JP5181418B2 - Thermosetting resin composition, epoxy resin composition, and cured product thereof - Google Patents

Description

  The present invention is a thermosetting resin composition that can be suitably used for a resin composition for a printed circuit board, a resin composition for an electronic component sealing material, a resist ink, a conductive paste, a paint, an adhesive, a composite material, and the like. The present invention relates to an epoxy resin composition and a cured product thereof.

  Conventionally, thermosetting resins using epoxy resin, phenol resin, or polyimide resin blended with a curing agent have been widely used as materials for electrical and electronic parts such as semiconductor sealing materials, printed wiring boards, and conductive pastes. Yes. However, due to the remarkable increase in integration and frequency of electronic components in recent years, these materials have increasingly required characteristics such as heat resistance, moisture resistance and dielectric characteristics, and these characteristics can be combined. There has been a strong demand. Therefore, for example, as a material having excellent heat resistance, a thermosetting composition having a bismaleimide compound and an amine curing agent as essential components has attracted attention. For example, a condensate of a phenol, a triazine compound, and an aldehyde. And 4,4′-diphenylmethane-bismaleimide in combination with a technology for improving various properties such as heat resistance, moisture resistance, dielectric properties, thermal expansion properties, and flame retardancy (see, for example, Patent Document 1) By combining a condensate of phenols, triazine compounds and aldehydes, bismaleimides and epoxy resins, various properties such as heat resistance, moisture resistance, dielectric properties, thermal expansion properties, and flame retardancy are improved. Techniques (see, for example, Patent Documents 2 and 3) are known.

Japanese Patent Laid-Open No. 9-124897 JP-A-9-124775 JP 2002-179772 A

  However, although 4,4'-diphenylmethane-bismaleimide has good heat resistance, it has a high dielectric loss tangent when used as a material for electric parts and electronic parts, so it can be applied to high frequency type electric and electronic parts. The heat generation at the time is extremely high, and it has been difficult to apply to electric and electronic parts that have been increasingly used in recent years. In addition, the simple method using a condensate of phenols, triazine compounds and aldehydes and maleimides has a high curing temperature of 200 ° C for complete curing, and it is dedicated to fully extract the required performance. Equipment was required, and it was difficult to use for anything other than special purposes. Furthermore, all of the above methods were characterized by heat resistance, particularly weak under conditions exposed to high temperatures for a long time (for example, heat-resistant oven test).

  Therefore, the problem to be solved by the present invention is that the bismaleimide-based material retains the curability capable of exhibiting performance in general-purpose equipment, and dramatically improves heat resistance while maintaining moisture resistance and dielectric properties. There is to make it.

  The present inventors have intensively studied to solve the above problems, and in the thermosetting composition mainly comprising a bismaleimide compound and a triazine compound, the cause of lowering the curability and heat resistance is the bismaleimide compound. And the triazine compound is not completely reacted, and the molecular structure itself of the triazine compound is found, and by introducing a predetermined structure into the triazine compound, it is possible to simultaneously improve the lowering of the curing temperature and the heat resistance, The present invention has been completed.

（式中、Ｒは、水素原子、脂肪族炭化水素基、芳香族炭化水素基、ハロゲン原子のいずれかを表し、ｎ、ｍは１〜５の整数を表す）
で示されるカルボキシル基とアミノ基とを有する化合物（ｘ２）と、アルデヒド類（ｘ３）とを反応させて得られる縮合物（Ｉ）を含有するフェノール樹脂組成物（Ａ）と、マレイミド類（Ｂ）とを、[フェノール樹脂組成物（Ａ）／マレイミド類（Ｂ）]の重量比で、通常、１／３〜３／１なる範囲で含有することを特徴とする含有する熱硬化性樹脂組成物、その硬化物を提供するものである。 That is, the present invention relates to phenols (x1) and the following structural formula (1)

(In the formula, R represents a hydrogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogen atom, and n and m represent an integer of 1 to 5).
A phenol resin composition (A) containing a condensate (I) obtained by reacting a compound (x2) having a carboxyl group and an amino group, and an aldehyde (x3), and a maleimide (B And a weight ratio of [phenol resin composition (A) / maleimides (B)], usually in a range of 1/3 to 3/1. Product, and its cured product.

