JP6519128B2 - Thermosetting resin composition and method for producing the same, and prepreg, laminate and printed wiring board using the same - Google Patents

Description

  The present invention relates to a thermosetting resin composition and a method for producing the same, and a prepreg, a laminate and a printed wiring board using the same.

  With the trend of miniaturization and high performance of electronic devices in recent years, in the printed wiring board, advancement of wiring density and high integration progress, and along with this, there is a demand for reliability improvement of wiring laminates. It is getting stronger.

As a prepreg used for a package substrate for semiconductors, it is common to integrally mold a resin composition mainly composed of a thermosetting resin such as an epoxy resin and a glass woven fabric. A substrate containing glass cloth and a thermosetting resin is excellent in various properties such as heat resistance, dimensional stability, mechanical properties, electrical insulation, etc., but the occurrence of warpage at the time of semiconductor chip mounting becomes a major issue ing.
At the time of mounting, the main cause of the warpage occurring in the semiconductor package is the difference in thermal expansion between the semiconductor package substrate and the semiconductor chip mounted on the surface of the substrate, and the low modulus of elasticity of the semiconductor package substrate. Therefore, low thermal expansion and high elasticity of the semiconductor package substrate are required.

As a method of reducing the thermal expansion and increasing the elasticity of the package substrate for a semiconductor, a method of increasing the amount of the inorganic filler in the resin composition is generally performed (see, for example, Patent Documents 1 and 2).
However, when the inorganic filler in the resin composition is highly filled, the melt viscosity of the resin composition is increased, and there is a problem that the press molding becomes difficult, so improvement is desired.
In Patent Document 3, as a prepreg in which the inorganic filler is not unevenly distributed when producing a prepreg, a silane coupling agent, a titanate coupling agent, and two or more siloxane repeating units in the molecule and a functional group at the end are disclosed. A varnish obtained by mixing an inorganic filler-containing treatment agent solution and a resin material in which an inorganic filler is added to a treatment agent solution containing one or more treatment agents selected from the group consisting of silicone oligomers having A prepreg used is disclosed.

Japanese Patent Application Laid-Open No. 6-263843 JP 2012-149155 A JP 2000-212309 A

According to the technique of Patent Document 3, although uneven distribution of the inorganic filler can be suppressed, the melt viscosity of the resin composition is high, and improvement has been desired.
An object of the present invention is to provide a thermosetting resin composition having a low melt viscosity and excellent moldability, a method for producing the same, and a prepreg, a laminate and a printed wiring board using the same.

As a result of investigations to solve the above problems, the present inventors have found that the problems can be solved by the present invention described below.
That is, the present invention provides the following [1] to [13].
[1] A thermosetting resin composition comprising (A) a thermosetting resin and (B) an inorganic filler, wherein (B) the inorganic filler is (C) a titanate coupling agent in the absence of a solvent The thermosetting resin composition which is surface-treated by this.
[2] In the above [1], the amount of the (C) titanate coupling agent used in the surface treatment is 0.2 to 10 parts by mass with respect to 100 parts by mass of the (b) untreated inorganic filler. The thermosetting resin composition as described.
[3] (b) The thermosetting resin composition according to the above [2], wherein the untreated inorganic filler is silica.
[4] The above [1] to [1], wherein the content of the (B) inorganic filler in the thermosetting resin composition is 10 to 400 parts by mass with respect to 100 parts by mass of the (A) thermosetting resin. The thermosetting resin composition in any one of 3].
[5] (A) Thermosetting resin is (A1) epoxy resin, (A2) maleimide compound having two or more N-substituted maleimide groups in one molecule, and two or more amino groups in one molecule A thermosetting compound according to any one of the above [1] to [4], which is one or more selected from a mixture with a compound having a and (A3) a compound having two or more cyanate groups in one molecule. Resin composition.
[6] The thermosetting resin composition according to any one of the above [1] to [5], which further contains (D) a silicone compound.
[7] The thermosetting resin composition according to [6] above, wherein the (D) silicone compound has one or more reactive functional groups.
[8] The thermosetting resin composition according to [7] above, wherein the reactive functional group is one or more selected from an amino group and a hydroxyl group.
[9] The thermosetting resin composition according to any one of the above [1] to [8], wherein the (C) titanate coupling agent is isopropyl triisostearoyl titanate.
[10] A prepreg formed by impregnating or coating a substrate with the thermosetting resin composition according to any one of the above [1] to [9].
[11] A laminated board obtained by laminating and forming the prepreg according to the above [10].
[12] A printed wiring board using the laminated board according to the above [11].
[13] The method for producing a thermosetting resin composition according to any one of the above [1] to [9], which comprises the following steps 1 to 3.
Step 1: (b) mixing the untreated inorganic filler and (C) a titanate coupling agent in the absence of solvent, (b) surface treating the untreated inorganic filler, (B) the inorganic filler Step 2: Obtain an organic solvent by adding the organic solvent to the (B) inorganic filler obtained in Step 1 and mixing to obtain a dispersion liquid of (B) inorganic filler Step 3: Obtained in Step 2 (B) A step of mixing a dispersion of an inorganic filler and (A) a thermosetting resin to obtain a thermosetting resin composition

  According to the present invention, it is possible to provide a thermosetting resin composition having a low melt viscosity and excellent moldability, a method for producing the same, a prepreg using the same, a laminate and a printed wiring board.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention is a thermosetting resin composition containing (A) a thermosetting resin and (B) an inorganic filler, and the (B) inorganic filler is free from solvents. And (C) a surface-treated by a titanate coupling agent.

