 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2′-bis [3-Methyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2′-bis [3,5-dimethyl-4- (4-maleimidophenoxy) phenyl] propane, 2,2′-bis [3 -Ethyl-4- (4-maleimidophenoxy) phenyl] propane, bis [3-methyl- (4-maleimidophenoxy) phenyl] methane, bis [3,5-dimethyl- (4-maleimidophenoxy) phenyl] methane, bis [3-Ethyl- (4-maleimidophenoxy) phenyl] methane, 3,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5,2,1, O ^2.6 ] decane, 4,8-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5.2.1. O ^2.6 ] decane, 3,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5.2.1. O ^2.6 ] decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5.2.1. O ^2.6 ] decane, polyether bismaleimide acetate and the like. Among these, N, N ′-(4,4-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, 2,2-bis [4- (4-maleimidophenoxy) Use of phenyl] propane is particularly preferred from the viewpoint of excellent heat resistance of the cured product, industrial supply stability, versatility, and the like.

  Although it does not specifically limit as a manufacturing method of the phenolic amino maleimide prepolymer resin (A) used by this invention, The phenol resin composition (a1) which has the said triazine ring, and the said maleimide compound (a2) are made to react. Examples thereof include a method obtained by heating reaction in a temperature range of 80 ° C. to 150 ° C., preferably 100 ° C. to 140 ° C. in a solvent. At this time, it is difficult for the resulting cured product that the weight ratio [(a1) / (a2)] of the phenol resin composition (A) and the maleimide compound (B) is 1/3 to 3/1. It is preferable from the viewpoint of good flammability, and it is particularly preferable that the ratio is in the range of 1 / 2.5 to 2.5 / 1. The reaction temperature is preferably 80 ° C. or higher from the viewpoint that the Michael addition reaction of the phenol resin composition (a1) having a triazine ring and the maleimide compound (a2) proceeds rapidly and is economical. The temperature is preferably 150 ° C. or lower from the viewpoint of easy reaction control.

  At this time, it is preferable to use an alkylene glycol alkyl ether (B) described later as a reaction solvent. The alkylene glycol alkyl ether (B) can easily dissolve the phenolic aminomaleimide prepolymer resin (A) and can be removed from the varnish as a volatile component even if it is not heated to high temperature. There is no adverse effect on the cured product as a residual solvent. Therefore, when used as a reaction solvent, it is not necessary to remove from the system after the reaction, and the manufacturing process is simplified.

  Furthermore, as a weight average molecular weight measured by gel permeation chromatography (GPC) of the phenolic aminomaleimide prepolymer resin (A), the content of unreacted maleimide compound (a2) is small and high molecular weight is contained. Since the amount is small, it is 1,000 to 6,000, preferably 1,500 to 4,500 from the viewpoint of excellent solvent solubility.

  Examples of the solvent that may be used for adjusting the viscosity of the varnish containing the phenolic aminomaleimide prepolymer resin (A) after the reaction include alcoholic solvents such as methanol, ethanol and isopropyl alcohol, and aromatics such as toluene and xylene. And a solvent having a boiling point of 160 ° C. or lower, such as a non-alcoholic polar solvent such as an aromatic hydrocarbon solvent, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and dimethylformamide.

  The alkylene glycol alkyl ether (B) used in the present invention is not particularly limited. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, Examples include propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and dipropylene glycol monomethyl ether. These may be used alone or in combination of two or more. As described above, the alkylene glycol alkyl ether may be used during the reaction of the phenol resin composition (a1) and the maleimide compound (a2), or may be used for adjusting the viscosity of the varnish after the reaction. At this time, the one used for the reaction and the one used for viscosity adjustment may be the same or different, and are appropriately selected according to the use, heat curing conditions, etc. when used as a thermosetting resin composition. Are preferably used.