Further, the present invention is a phenol resin composition containing the phenol (x1) and the compound having a carboxyl group and an amino group (x2) and aldehydes (x3) and condensates obtained by reacting (I) An epoxy resin composition containing (A), a maleimide (B), and an epoxy resin (C), and a cured product thereof are also provided.

Further, the present invention is phenol (x1) and the carboxyl group and the amino group of the compound having at the same time (x2) and aldehydes (x3) and the compound having a triazine ring (x4) condensates obtained by reacting (II) The thermosetting resin composition characterized by containing the phenol resin composition (D) and maleimides (B) containing this, and its hardened | cured material are also provided.

The present invention also phenols (x1) and the carboxyl group and the amino group of the compound having at the same time (x2) and aldehydes (x3) and the compound having a triazine ring (x4) condensates obtained by reacting (II ) -Containing phenol resin composition (D), maleimides (B), and epoxy resin (C), and an epoxy resin composition and a cured product thereof.

In addition to the phenol resin composition (A) and / or the phenol resin composition (D), the present invention reacts a phenol (x1), an aldehyde (x3), and a compound (x4) having a triazine ring. A thermosetting resin composition containing a phenol resin composition (E) containing a condensate (III) and a maleimide (B), and a cured product thereof. .

  Furthermore, in the present invention, in addition to the phenol resin composition (A) and / or the phenol resin composition (D), a phenol (x1), an aldehyde (x3), and a compound (x4) having a triazine ring are reacted. An epoxy resin composition containing a phenol resin composition (E) containing a condensate (III) obtained in the above, a maleimide (B), and an epoxy resin (C), and a cured product thereof To do.

  According to the present invention, the bismaleimide-based material can maintain the curability capable of exhibiting performance with general-purpose equipment, and can drastically improve heat resistance while maintaining moisture resistance and dielectric properties.

  Therefore, the thermosetting composition of the present invention is useful as a material for electrical and electronic parts such as a resin composition for printed circuit boards, a resin composition for sealing materials, and a conductive paste.

  Hereinafter, the present invention will be described in detail.

  As a phenol resin composition (A) used by this invention, if the said condensate (I) is contained, it will not specifically limit as the manufacturing method. The condensate (I) can be obtained, for example, by subjecting a phenol (x1), a compound (x2) having a carboxyl group and an amino group at the same time, and an aldehyde (x3) to a condensation reaction. In addition to the condensate (I) of the phenols (x1), the compound (x2) having a carboxyl group and an amino group at the same time, and the aldehydes (x3), the phenols (x1) and the aldehydes (x3) Condensate, condensate of compound (x2) having carboxyl group and amino group at the same time and aldehydes (x3), unreacted phenols (x1), or compound having unreacted carboxyl group and amino group at the same time ( It may be a mixture containing x2) and the like.

  As said phenol resin composition (A), the compound (x2) which has phenols (x1), a carboxyl group, and an amino group simultaneously from the point which can suppress generation | occurrence | production of the volatile matter at the time of shaping | molding, and can obtain a uniform hardened | cured material. The condensate (I) of aldehydes (x3) preferably contains no unreacted aldehydes and no methylol group.

  The content of monofunctional phenols remaining in the phenol resin composition (A) is preferably 3% by weight or less in the phenol resin composition (A). 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. Further, these phenols are not limited to one type in use, and two or more types can be used in combination.

  The compound (x2) having a carboxyl group and an amino group at the same time is not particularly limited, but is preferably a compound represented by the following general formula (1) (wherein R is a hydrogen atom, An aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a halogen atom is represented, and n and m represent an integer of 1 to 5.)

  The use of the compound (x2) having the carboxyl group and the amino group at the same time is not limited to the use of the compound (x2), and the compound (x4) having a triazine ring can be used in combination.

  The compound (x4) having a triazine ring is not particularly limited, but the following general formula (2)

(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 (2) 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.