<(A) Thermosetting resin>
The thermosetting resin composition of the present invention contains (A) a thermosetting resin.
The thermosetting resin (A) is not particularly limited as long as it is a thermosetting resin. For example, epoxy resin, xylene resin, guanamine resin, diallyl phthalate resin, vinyl ester resin, phenol resin, unsaturated polyester resin And imide resins, urethane resins, maleic resins, melamine resins, cyanate resins, urea resins and the like. These (A) thermosetting resins can be used alone or in combination of two or more.
Among these, (A1) epoxy resin, (A2) a maleimide compound having two or more N-substituted maleimide groups in one molecule, and two or more in one molecule from the viewpoint of cured product physical properties and moldability. One or more selected from a mixture with a compound having an amino group, and a compound having two or more cyanate groups in one molecule (A3) are preferable. Each component will be described below.

((A1) Epoxy resin)
(A1) As an epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac Type epoxy resin, stilbene type epoxy resin, triazine skeleton containing epoxy resin, fluorene skeleton containing epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenylaralkyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, fat Examples thereof include cyclic epoxy resins, polyfunctional phenols, and diglycidyl ether compounds of polycyclic aromatics such as anthracene. Among these, from the viewpoint of moldability, a bisphenol A novolac epoxy resin is preferable.
You may use these epoxy resins individually or in combination of 2 or more types.
The epoxy equivalent of the epoxy resin (A1) is preferably 100 to 1000 g / mol, more preferably 130 to 500 g / mol, and still more preferably 150 to 300 g / mol from the viewpoint of cured product physical properties and moldability.

When using (A1) epoxy resin as a thermosetting resin (A1), it is preferable to use the curing agent for epoxy resins together.
As curing agents for epoxy resins, phenol resins; amine compounds such as dicyandiamide, diaminodiphenylmethane, diaminodiphenyl sulfone; acid anhydrides such as phthalic anhydride, pyromellitic anhydride, maleic anhydride, maleic anhydride copolymer, etc .; polyimide Etc. can be used.
Among these, phenol resins are preferable from the viewpoint of cured product physical properties and moldability. These epoxy resin curing agents may be used alone or in combination of two or more.

The phenolic resin is not particularly limited as long as it is a compound having two or more phenolic hydroxyl groups in one molecule, and, for example, in one molecule such as resorcinol, catechol, bisphenol A, bisphenol F and substituted or unsubstituted biphenol Compounds having two phenolic hydroxyl groups, aralkyl type phenol resin, dicyclopentadiene type phenol resin, triphenylmethane type phenol resin, novolak type phenol resin, benzaldehyde type phenol and copolymerization type phenol resin of aralkyl type phenol, Paraxylylene and / or metaxylylene modified phenolic resin, melamine modified phenolic resin, terpene modified phenolic resin, dicyclopentadiene type naphthol resin, cyclopentadiene modified phenolic resin, polycyclic aromatic ring modified Phenol resins, biphenyl type phenol resins, and phenolic resins obtained by copolymerizing two or more of these.
The hydroxyl group equivalent of the phenol resin is not particularly limited, but is preferably 50 to 200 g / mol, more preferably 60 to 150 g / mol, still more preferably 80 to 120 g / mol from the viewpoint of cured product physical properties and moldability. .
The content of the phenol resin in the thermosetting resin composition is preferably 10 to 100 parts by mass, more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the epoxy resin from the viewpoint of cured product physical properties and moldability. Part, more preferably 30 to 70 parts by mass.
The equivalent ratio [(OH) / (Ep)] of the hydroxyl group of the phenol resin in the thermosetting resin composition and the epoxy group of the epoxy resin is preferably 0.7 to 1 from the viewpoint of the physical properties of the cured product and the moldability. .3, more preferably 0.8 to 1.2, still more preferably 0.9 to 1.1.

When using (A1) epoxy resin as a thermosetting resin (A1), you may use a hardening accelerator together as needed.
As the curing accelerator, conventionally known curing accelerators can be used. Specifically, a heterocyclic compound such as an imidazole compound or an epoxy adduct or a microencapsulate thereof, DBU (1,8-diazabicyclo (4.5.0) undecen-7) or a derivative thereof; a secondary amine compound; Tertiary amine compounds; organic phosphine compounds such as triphenylphosphine; and onium salt compounds such as quaternary ammonium salts, tetraphenylphosphonium salts, and tetraphenyl borate salts. These curing accelerators may be used alone or in combination of two or more.
The content of the curing accelerator in the thermosetting resin composition is preferably 0.01 to 5 parts by mass, more preferably 100 parts by mass of the epoxy resin, from the viewpoint of achieving both curability and storage stability. Is 0.05 to 2 parts by mass, more preferably 0.1 to 1 parts by mass.