  The thermosetting resin composition of the present invention may be used in combination with an epoxy resin (C) as necessary in order to further impart performances such as flame retardancy, heat resistance and moisture resistance of the resulting cured product. I can do it. As the epoxy resin (C) that can be used in combination, various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin , Epoxy resin derived from divalent phenols such as resorcinol type epoxy resin, hydroquinone 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 novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modified epoxy resin, phenol alla Kill 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 novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified Examples include, but are not limited to, epoxy resins derived from trihydric or higher phenols such as phenol resin epoxy resins, biphenyl modified novolak epoxy resins, and various modified epoxy resins containing phosphorus atoms in the structure. is not. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  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 It is preferable to use an epoxy resin or a biphenyl-modified novolac type epoxy resin, and 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 It is preferable to use a bifunctional epoxy resin such as an epoxy resin or a tetramethylbiphenyl type epoxy resin, or various modified epoxy resins containing phosphorus atoms in the structure. In order to improve the heat resistance, a phenol novolac type epoxy resin It is particularly preferable to use a polyfunctional epoxy resin such as a cresol novolac epoxy resin, a triphenylmethane epoxy resin, a tetraphenylethane epoxy resin, or a naphthol novolac epoxy resin.

  Further, a curing accelerator can be used as appropriate, and examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. In addition, two or more types can be used in combination.

  If necessary, the thermosetting resin composition of the present invention is an inorganic filler, a thermosetting and thermoplastic resin used as a modifier, a flame retardant, a pigment, a silane coupling agent, a release agent. Various compounding agents such as can be added.

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum 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 novolak 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, Ammonium polyphosphate, polyphosphate amide, red phosphorus, guanidine phosphate, dialkylhydroxymethylphosphine Phosphorus atom-containing compounds such as condensed phosphoric acid ester compounds such as sulfonates, 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 thermosetting resin composition of the present invention is not particularly limited, and for example, for printed circuit boards, electronic component sealing materials, conductive pastes, resin casting materials, adhesives, and insulating paints. Among these, among these, it is suitable for use as a resin composition for printed circuit boards, a resin composition for encapsulants for electronic parts, and a conductive paste because of the excellent dielectric properties of the resulting cured product. It can be suitably used for an adhesive because it has excellent moisture resistance, and can be suitably used for 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 thermosetting resin composition of the present invention into a resin composition for a prepreg for a printed circuit board, it is preferable to form a resin composition for a prepreg by varnishing using an organic solvent. Examples of the organic solvent include the alkylene glycol alkyl ether (B), and other solvents include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, toluene, xylene, and the like. Non-alcoholic polar solvents such as aromatic hydrocarbon solvents, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, and the like. Solvents having a boiling point of 160 ° C. or lower are used, and two or more mixed solvents are used as appropriate. can do. 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 thermosetting resin composition of the present invention, it is the same as the above method for preparing a resin composition for a prepreg, and the obtained prepreg is, for example, JP-A-7-41543. It is possible to obtain a copper-clad laminate by laminating as described in the official gazette, stacking copper foils as appropriate, and thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa. it can.

  A method for obtaining an interlayer insulating material for a build-up substrate from the thermosetting resin composition of the present invention is not particularly limited. For example, JP-B-4-6116, JP-A-7-304931, JP-A-8-64960 Various methods described in Japanese Patent Laid-Open No. 9-71762, Japanese Patent Laid-Open No. 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 base can be obtained by alternately building up and forming the resin insulating layer and the 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 prepare the thermosetting resin composition of the present invention for a semiconductor sealing material, the phenolic aminomaleimide prepolymer resin (A), the alkylene glycol alkyl ether (B), and an epoxy compounded as necessary Resin (C), other coupling agents, release agents, and other additives and inorganic fillers are premixed, and then mixed thoroughly until uniform using an extruder, kneader, roll, etc. The technique to do 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 thermosetting resin composition of the present invention as an underfill resin is not particularly limited. However, the thermosetting resin composition of the present invention is semi-cured on a substrate or a semiconductor element in advance and then heated. A compression flow method in which the semiconductor element and the substrate are brought into close contact with each other and completely cured.