  The aldehydes (x3) are not particularly limited as long as they are compounds having one or more aldehyde groups in one molecule. For example, aliphatic aldehydes such as formaldehyde, acetaldehyde, crotonaldehyde, Aromatic aldehydes such as benzaldehyde, 4-methylbenzaldehyde, 3,4-dimethylbenzaldehyde, biphenylaldehyde, naphthylaldehyde, salicylaldehyde, 2-, 3-, and 4-hydroxy substituted benzaldehydes, 2-hydroxy-4- Hydroxy such as methylbenzaldehyde, 2-hydroxy-3,4-dimethylbenzaldehyde, 4-hydroxybiphenylaldehyde, 2-, 5-, 6-hydroxy substituted-1-naphthaldehyde, 7-hydroxy-2-naphthaldehyde, etc. In particular, formaldehyde, benzaldehyde, and salicylaldehyde are preferable from the viewpoints of industrial supply stability, versatility, and excellent heat resistance, flame retardancy, and dielectric properties of the resulting cured product. These can be used in combination.

  The method for obtaining the phenol resin composition (A) used by this invention below is demonstrated. First, the phenols (x1), the compound (x2) having a carboxyl group and an amino group at the same time, 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 the pH is preferably in the range of 3.0 to 9.0. In addition, the reaction order of each raw material is not particularly limited. Even if a compound (x2) having a carboxyl group and an amino group is added after reacting phenols (x1) and aldehydes (x3) first, The phenol (x1) may be added after reacting the compound (x2) having the group and amino group simultaneously with the aldehyde (x3), or all the 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 preferably the aldehydes (x3) / phenols (x1) = 0.1 to 1.1 (moles). Ratio), and more preferably 0.2 to 0.8 as the ratio.

  The molar ratio of the carboxyl group and the compound (x2) having an amino group simultaneously with respect to the phenol (x1) is that the reaction system is uniform and the reaction product is uniform, and the resulting cured product is crosslinked. From the point that the density is appropriate and the cured product has excellent physical properties, it is preferably a compound having a carboxyl group and an amino group (x2) / phenols (x1) = 0.05 to 1.50 (molar ratio). Particularly preferably, the ratio is 0.05 to 0.50.

  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, sulfonic acid and phosphoric acid, oxalic acid and acetic acid. And organic acids such as Lewis acids and divalent metal salts such as zinc acetate.

  When the epoxy 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, so that basic catalysts include amines and acidic catalysts. It is preferable to use an organic acid, and 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, condensed water, 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, it is preferable from the viewpoint of preventing gelation that the methylol group is substantially reduced to a state where the presence of the methylol group cannot be confirmed. In order to obtain a resin composition in which substantially no methylol group can be confirmed, it is preferable to perform a heat treatment at 120 ° C. or higher. If the temperature is 120 ° C. or higher, it can be reduced to a state where the presence of a methylol group cannot be substantially confirmed by taking a sufficient time. However, a higher temperature, preferably 150 ° C. or higher, is required for efficient reduction. It is preferable to carry out. 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. Further, as described above, the monofunctional phenols in the phenol resin composition (A) are preferably 3% by weight or less.

  Here, the state in which the presence of a methylol group cannot be substantially confirmed in the target resin refers to a state below the detection limit when measured under the following conditions.

<Measurement conditions of methylol group content>
GSX270 proton manufactured by JEOL Ltd .: 270 MHz C13-NMR is used under the following conditions.

Measurement solvent: heavy methanol or heavy acetone, heavy dimethyl sulfoxide,
Reference substance: Tetramethylsilane Focusing on 60 to 70 ppm of the obtained chart, determination is performed using a peak that can be clearly distinguished from noise.

  Moreover, as a phenol resin composition (A), you may mix and use the multiple types of composition obtained similarly using a different raw material, and may use it for the epoxy resin composition of this invention.