((A2) A mixture of a maleimide compound having two or more N-substituted maleimide groups in one molecule and a compound having two or more amino groups in one molecule)
The thermosetting resin composition of the present invention is a maleimide compound having two or more N-substituted maleimide groups in one molecule as (A) a thermosetting resin (hereinafter simply referred to as “(A2-1) It is preferable to use a mixture of a maleimide compound ") and a compound having two or more amino groups in one molecule (hereinafter, also simply referred to as" (A2-2) amine compound ").

[(A2-1) maleimide compound]
The (A2-1) maleimide compound is not particularly limited as long as it is a compound having two or more N-substituted maleimide groups in one molecule, and, for example, N, N'-ethylenebismaleimide, N, N'-hexa Methylene bis maleimide, N, N'- (1, 3- phenylene) bis maleimide, N, N'- [1, 3- (2- methyl phenylene)] bis maleimide, N, N'- [1, 3- (3- 4-Methylphenylene)] bismaleimide, N, N '-(1,4-phenylene) bismaleimide, bis (4-maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, bis (4-mer) Imidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) methane, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4 -Bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4 4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1, 2-Bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2 Bis [4- (4-maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) Phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoro Propane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, bis [4- (3-maleimidophenoxy] C) Phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2'-bis (4-maleimidophenyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-) Maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-Maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) ) Phenyl] ether, 1,4-bis [4 -(4-Maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- ( 3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4- Maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1 , 4-Bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy) -3 Examples thereof include 5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmethane maleimide and the like.
Among these, bis (4-maleimidophenyl) methane is preferable from the viewpoint of solubility in a solvent.
You may use these (A2-1) maleimide compounds individually or in combination of 2 or more types.

  (A2-1) As a maleimide compound, For example, "BMI", "BMI-70", "BMI-80" (above, Kei-I Kasei Co., Ltd. product), "BMI-1000", "BMI-1100" , "BMI-2000", "BMI-2300", "BMI-3000", "BMI-4000", "BMI-5100", "BMI-7000" (all manufactured by Daiwa Kasei Kogyo Co., Ltd., trade names) Etc. are commercially available.

[(A2-2) amine compound]
Examples of the amine compound (A2-2) include aromatic amine compounds, aliphatic amine compounds, triazine compounds, and the like.
As an aromatic amine compound, for example, m-phenylenediamine, p-phenylenediamine, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,3,5,6-tetra Methyl-p-phenylenediamine, 2,4-diaminomesitylene, m-xylene-2,5-diamine, m-xylylenediamine, p-xylylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-bis (amino-t-butyl) toluene, 2,4-diaminoxylene, 2,4-diaminopyridine, 2,6-diaminopyridine, 2,5-diaminopyridine, 2,4-diaminodurene, 4 5-Diamino-6-hydroxy-2-mercaptopyrimidine, 3-bis (3-aminobenzyl) benzene, 4-bis ( -Aminobenzyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-Aminophenoxy) benzene, 3-bis (3- (3-aminophenoxy) phenoxy) benzene, 4-bis (4- (4-aminophenoxy) phenoxy) benzene, 3-bis (3- (3- 3-Aminophenoxy) phenoxy) phenoxy) benzene, 4-bis (4- (4- (4-aminophenoxy) phenoxy) phenoxy) benzene, 3-bis (α, α-dimethyl-3-aminobenzyl) benzene, 1 , 4-Bis (α, α-dimethyl-3-aminobenzyl) benzene, 3-bis (α, α-dimethyl-4-aminobenzyl) benzene, bis 4-Methylaminopentyl) benzene, p-bis (2-methyl-4-aminopentyl) benzene, 1,4-bis (3-aminopropyldimethylsilyl) benzene, bis [(4-aminophenyl) -2-propyl] 1,4-benzene, 2,5-diaminobenzenesulfonic acid, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3 ', 5,5'-Tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3'-dimethyl-5,5'-diethyl-4,4 '-Diaminodiphenylmethane, 4,4'-methylene-bis (2-chloroaniline), 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenyl Ethane, 2,2′-diaminodiphenylpropane, 3,3′-diaminodiphenylpropane, 4,4′-diaminodiphenylpropane, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, 2, 2′-Bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 3- (2 ′, 4′-diaminophenoxy) propanesulfonic acid, bis (4-aminophenyl) diethylsilane, 3,3′- Diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, bis (4-amino-t- Butylphenyl) ether, 4,4'-diaminodiphenylether-2,2'-disulfonic acid, 3,3'-di Aminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, benzidine, 2,2'-dimethyl- 4,4'-Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'- Diaminobiphenyl-6,6'-disulfonic acid, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 3,3'-dichloro-4,4'-diaminobiphenyl, 3,3 '-Dichloro-4,4'-diaminobiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenyl sulfide, 4,4'-diamino-3,3'- Phenyldiol, 1,5-diaminonaphthalene, 1,4-diaminonaphthalene, 2,6-diaminonaphthalene, 9,9'-bis (4-aminophenyl) fluorene, 9,9'-bis (4-aminophenyl) Examples include fluorene-2,7-disulfonic acid, 9,9'-bis (4-aminophenoxyphenyl) fluorene, diaminoanthraquinone, 3,7-diamino-2,8-dimethyldibenzothiophene sulfone and the like.