  When the thermosetting resin composition of the present invention is used as a semiconductor interlayer insulating material, for example, a method described in JP-A-6-85091 can be employed. When used for an interlayer insulating film, it is directly applied to the semiconductor, so it is required that the linear expansion coefficient of the insulating material be close to that 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 thermosetting resin composition of the present invention is used as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition for use in an anisotropic conductive film. A paste resin for circuit connection which is liquid at room temperature as disclosed in a method for forming a composition, such as JP 62-40183, JP 62-76215, JP 62-176139, etc. Examples thereof include a method of using a composition or an anisotropic conductive adhesive.

  When the thermosetting resin composition of the present invention is used as a resin composition for an adhesive, for example, the phenolic aminomaleimide prepolymer resin (A), alkylene glycol alkyl ether (B), and blended as necessary. Epoxy resin (C), curing accelerator, solvent, additive, etc. can be obtained by uniformly mixing with a mixing mixer or the like at room temperature or under heating. The substrate can be adhered by leaving it to stand under heating.

  In order to obtain a composite material from the thermosetting resin composition of the present invention, it is varnished with an organic solvent in order to adjust the viscosity according to the use, the varnish is impregnated into a reinforcing substrate, and heated to heat the prepreg. There is a method in which, after being obtained, the direction of the fiber is changed little by little, the layers are laminated so as to have pseudo-isotropic properties, and then heated to be cured and molded. Examples of the organic solvent include alcoholic solvents such as the alkylene glycol alkyl ether (B), methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, acetone, and methyl ethyl ketone. Non-alcoholic polar solvents such as methyl isobutyl ketone, cyclohexanone, dimethylformamide and the like, and solvents having a boiling point of 160 ° C. or lower can be used, and two or more mixed solvents can be used as appropriate. 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 thermosetting 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, phenolic aminomaleimide prepolymer resin (A), alkylene glycol alkyl ether (B), epoxy resin (C) blended as necessary, other resins Examples thereof include a method in which various compounding agents and the like are uniformly mixed and then heat-cured at room temperature or 80 to 200 ° C. Moreover, it is preferable to employ | adopt suitably the hardening method according to the use to which the thermosetting resin composition prepared according to the above-mentioned various uses.

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

  Presence / absence of methylol groups in the phenol resin compositions (a1) obtained in the following synthesis examples and synthesis comparative examples, and monofunctional phenols were determined as follows.

<Presence or absence of methylol group>
^The methylol group present in the resin composition was measured using ¹³ C-NMR.
Apparatus: GSX270 proton made by JEOL Ltd .: 270 MHz, measurement solvent: heavy methanol or heavy acetone, heavy dimethyl sulfoxide, reference material: tetramethylsilane. Judgment was made using a peak appearing at 60 to 70 ppm of the obtained chart and clearly distinguishable from noise. The case where a peak was observed was “present”, and the case where a peak was not observed was “not present”.

<Amount of monofunctional phenols>
Column: 30% Celite 545 carnauba wax 2 m × 3 mmφ, column temperature: 170 ° C., inlet temperature: 230 ° C., detector: FID, carrier gas: N ₂ gas 1.0 kg / cm ² , measurement method: internal standard method Under the measurement conditions, the amount of monofunctional phenol in the phenol resin composition (a1) was measured.