  The phenol resin containing a condensate (II) obtained by reacting a phenol (x1), a compound (x2) having a carboxyl group and an amino group simultaneously, an aldehyde (x3) and a compound (x4) having a triazine ring In addition to the composition (D) or the phenol resin composition (A) and / or the phenol resin composition (D), a phenol (x1), an aldehyde (x3), and a compound (x4) having a triazine ring In the case of the phenol resin composition (E) containing the condensate (III) obtained by the reaction, it can be obtained by the same production method as the phenol resin composition (A), and the phenols (x1) to be used, As a compound (x2) having a carboxyl group and an amino group at the same time, an aldehyde (x3), and a compound (x4) having a triazine ring, Serial phenolic resin composition as mentioned in (A) both can be used.

  When the compound (x4) having a triazine ring is used in the phenol resin composition used in the present invention, the compound (x4) / phenols (x1) having a triazine ring = 0.01 to 1.50 (molar ratio). It is preferable that the ratio is preferably 0.01 to 0.50.

Examples of maleimides (B) used in the present invention include 4,4′-diphenylmethane bismaleimide, polyphenylmethane bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethanebis. Maleimide, N, N′-4,4 ′-[3,3′-dimethyl-diphenylmethane] bismaleimide, N, N′-4,4 ′-[3,3′-diethyldiphenylmethane] bismaleimide, N, N '-(4,4-diphenylmethane) bisreimide, 2,2'-bis [4- (4-maleimidophenoxy) phenyl] propane, N, N'-m-phenylenebismaleimide, 4-methyl-1,3-phenylene Bismaleimide, N, N′-4,4′-biphenylenebismaleimide, N, N′-4,4 ′-[3,3′-dimethyl-biphenylene] bismaleimide, 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-maleimidophenoxy) -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-maleimide) Phenoxy) phenyl] -tricyclo- [5,2,1, O ^2.6 ] decane, 4,9-bis [4- (4-maleimidophenoxy) phenyl] -tricyclo- [5,2,1, O ^2.6 ] decane, However, the present invention is not particularly limited thereto.

  Among such maleimide compounds (B), in particular, 4,4′-diphenylmethane bismaleimide, polyphenylmethane bismaleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl. -5,5'-diethyl-4,4'-diphenylmethane bismaleimide is preferred from the viewpoint of easy industrial availability.

  In the thermosetting composition of the present invention, the blending ratio of the phenol resin composition (A) and the maleimides (B) is not particularly limited, and [phenol resin composition (A) / maleimides ( B)] is usually in the range of 1/3 to 3/1, and particularly preferably in the range of 1 / 2.5 to 2.5 / 1 from the viewpoint of flame retardancy.

  In addition to the phenol resin composition (A) and the maleimides (B), the thermosetting composition of the present invention can be used in combination with an epoxy resin (C) to form an epoxy resin composition.

  Various epoxy resins can be used as the epoxy resin (C) that can be used in the epoxy resin resin composition of the present invention. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S can be used. From divalent phenols such as epoxy resin, bisphenol AD 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 Induced epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol modification Type 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 novolac type epoxy resin, aromatic Examples include, but are not limited to, epoxy resins derived from trivalent or higher phenols such as hydrocarbon formaldehyde resin-modified phenolic resin-type epoxy resins and biphenyl-modified novolac-type epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  Furthermore, 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 novolac 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 Resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensation novolac type epoxy resin, naphthol-cresol co-condensation It is preferable to use a borak type epoxy resin or a biphenyl-modified novolak type epoxy resin. In order to improve the heat resistance of bifunctional epoxy resins such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenyl It is particularly preferable to use a polyfunctional epoxy resin such as an ethane type epoxy resin or a naphthol novolac type epoxy resin.

  Although the usage-amount of the said epoxy resin can be suitably selected according to a use, resin obtained by condensation reaction of the compound (x2) and aldehydes (x3) which have phenols (x1), a carboxyl group, and an amino group simultaneously. The equivalent ratio of the phenolic hydroxyl group (a) contained in the epoxy resin (C) to the epoxy group (c) contained in the epoxy resin (C), [(c) / (a)] in the range of 0.3 to 2.0. It is preferable from the point that both can fully react.