Examples of aliphatic amine compounds include ethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,5-dimethylhexamethylenediamine, Methoxy hexamethylene diamine, 2, 5- dimethyl hepta methylene diamine, 3- methyl hepta methylene diamine, 4, 4- dimethyl hepta methylene diamine, 5- methyl nona methylene diamine, 1, 4- diamino cyclohexane, 1,3- bis ( 3-aminopropyl) tetramethyldisiloxane, 2,5-diamino-1,3,4-oxadiazoyl, bis (4-aminocyclohexyl) methane and the like.
Examples of the triazine compounds include melamine; benzoguanamine, acetoguanamine, 2,4-diamino-6-vinyl-s-triazine, 2,4-diamino-6-allyl-s-triazine, 2,4-diamino-6- Guanamine compounds such as acryloyloxyethyl-s-triazine and 2,4-diamino-6-methacryloyloxyethyl-s-triazine are exemplified.

Among these, m-phenylenediamine, p-phenylenediamine, 1,4-bis (4-aminophenoxy) benzene, 4,4 ′ which are aromatic amine compounds from the viewpoint of having excellent reactivity and heat resistance. -Diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 2,2'-bis [4- (4-aminophenoxy) phenyl Propane, 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylether, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone , Benzidine, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenylsul P-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-biphenyldiol and benzoguanamine which is a guanamine compound are preferable, and are inexpensive. '-Diaminodiphenylether, 3,3'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'- Diaminodiphenylmethane and benzoguanamine are more preferable, and 3,3'-diaminodiphenylsulfone and 3,3'-diethyl-4,4'-diaminodiphenylmethane are more preferable from the viewpoint of toxicity and solubility in a solvent.
These (A2-2) amine compounds may be used alone or in combination of two or more.

  The amount of the (A2-2) amine compound used in the thermosetting resin composition of the present invention is preferably 30 parts by mass with respect to 100 parts by mass of the (A2-1) maleimide compound from the viewpoint of cured product physical properties and moldability. The amount is 100 to 100 parts by mass, more preferably 45 to 85 parts by mass, and still more preferably 55 to 75 parts by mass.

((A3) a compound having two or more cyanate groups in one molecule)
The thermosetting resin composition of the present invention is a compound (A3) having two or more cyanate groups in one molecule as the thermosetting resin (A) (hereinafter, also simply referred to as "(A3) cyanate compound") It is preferable to use
(A3) The cyanate compound is not particularly limited as long as it is a compound having two or more cyanate groups in one molecule, and, for example, novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, bisphenol F Type cyanate resin, tetramethyl bisphenol F type cyanate resin, and the like. These (A3) cyanate compounds may be used alone or in combination of two or more.
Among these, novolak-type cyanate resins and bisphenol A-type cyanate resins are preferable from the viewpoint of being excellent in dielectric properties, heat resistance, low thermal expansion and flame retardancy, and inexpensive.

The average repeat number of the novolac-type cyanate resin is not particularly limited, but is preferably 1 to 30, and more preferably 1 to 25. When the average number of repeats is 1 or more, crystallization is difficult and handling becomes easy, and when it is 30 or less, the cured product has an appropriate hardness.
As bisphenol A type cyanate resin, for example, “Arocy B-10”, “Primaset (registered trademark) BADCy” (trade name, manufactured by Ronza Japan Co., Ltd.), and as the novolac type cyanate resin, “primaset”. (Registered trademark) PT-30 "(weight average molecular weight 500 to 1,000)," Primaset (registered trademark) PT-60 "(weight average molecular weight 2,000 to 3,000) (all, Lonza Japan Co., Ltd.) (Trade names) are commercially available.

  The cyanate equivalent of the cyanate compound (A3) is not particularly limited, but is preferably 60 to 300 g / mol, more preferably 90 to 200 g / mol, still more preferably 120 to 160 g / mol from the viewpoint of cured physical properties and moldability. It is.

In the case of using the (A3) cyanate compound as the thermosetting resin (A3), it is preferable to use a curing accelerator for the (A3) cyanate compound from the viewpoint of improving heat resistance, flame retardancy, copper foil adhesion, etc. .
(A3) As a curing accelerator for cyanate compounds, organic metal salts such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, etc .; imidazoles and derivatives thereof; tertiary amines; quaternary ammonium Salt etc. are mentioned.
The amount of the curing accelerator for the (A3) cyanate compound used is preferably 0.000005 to 0.001 parts by mass, and more preferably 0.00005 to 0.0002 parts by mass with respect to 100 parts by mass of the (A3) cyanate compound. It is a mass part.