<Weight average molecular weight>
Device: HLC-8220 manufactured by Tosoh Corporation, column: TSK-GEL G4000HXL 1, G3000HXL 1, G2000HXL 2 HLC-8220, carrier solvent: THF, measurement temperature: 40 ° C., measurement flow rate: 1 mL / min, detector: RI, measured concentration: 0.5 wt% (resin content)

Synthesis example 1
A reactor equipped with a condenser and an atmospheric and vacuum distillation apparatus was charged with 94 parts of phenol, 18.8 parts of melamine, and 36.1 parts of 41.5% formalin, heated to 100 ° C. and refluxed for 2 hours. Reacted. Next, the temperature was raised to 135 ° C. during atmospheric distillation, and the reflux reaction was continued for 2 hours, and the temperature was raised to 180 ° C. again under atmospheric distillation, followed by distillation under reduced pressure at 180 ° C. to remove unreacted monomers, water, etc. Low-boiling components were removed, and 67 parts of a phenol resin composition having a triazine ring with a softening point of 136 ° C. was obtained. Let this resin composition be (a1-1). In the solid content of the obtained phenol resin composition, no methylol group was present, the monofunctional phenols were 0.9% by weight, and the hydroxyl group equivalent was 146 g / eq. Met.

Synthesis example 2
In a reactor equipped with a condenser, 135 parts of the resin composition (a1-1) obtained in Synthesis Example 1, 165 parts of bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, ethylene glycol monomethyl ether After 200 parts were charged and heated and stirred at 125 ° C. for 30 minutes and cooled to room temperature, 500 parts of a phenolic aminomaleimide prepolymer resin (A-1) solution was obtained. The weight average molecular weight measured by GPC of the solid content (phenolic aminomaleimide prepolymer resin) was 2,905.

Synthesis example 3
In a reactor equipped with a condenser, 135 parts of the resin composition (a1-1) obtained in Synthesis Example 1, 134 parts of N, N ′-(4,4-diphenylmethane) bismaleimide, 179 parts of ethylene glycol monomethyl ether Was heated and stirred at 105 ° C. for 10 minutes and cooled to room temperature to obtain 448 parts of a phenolic aminomaleimide prepolymer resin (A-2) solution. The weight average molecular weight measured by GPC of the solid content (phenolic aminomaleimide prepolymer resin) was 3,923.

Synthesis example 4
In a reactor equipped with a condenser, 135 parts of the resin composition (a1-1) obtained in Synthesis Example 1, 213 parts of 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, ethylene glycol monomethyl After charging 232 parts of ether and heating and stirring at 110 ° C. for 10 minutes and cooling to room temperature, 580 parts of a phenolic aminomaleimide prepolymer resin (A-3) solution was obtained. The weight average molecular weight measured by GPC of the solid content (phenolic aminomaleimide prepolymer resin) was 3,452.

Comparative Synthesis Example 1
The synthesis was carried out with reference to Example 1 of JP-A-5-230242. A reactor equipped with a condenser was charged with 150 parts of N, N ′-(4,4-diphenylmethane) bismaleimide, 30 parts of 4,4-diaminodiphenylmethane, and 180 parts of ethylene glycol monomethyl ether, and heated and stirred at 125 ° C. for 30 minutes. Then, 120 parts of a bisphenol F type epoxy resin (trade name [EPICLON 830-S], epoxy equivalent 171 g / eq.) Manufactured by Dainippon Ink & Chemicals, Inc. was added, and further reacted at 90 ° C. for 30 minutes. After cooling to room temperature, 7.4 parts of dicyandiamide and 120 parts of methyl ethyl ketone were added to adjust the nonvolatile content (NV) of the composition to 50%. This resin solution is designated as A′1.

Examples Examples 1 to 6, Comparative Example 1
A varnish was prepared by the following method according to the formulation shown in Table 1 and cured under the following conditions to produce a double-sided copper-clad laminate, and various evaluations were performed. The results are shown in Table 1.

[Adjustment of varnish]
The varnish was mixed with a solution of the phenolic aminomaleimide prepolymer resins (A-1) to (A-3) obtained in Synthesis Examples 2 to 4 alone or with the epoxy resin (C), and finally heated. It adjusted so that the non volatile matter (NV) of curable resin composition might be 50%. A′1 synthesized in the comparative synthesis example was used as it was.