Moreover, when using an epoxy resin (C), a phenolic curing agent can be used together as a curing agent used for curability control. For example, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin , Dicyclopentadiene phenol addition resin, phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin, biphenyl modified phenol aralkyl resin, phenol trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin Naphthol-cresol co-condensed novolak resin, biphenyl modified phenolic resin, aminotriazine modified phenolic resin, bisphenol A novolak resin, bisphenol Polyhydric phenol compounds including Lumpur F novolac resin, and include modified products of these.
Further, a curing accelerator can be used in the thermosetting resin composition and the epoxy resin composition of the present invention as required. Examples of the curing accelerator include carboxylic acid compounds, phosphorus compounds, and tertiary compounds. Examples include amines, imidazoles, organic acid metal salts, Lewis acids, organic peroxides, inorganic peroxides, and amine complex salts.

  In addition, the thermosetting resin composition and the epoxy resin composition of the present invention include various inorganic fillers, flame retardants, pigments, silane coupling agents, mold release agents, modifiers, and the like as necessary. The compounding agent can be added.

  Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When it is desired to increase the blending amount of the inorganic filler, fused silica is preferable. The fused silica may be either crushed or spherical, but a spherical one is preferred in order to increase the blending amount of fused silica and to suppress an increase in the melt viscosity of the molding material. The filling rate can be appropriately selected depending on the application and desired characteristics. For example, when used for a semiconductor encapsulant, the higher one is preferable from the viewpoint of linear expansion coefficient and flame retardancy, specifically, 65% by weight or more, preferably 85% by weight or more with respect to the total amount of the composition. It is. 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.

  Examples of the flame retardant imparting agent include phosphorus atom-containing compounds, nitrogen atom-containing compounds, inorganic flame retardant compounds, and the like, and halogen-based flame retardants may be used in applications where there is no requirement for halogen-free. Specifically, 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, triphenyl phosphate, triphenyl phosphate Cresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, tris (2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, phosphate esters, ammonium polyphosphate, polyphosphorus Condensed amides such as acid amide, red phosphorus, guanidine phosphate, dialkylhydroxymethylphosphonate Phosphorus atom-containing compound such as ester compounds, nitrogen-containing compounds such as melamine, aluminum hydroxide, magnesium hydroxide, zinc borate, and inorganic flame retardant compounds such as calcium borate.

  Examples of the modifier include phenoxy resin, polyamide resin, polyimide resin, polyetherimide resin, polyether sulfone resin, polyphenylene ether resin, polyphenylene sulfide resin, polyester resin, polystyrene resin, and polyethylene terephthalate resin. It is done.

  The thermosetting resin composition and the epoxy resin composition of the present invention can be preferably used for so-called electrical and electronic component applications, for example, for printed circuit boards such as prepregs for copper foil laminates and interlayer insulation materials for build-up printed circuit boards. Applications such as resin compositions, semiconductor chip sealing materials, tape-like sealants, potting type liquid sealing materials, underfill materials, sealing resin compositions for semiconductor interlayer insulation materials, and conductive pastes Can be mentioned. Moreover, the hardened | cured material of this invention can be obtained by heat-hardening the said thermosetting resin composition by a conventional method according to each use.

  The resin composition for prepreg for printed circuit boards can be prepared by varnishing the above components with an organic solvent. Examples of the organic solvent include alcohol 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. Examples include solvents having a boiling point of 160 ° C. or lower, such as aprotic polar solvents. These can be used as a mixed solvent of two or more as appropriate. Here, among the organic solvents used, an alcohol solvent and an aprotic polar solvent are particularly preferable in terms of low volatility and good solubility.

  In order to produce a prepreg that is a cured product from such a resin composition for a prepreg for a printed circuit board, the varnish obtained as described above is made of paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat. And a method of impregnating various reinforcing base materials such as glass roving cloth and heating and curing at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C. At this time, the weight ratio of the resin composition to be used and the reinforcing substrate is not particularly limited, but it is usually preferable to adjust the resin content in the prepreg to be 20 to 60% by weight.