The (A3) cyanate compound may be reacted before blending the (B) inorganic filler, and the reaction rate is preferably 30 to 70 mol%, more preferably 40 to 65 mol%. (A3) It can suppress that the fluidity of the prepreg obtained by coating becomes too large that the reaction rate of the cyanate compound is 30 mol% or more, and it is obtained by coating when it is 70 mol% or less. The flowability of the prepreg can be improved.
The silicone compound (D) described later may be added after the reaction of the (A3) cyanate compound, but is preferably added at the time of the reaction of the (A3) cyanate compound.
Here, the reaction rate of the (A3) cyanate compound is determined from the measurement result of GPC (gel permeation chromatography) measurement, and specifically, can be measured by the method described in the examples.

In the thermosetting resin composition of the present invention, the content of the (A) thermosetting resin is preferably 25 to 90% by mass, more preferably 30 to 70% by mass, and still more preferably 35 to 55% by mass. . When the content of the thermosetting resin (A) is 25% by mass or more, excellent chemical resistance can be obtained, and when the content is 90% by mass or less, excellent low thermal expansion can be obtained. .
In addition, in this specification, "the mass of (A) thermosetting resin" means that mass, when using said (A) thermosetting resin independently, and it uses together a hardening agent, a hardening accelerator, etc. When it does, it means the total mass which added these masses. However, (D) silicone compound mentioned later shall not be included in the mass of (A) thermosetting resin. Moreover, the mass of the organic solvent mentioned later shall be not included in "mass of a thermosetting resin composition."

<(B) Inorganic filler>
The thermosetting resin composition of the present invention comprises (B) an inorganic filler surface-treated with (C) a titanate coupling agent in the absence of a solvent.
The content of the (B) inorganic filler in the thermosetting resin composition of the present invention is preferably 10 to 400 parts by mass, more preferably 50 to 400 parts by mass with respect to 100 parts by mass of (A) thermosetting resin. It is a mass part, More preferably, it is 100-250 mass parts, Especially preferably, it is 120-180 mass parts.

The average particle size of the inorganic filler (B) is preferably 0.05 to 30 μm, more preferably 0.1 to 10 μm, still more preferably 0.15 to 8 μm, particularly preferably 0.2 to 2 μm, and very preferably 0.2 to 1 μm.
(B) By setting the average particle diameter of the inorganic filler to 0.05 μm or more, the physical properties of the thermosetting resin composition can be improved, and by setting the average particle diameter to 30 μm or less, the mixing probability of coarse particles is reduced. The occurrence of defects caused by coarse particles can be suppressed.
In addition, two or more types of inorganic fillers having different average particle sizes may be used in combination.
Here, the average particle diameter is the particle diameter of a point corresponding to 50% volume when the cumulative frequency distribution curve by particle diameter is determined with the total volume of particles as 100%, and the particle diameter using the laser diffraction scattering method It can measure with a distribution measuring device etc.

The (b) untreated inorganic filler (hereinafter also referred to as "(b) untreated inorganic filler") used for the preparation of the inorganic filler is not particularly limited, but, for example, silica; alumina; talc Mica, kaolin, aluminum hydroxide, boehmite, magnesium hydroxide, zinc borate, zinc stannate, zinc oxide, titanium oxide, titanium oxide, boron nitride, calcium carbonate, barium sulfate, aluminum borate, potassium titanate, E glass, T Glass, glass powder such as D glass, hollow glass beads, and the like.
Among these, silica is preferable from the viewpoint of dielectric properties, heat resistance, moldability, and low thermal expansion, and spherical silica is more preferable from the viewpoint of improving the flowability of the thermosetting resin composition.
Although the shape of the (b) untreated inorganic filler is not particularly limited, it is preferably spherical from the viewpoint of improving the flowability of the thermosetting resin composition.
Moreover, the average particle diameter of (b) untreated inorganic filler is the same as the average particle diameter of the said (B) inorganic filler, and its preferable aspect is also the same.
You may use these (b) untreated inorganic fillers individually or in combination of 2 or more types.

  Next, the (C) titanate coupling agent used for (b) surface treatment of an untreated inorganic filler will be described.

((C) Titanate coupling agent)
As the titanate coupling agent (C), for example, one having a structure represented by the following general formula (1) is preferably mentioned.
(R) _4-n- Ti-(X) _n (1)
(In general formula (1), X is an alkoxy group, R is an organic group, and n is an integer of 1 to 4.)

In general formula (1), X shows an alkoxy group. The carbon number of the alkoxy group is preferably 1 to 8, more preferably 2 or 3, and still more preferably 3.
Specific examples of the alkoxy group include, for example, ethylenedioxy group, isopropoxy group and the like, and among these, isopropoxy group is preferable. In addition, when X is ethylenedioxy, General formula (1) is represented by (R) ₂ -Ti-X.
In general formula (1), R shows an organic group. Specific examples of R include, for example, stearoyl group, isostearoyl group, octanoyl group, dioctyl pyrophosphate group, dioctyl phosphate group, N-aminoethyl-aminoethyl group, cumylphenyl group, dodecylbenzene sulfonyl group and the like. Among these, dodecylbenzenesulfonyl group or isostearoyl group is preferable, and isostearoyl group is more preferable.
n is an integer of 1 to 4, preferably an integer of 1 to 2, more preferably 1.