[Laminate production conditions]
Substrate: 180 μm; glass cloth “WEA 7628 H258” manufactured by Nitto Boseki Co., Ltd.
Number of plies: 8 Pre-pregation conditions: 160 ° C./4 minutes Copper foil: 35 μm; Furukawa Sark Wheel Co., Ltd. Curing conditions: 1.5 hours at 200 ° C. and 40 kg / cm 2 Thickness after molding: 1.6 mm Resin Content: 40%

[Physical property test conditions]
Molded state: After removing the copper foil by etching, visual inspection was performed, and a product that was uniformly molded without defects, scraping, and mising was marked as ◯.
Glass transition temperature: Measured by DMA method after removing copper foil by etching. Temperature rising speed 3 ° C / min.
Moisture absorption: Using a pressure cooker tester, a test piece (25 mm × 50 mm) was held for 2 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.
Dielectric characteristics: Dielectric constant and dielectric loss tangent at frequencies of 100 MHz and 1 GHz were measured using a dielectric characteristic evaluator (test piece size 75 × 25 × 2 mm).
Combustion test: Conforms to UL-94 vertical test.

The raw materials and abbreviations in Table 1 are as follows.
"830-S": Bisphenol F type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name [EPICLON 830-S], epoxy equivalent 171 g / eq.)
"MEK": Methyl ethyl ketone

Claims (16)

Thermosetting comprising a phenolic aminomaleimide prepolymer resin (A) obtained from a phenol resin composition (a1) having a triazine ring and a maleimide compound (a2) and an alkylene glycol alkyl ether (B) Resin composition. The phenol resin composition (a1) contains a condensate obtained by reacting a phenol (x1), a compound (x2) having a triazine ring and an aldehyde (x3), and is unreacted in the condensate The thermosetting resin composition according to claim 1, which is a resin composition which does not contain aldehydes and does not contain a methylol group. The thermosetting resin composition according to claim 2, wherein the compound (x2) having a triazine ring is one or more compounds selected from the group consisting of melamine, acetoguanamine and benzoguanamine. The thermosetting resin composition according to claim 2, wherein the compound (x2) having a triazine ring contains melamine. The thermosetting resin composition according to claim 2, wherein the content of monofunctional phenols remaining in the phenol resin composition (a1) is 3% by weight or less. The thermosetting resin composition according to claim 1, wherein the phenolic aminomaleimide prepolymer resin (A) has a weight average molecular weight of 1,000 to 6,000 as measured by gel permeation chromatography. The maleimide compound (a2) is N, N ′-(4,4-diphenylmethane) bismaleimide, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane and 2,2-bis [4- (4 The thermosetting resin composition according to any one of claims 1 to 5, which is one or more compounds selected from the group consisting of -maleimidophenoxy) phenyl] propane. The thermosetting resin composition according to claim 1, wherein a weight ratio [(a1) / (a2)] of the phenol resin composition (a1) and the maleimide compound (a2) is 1/3 to 3/1. The phenolic aminomaleimide prepolymer resin (A) is obtained by reacting a phenol resin composition (a1) having a triazine ring with a maleimide compound (a2) in an alkylene glycol alkyl ether (B). The thermosetting resin composition according to claim 1. Furthermore, the thermosetting resin composition of any one of Claims 1-9 containing an epoxy resin (C). It is a resin composition for printed circuit boards, The thermosetting resin composition in any one of Claims 1-10. The thermosetting resin composition according to any one of claims 1 to 10, which is a resin composition for a sealing material for electronic parts. The thermosetting resin composition according to claim 1, which is used for resist ink. The thermosetting resin composition according to any one of claims 1 to 10, which is used for a conductive paste. The thermosetting resin composition according to any one of claims 1 to 10, which is used for an interlayer insulating material. A cured product obtained by curing the thermosetting resin composition according to any one of claims 1 to 15.