  In addition, the copper-clad laminate is obtained by laminating a plurality of prepregs obtained in this manner, appropriately stacking copper foil, and heating at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa. It can manufacture by making it crimp.

  Next, the interlayer insulating material for build-up substrates can be adjusted, for example, by appropriately blending rubber, filler and the like with the above-described thermosetting composition of the present invention. The cured product in such an application is obtained by applying the obtained composition to a wiring board on which a circuit has been formed using a spray coating method, a curtain coating method, or the like, and then curing by heating. 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. 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.

  Next, the method for preparing the semiconductor encapsulating material is prepared by premixing the thermosetting composition of the present invention together with additives such as a coupling agent and a release agent, followed by an extruder, A method of thoroughly mixing until uniform using a roll, roll or the like can be mentioned.

  When using the thus obtained semiconductor encapsulating material as a tape-shaped encapsulant, the resin composition obtained by the above-described method is heated to produce a semi-cured sheet, After that, this sealing agent tape is placed on a semiconductor chip, heated to 100 to 150 ° C., softened and molded, and completely cured at 170 to 250 ° C ..

  When used as a potting liquid sealant, the resin composition obtained by the above-described method is dissolved in a solvent as necessary, and then applied to a semiconductor chip or electronic component and directly cured. Just do it.

  When the thermosetting resin composition and the epoxy resin composition of the present invention are used as an underfill resin, 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 and the epoxy resin composition of the present invention are used as an interlayer insulating material for a semiconductor, the interlayer insulating material can be adjusted by, for example, a method described in JP-A-6-85091. Note that when used for an interlayer insulating film, it is in direct contact with the semiconductor, so that the linear expansion coefficient of the insulating material can be made close to the linear expansion coefficient of the semiconductor so that cracks due to differences in the linear expansion coefficient do not occur in a high temperature environment. preferable. 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.

  When the thermosetting resin composition and the epoxy resin composition of the present invention are used as a conductive paste, for example, as described in JP-A-3-46707, fine conductive particles are contained in the resin composition. In addition to being able to adjust the composition for anisotropic conductive film by dispersing it in JP-A-62-40183, JP-A-62-76215, JP-A-62-176139, etc. By the method, it is possible to obtain a paste resin composition for circuit connection or an anisotropic conductive adhesive that is liquid at room temperature.

  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.

  As a compound (x2) having both a carboxyl group and an amino group used in the following synthesis examples, BAG manufactured by Nissei Chemical Industry Co., Ltd. represented by Chemical Formula 3 was used.

  Presence / absence of methylol groups in the phenol resin composition (A) obtained in the following synthesis examples and synthesis comparative examples, and the amount of unreacted phenol monomer were determined as follows.

<Presence or absence of methylol group>
The methylol group present in the resin composition was measured using C13-NMR. The equipment used, measurement conditions, and judgment criteria are as follows.

Apparatus: GSX270 proton manufactured by JEOL Ltd .: 270 MHz,
Measurement solvent: heavy methanol or heavy acetone, heavy dimethyl sulfoxide,
Reference substance: tetramethylsilane.

  Judgment criteria: Focusing on 60 to 70 ppm of the obtained chart, judgment was made using a peak that can be clearly distinguished from noise. The case where a peak was observed was “present”, and the case where a peak was not observed was “absent”.

<Amount of monofunctional phenols>
Measurement was performed under the following conditions using gas chromatography.

Column: 30% Celite 545 carnauba wax 2m x 3mmΦ,
Column temperature: 170 ° C.
Inlet temperature: 230 ° C
Detector: FID,
Carrier gas: N ₂ gas 1.0 kg / cm ² ,
Measurement method: Under the measurement conditions of the internal standard method, the amount of unreacted monofunctional phenol monomer in the phenol resin composition (A) was measured.

<Presence / absence of unreacted aldehydes>
The presence or absence of unreacted aldehydes present in the phenol resin composition during the reaction was measured using FT-IR.