(C) As the titanate coupling agent, specifically, tetraoctyl bis (didodecyl phosphite) titanate, isopropyl (N-aminoethyl-aminoethyl) titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl triiso Stearoyl titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) ethylene titanate, tetraisopropyl bis (dioctyl phosphite) titanate, isopropyl trikamyl phenyl titanate Isopropyl tri (dioctyl phosphate) titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tridecyl benzene sulfonyl Titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl trioctanoyl titanate.
You may use these (C) titanate coupling agents individually or in combination of 2 or more types.

  (C) As a titanate coupling agent, for example, “Prenact (registered trademark) TTS”, “Prenact (registered trademark) 46 B”, “Prenact (registered trademark) 55”, “Prenact (registered trademark) 38 S”, “Prenact (Registered trademark) 41B, "Plenact (registered trademark) 138S", "Plenact (registered trademark) 238S", "Prenact (registered trademark) 338X", "Prenact (registered trademark) 9SA", "Prenact (registered trademark) 44" The Prenact series of E. et al. (Trade names, manufactured by Ajinomoto Fine Techno Co., Ltd.) are commercially available.

  The amount of the (C) titanate coupling agent used is preferably 0.2 to 10 parts by mass, more preferably 0.3 to 5 parts by mass, and further preferably 100 parts by mass of the untreated inorganic filler (b). Is 0.4 to 3 parts by mass, particularly preferably 0.5 to 1.5 parts by mass. The chemical resistance can be improved by setting the use amount of (C) titanate coupling agent to 0.2 parts by mass or more with respect to 100 parts by mass of (b) untreated inorganic filler, 10 parts by mass Heat resistance can be improved by setting it as the following.

<(D) silicone compound>
The thermosetting resin composition of the present invention preferably further contains (D) a silicone compound.
The silicone compound (D) is not particularly limited, but those having one or more reactive functional groups in the molecular structure are preferable, and those having two or more reactive functional groups in the molecular structure are more preferable. preferable.
Examples of the reactive functional group include one or more selected from an epoxy group, an amino group, a hydroxyl group, a methacryl group, a mercapto group, a carboxy group, an alkoxy group and the like. And one or more selected from an amino group and a hydroxyl group.

As a silicone compound which has an epoxy group in molecular structure, a commercial item can be used, for example, "X-22-163" (functional equivalent 200) which has an epoxy group at both ends, "KF-105" ( Functional group equivalent 490), "X-22-163A" (functional group equivalent 1000), "X-22-163B" (functional group equivalent 1750), "X-22-163C" (functional group equivalent 2700), both ends “X-22-169AS” (functional group equivalent weight 500) having an alicyclic epoxy group, “X-22-169B” (functional group weight equivalent 1700), and “X-22-1730X having an epoxy group at one end. (Functional group equivalent of 4500), “X-22-9002” (functional group equivalent of 5000) having epoxy groups at side chains and both ends, “X-22-343” (functional groups having epoxy groups at side chains Equivalent 525), “KF-101” (functional equivalent 350), “KF-1001” (functional equivalent 3500), “X-22-2000” (functional equivalent 620), “X-22-4741” Functional group equivalent 2500), "KF-1002" (functional group equivalent 4300), "X-22-2046" (functional group equivalent 600) having an alicyclic epoxy group in the side chain, "KF-102" (functional group Equivalent amount 3600) (above, Shin-Etsu Chemical Co., Ltd. product) is mentioned. You may use these individually or in combination of 2 or more types.
Among these, from the viewpoint of improving the heat resistance of the cured product to be obtained, “X-22-163A”, “X-22-163B”, “X-22-343”, “X-22-9002” KF-101 "is preferable," X-22-163A "and" X-22-163B "are more preferable, and" X-22-163B "is more preferable from the viewpoint of reducing the thermal expansion coefficient of the cured product to be obtained .

A commercial item can be used as a silicone compound which has an amino group in molecular structure, For example, "KF-8010" (functional group equivalent 430) which has an amino group at both ends, "X-22-161A" ( Functional group equivalent 800), "X-22-161B" (functional group equivalent 1500), "KF-8012" (functional group equivalent 2200), "KF-8008" (functional group equivalent 5700), "X-22-9409" (Functional group equivalent weight 700), "X-22-1660B-3" (functional group weight equivalent 2200) (above, Shin-Etsu Chemical Co., Ltd. product), "BY-16-853U" (functional group weight 460), " BY-16-853 "(functional group equivalent 650)," BY-16-853 B "(functional group equivalent 2200) (all available from Toray Dow Corning Co., Ltd.)," KF-868 having an amino group in the side chain " Functional group equivalent 8800), "KF-865" (functional group equivalent 5000), "KF-864" (functional group equivalent 3800), "KF-880" (functional group equivalent 1800), "KF-8004" (functional group Equivalent weight 1500) (above, Shin-Etsu Chemical Co., Ltd. product) are mentioned. You may use these individually or in combination of 2 or more types.
Among these, “X-22-161A”, “X-22-161B”, “KF-8012”, “KF-8008”, and “X-22-2” from the viewpoint of reducing the water absorption rate of the obtained cured product. 1660B-3 "and" BY-16-853B "are preferable, and from the viewpoint of reducing the thermal expansion coefficient of the obtained cured product," X-22-161A "," X-22-161B ", and" KF-8012 " Is more preferred.