Apparatus: FT / IR-500 manufactured by JASCO Corporation. The reaction mixture was applied to a KBr plate and judged using a peak derived from an aldehyde group observed in the vicinity of 1700 cm ⁻¹ of the obtained chart. The case where a peak was observed was “present”, and the case where a peak was not observed was “absent”.

Example 1
A reactor equipped with a condenser and an atmospheric pressure and vacuum distillation apparatus was charged with 940 parts of phenol, 185 parts of BAG, 434 parts of 41.5% formalin, and 3 parts of triethylamine, and the temperature was raised to 115 ° C. and reacted for 2 hours. . Next, the temperature was raised to 135 ° C. during atmospheric distillation and reacted for 2 hours as it was, and the temperature was raised to 180 ° C. again while performing atmospheric distillation, followed by distillation under reduced pressure at 180 ° C., and low boiling points such as unreacted monomers and water. The component was removed to obtain 780 parts of a resin having a softening point of 123 ° C. 60 parts of the obtained resin was dissolved in 40 parts of methyl ethyl ketone at 75 ° C. to obtain a resin solution having a solid content of 60%. This resin solution is designated as “N1”. The solid content in the obtained phenol resin composition had a methylol group amount of “no”, unreacted aldehydes of “no”, and an unreacted phenol monomer amount of 0.1% by weight.

Example 2
The reaction was conducted in the same manner as in Example 1 except that the charging ratio was changed to 1080 parts of o-cresol, to obtain 840 parts of a resin having a softening point of 116 ° C. 60 parts of the obtained resin was dissolved in 40 parts of methyl ethyl ketone at 75 ° C. to obtain a resin solution having a solid content of 60%. This resin solution is designated as “N2”. The solid content in the obtained phenol resin composition was “no” for methylol groups, “no” for unreacted aldehydes, and 0.2% by weight for the amount of unreacted cresol monomer.

Example 3
A reactor equipped with a condenser and an atmospheric pressure and vacuum distillation apparatus was charged with 940 parts of phenol, 92 parts of BAG, 50 parts of melamine, 434 parts of 41.5% formalin, and 3 parts of triethylamine. Reacted for hours. Next, the temperature was raised to 135 ° C. with atmospheric distillation, reacted for 2 hours as it was, heated again to 150 ° C. with atmospheric distillation again, reacted for 2 hours, and then lowered to 95 ° C. 170 parts of 41.5% formalin was added dropwise to the reaction system, and the temperature was raised to 100 ° C. and reacted for 2 hours. Next, the temperature was raised to 135 ° C. during atmospheric distillation and reacted for 2 hours as it was, and the temperature was raised to 180 ° C. again while performing atmospheric distillation, followed by distillation under reduced pressure at 180 ° C., and low boiling points such as unreacted monomers and water. The component was removed to obtain 730 parts of a resin having a softening point of 117 ° C. 60 parts of the obtained resin was dissolved in 40 parts of methyl ethyl ketone at 75 ° C. to obtain a resin solution having a solid content of 60%. This resin solution is designated as “N3”. The solid content in the obtained phenol resin composition had a methylol group amount of “no”, unreacted aldehydes of “no”, and an unreacted phenol monomer amount of 0.2% by weight.

Example 4
A reactor equipped with a condenser and an atmospheric pressure and vacuum distillation apparatus was charged with 940 parts of phenol, 151 parts of melamine, and 434 parts of 41.5% formalin, heated to 100 ° C., and allowed to react for 2 hours. 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 to obtain 740 parts of a resin having a softening point of 136 ° C. 60 parts of the obtained resin was dissolved in 40 parts of methyl ethyl ketone at 75 ° C. to obtain a resin solution having a solid content of 60%. This resin solution is designated as “N4”. The solid content in the obtained phenol resin composition was “no” methylol group, “no” unreacted aldehydes, and 0.9% by weight unreacted phenol monomer.

Examples 5-8 and Comparative Examples 1-6
In accordance with the ratios shown in Table-1 and Table-2, varnishes were prepared by the following method, 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 to Table-2.

[Preparation of varnish]
In the varnish, the phenol resin composition (A) represented by N1 to N4, the maleimide compound (B), and the epoxy resin (C) were mixed, and finally the non-volatile content (NV) of the composition was 55. %.