  A commercial item can be used as a silicone compound which has a hydroxyl group in molecular structure, For example, "KF-6001" (functional group equivalent 900) which has a hydroxyl group at both ends, "KF-6002" (functional group equivalent 1600) ) “X-22-1821” (functional group equivalent 1470) having phenolic hydroxyl groups at both ends (above, Shin-Etsu Chemical Co., Ltd. product), “BY-16-752A” (functional group equivalent 1500) (above Toray Dow Corning Co., Ltd., “X-22-170BX” (functional group equivalent 2800) having a hydroxyl group at one end, “X-22-170DX” (functional group equivalent 4670), a hydroxyl group at the side chain And “X-22-4039” (functional group equivalent 970), “X-22-4015” (functional group equivalent 1870) (all manufactured by Shin-Etsu Chemical Co., Ltd.).

  As a silicone compound which has a methacryl group in molecular structure, a commercial item can be used, for example, "X-22-164A" (functional equivalent 860) which has a methacryl group at both ends, "X-22-164B. (Functional group equivalent 1630), “X-22-174DX” (functional group equivalent 4600) (all from Shin-Etsu Chemical Co., Ltd.) having a methacrylic group at one end can be mentioned.

  A commercial item can be used as a silicone compound which has a mercapto group in molecular structure, For example, "X-22-167B" (functional group equivalent 1670) which has a mercapto group at both ends, a mercapto group in a side chain And “KF-2001” (functional group equivalent 1900) and “KF-2004” (functional group equivalent 30000) (all manufactured by Shin-Etsu Chemical Co., Ltd.).

  As a silicone compound which has a carboxy group in molecular structure, a commercial item can be used, for example, "X-22-162C" (functional group equivalent 2300) which has a carboxy group at both ends, a carboxy group at one end And “X-22-3701E” (functional group equivalent weight 4000) (all from Shin-Etsu Chemical Co., Ltd.) having a carboxy group in the side chain. .

  As the silicone compound having an alkoxy group in the molecular structure, commercially available products can be used. For example, “FZ-3704” (functional equivalent weight 150) having an alkoxy group in the side chain (all, Toray Dow Corning (strain) Made).

  The functional group equivalent of the silicone compound (D) is not particularly limited, but is preferably 400 to 30,000, more preferably 1,000 to 10,000, and still more preferably 1,1, from the viewpoint of cured product physical properties and moldability. It is 500-3,000.

  The above (D) silicone compounds may be used alone or in combination of two or more.

The compounding amount of the (D) silicone compound is preferably 1 to 100 parts by mass, more preferably 3 to 80 parts by mass, and still more preferably 5 to 50 parts by mass, with respect to 100 parts by mass of the (A) thermosetting resin. Particularly preferably, it is 7 to 20 parts by mass.
By setting the compounding amount of the silicone compound (D) to 1 part by mass or more with respect to 100 parts by mass of the thermosetting resin (A), the flowability of the thermosetting resin composition is improved, and 100 parts by mass or less By doing this, copper foil adhesion can be secured.

<Optional component>
The thermosetting resin composition of the present invention is a thermoplastic resin, an elastomer, an organic filler, a flame retardant, an ultraviolet absorber, an antioxidant, a photopolymerization initiator, and a fluorescent whitening insofar as the effects of the present invention are not impaired. You may contain an agent, an adhesive improvement agent, etc.

  As a thermoplastic resin, for example, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polycarbonate resin, polyester resin, polyamide resin, polyamide imide resin, polyimide resin, xylene resin, polyphenylene sulfide resin, polyether imide resin, poly Ether ether ketone resin, polyether imide resin, silicone resin, tetrafluoroethylene resin etc. are mentioned.

  Examples of the elastomer include polybutadiene, acrylonitrile, epoxy-modified polybutadiene, maleic anhydride-modified polybutadiene, phenol-modified polybutadiene and carboxy-modified acrylonitrile.

  The organic filler is, for example, a resin filler made of polyethylene, polypropylene, polystyrene, polyphenylene ether resin, silicone resin, tetrafluoroethylene resin, etc .; acrylic ester resin, methacrylic ester resin, conjugated diene resin etc. Examples thereof include resin fillers having a core-shell structure having a core layer in a rubber state, and a shell layer in a glass state made of an acrylic ester resin, a methacrylic ester resin, an aromatic vinyl resin, and a vinyl cyanide resin.

  Flame retardants include, for example, halogen-containing flame retardants containing bromine, chlorine and the like; triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphoric acid ester compounds, phosphorus flame retardants such as red phosphorus; sulfamine Nitrogen flame retardants such as acid guanidine, melamine sulfate, melamine polyphosphate and melamine cyanurate; phosphazene flame retardants such as cyclophosphazene and polyphosphazene; inorganic flame retardants such as antimony trioxide and the like.