[Laminate production conditions]
Base material: 180 μm; Nitto Boseki Co., Ltd. glass cloth “WEA 7628 H258” ply number: 8, prepregization condition: 160 ° C./4 minutes, copper foil: 35 μm; Furukawa Sark Wheel Co., Ltd. Molded at / cm ² for 1.0 hour. Plate thickness: 1.6 mm, resin content: 40%.

[Physical property test conditions]
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 properties: After removing the copper foil by etching, the dielectric constant and dielectric loss tangent were measured at a frequency of 100 MHz and 1 GHz using a dielectric property evaluator (test piece size 75 × 25 × 2 mm).
Combustion test: Compliant with UL-94 vertical test.
Oven heat resistance: Using a constant temperature bath with an air circulation device, test pieces (50 mm x 50 mm) are treated for 1 hour under the conditions of 220 ° C, 240 ° C, 260 ° C. ○, a case where several blisters having a diameter of 5 mm or less occurred was evaluated as Δ.

  In addition, each raw material and symbol in Table-1 to Table-2 are as follows.

BMI-5000: bis (3-ethyl-5-methyl-4-maleimidophenyl) methane (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
"830-S": Bisphenol F type epoxy resin (Dainippon Ink and Chemicals, trade name [EPICLON 830-S], epoxy equivalent 171 g / eq.), "N-690": Cresol novolac type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name [EPICLON N-690], epoxy equivalent 216 g / eq.), “1121N-80M”: Brominated epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name [ EPICLON 1121N-80M], epoxy equivalent 490 g / eq. (Solid content), non-volatile content 80%), “MEK”: methyl ethyl ketone, “DMF”: dimethylformamide

Claims (9)

Phenols (x1) and the following structural formula (1)

A phenol resin composition (A) containing a condensate (I) obtained by reacting a compound (x2) having a carboxyl group and an amino group, and an aldehyde (x3), and a maleimide (B And a weight ratio of [phenol resin composition (A) / maleimides (B)], usually in a range of 1/3 to 3/1. object. The thermosetting resin composition according to claim 1, wherein the aldehyde (x3) is one or more compounds selected from the group consisting of formaldehyde, hydroxybenzaldehyde, hydroxybiphenylaldehyde, and hydroxynaphthaldehyde. The maleimides (B) are 4,4′-diphenylmethane bismaleimide, polyphenylmethane maleimide, 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane, 3,3′-dimethyl-5,5. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is one or more compounds selected from the group consisting of '-diethyl-4,4'-diphenylmethane bismaleimide. In addition to the phenols (x1), the compound (x2) having the carboxyl group and the amino group, and the aldehydes (x3), the condensate (I) may contain (x1), (x2), or ( The thermosetting resin composition according to any one of claims 1 to 3 , which is obtained by adding a triazine ring-containing compound (x4) other than x3) to react. The thermosetting resin composition according to claim 4, wherein the triazine ring-containing compound (x4) is one or more compounds selected from the group consisting of melamine, acetoguanamine and benzoguanamine. A condensate obtained by reacting a phenol (x1), an aldehyde (x3), and a triazine ring-containing compound (x4) in addition to the thermosetting resin composition according to any one of claims 1 to 5. (III) is used as a raw material of the compound (x4) having a triazine ring in the finally obtained thermosetting resin composition [compound having a triazine ring (x4) / phenols (x1) ) = 0.01 to 1.50 (molar ratio)] . The thermosetting resin composition according to claim 6, wherein the triazine ring-containing compound (x4) is one or more compounds selected from the group consisting of melamine, acetoguanamine and benzoguanamine. The thermosetting resin composition according to any one of claims 1 to 7 and the epoxy resin (C) are contained in the phenolic hydroxyl group (a) and the epoxy resin (C) in the composition. The epoxy resin composition which contains in the range whose equivalent ratio with an epoxy group (c), [(c) / (a)] is 0.3-2.0 . A cured product obtained by heat-curing the composition according to any one of claims 1 to 8.