As an ultraviolet absorber, a benzotriazole type ultraviolet absorber is mentioned, for example.
Examples of the antioxidant include hindered phenol-based and hindered amine-based antioxidants.
Examples of the photopolymerization initiator include benzophenones, benzyl ketals and thioxanthone photopolymerization initiators.
Examples of the fluorescent whitening agents include fluorescent whitening agents of stilbene derivatives.
Examples of the adhesion improver include urea compounds such as ureasilane; and coupling agents such as silanes and aluminates.

<Organic solvent>
The thermosetting resin composition of the present invention may be dissolved in an organic solvent to form an organic solvent solution (hereinafter also referred to as "varnish").
The organic solvent is not particularly limited as long as it can dissolve the resin component constituting the thermosetting resin composition of the present invention and can disperse the (B) inorganic filler, for example, Alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as acetic acid ethyl ester and γ-butyrolactone; Ether solvents such as toluene; aromatic solvents such as toluene, xylene and mesitylene; nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; sulfur atom-containing solvents such as dimethyl sulfoxide That. You may use these organic solvents individually or in combination of 2 or more types.
Among these, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether, methyl cellosolve, γ-butyrolactone, and dimethylacetamide are preferable from the viewpoint of solubility of the resin component, and low toxicity, and high volatility. Cyclohexanone, propylene glycol monomethyl ether, and methyl ethyl ketone are more preferable because they are unlikely to remain as a residual solvent during the production of the prepreg.

The amount of the organic solvent used is preferably 25 to 300 parts by mass, more preferably 40 to 250 parts by mass, with respect to 100 parts by mass of the thermosetting resin composition of the present invention, from the viewpoint of solubility of the resin component .
The content (hereinafter, also referred to as “solid content”) of the thermosetting resin composition in the finally obtained varnish is preferably 40 to 90 mass%, more preferably 50 to 80 mass%. By making content of the thermosetting resin composition in a varnish in the said range, coating property can be kept favorable and the prepreg of the appropriate thermosetting resin composition adhesion amount can be obtained.
Next, the method for producing the thermosetting resin composition of the present invention will be described.

[Method of producing thermosetting resin composition]
The method for producing a thermosetting resin composition of the present invention includes the following steps 1 to 3.
Step 1: Mix (b) untreated inorganic filler and (C) titanate coupling agent without solvent, (b) surface-treat untreated inorganic filler to obtain (B) inorganic filler Step 2: The organic solvent is added to (B) the inorganic filler obtained in Step 1 and mixed to obtain a dispersion of the inorganic filler (B) Step 3: obtained in Step 2 (B ) A step of mixing a dispersion of an inorganic filler and (A) a thermosetting resin to obtain a thermosetting resin composition

(Step 1)
Step 1 mixes (b) untreated inorganic filler and (C) titanate coupling agent in the absence of solvent, (b) performs surface treatment of the untreated inorganic filler, and (B) inorganic filler It is a process to obtain.
The present invention is a method of surface treatment by mixing with other components and surface treatment in a solvent by surface treatment of (b) untreated inorganic filler with (C) titanate coupling agent under no solvent. The effect of reducing the melt viscosity can be made greater than the method of
The amount of (C) titanate coupling agent mixed with (b) untreated inorganic filler under no solvent is preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of (b) untreated inorganic filler. The amount is more preferably 0.3 to 5 parts by mass, further preferably 0.4 to 3 parts by mass, and particularly preferably 0.5 to 1.5 parts by mass. The chemical resistance can be improved by setting the use amount of (C) titanate coupling agent to 0.2 parts by mass or more with respect to 100 parts by mass of (b) untreated inorganic filler, 10 parts by mass Heat resistance can be improved by setting it as the following.
The mixing temperature in step 1 is preferably 5 to 50 ° C., more preferably 10 to 40 ° C., and still more preferably 15 to 35 ° C., from the viewpoint of productivity and in view of performing good surface treatment.
The mixing time in step 1 is preferably 5 to 240 minutes, more preferably 10 to 180 minutes, and still more preferably 30 to 120 minutes, from the same viewpoint.

(Step 2)
Step 2 is a step of adding an organic solvent to the (B) inorganic filler obtained in step 1 and mixing to obtain a dispersion liquid of (B) inorganic filler.
Examples of the organic solvent used in the step 2 include the same organic solvents as those contained in the thermosetting resin composition solution, and preferred embodiments are also the same.
The addition amount of the organic solvent may be appropriately adjusted so that the solid concentration of the final thermosetting resin composition becomes the content of the thermosetting resin composition in the varnish, but preferably 20 to 20. It is 150 parts by mass, more preferably 25 to 120 parts by mass, and still more preferably 30 to 100 parts by mass.
The mixing temperature in step 2 is preferably 5 to 50 ° C., more preferably 10 to 40 ° C., still more preferably 15 to 35 ° C. from the viewpoint of productivity and in view of obtaining a dispersion having good dispersibility.
The mixing time in step 2 is preferably 5 to 240 minutes, more preferably 10 to 180 minutes, still more preferably 30 to 120 minutes, from the same viewpoint.

(Step 3)
Step 3 is a step of mixing the dispersion of (B) inorganic filler obtained in step 2 and (A) thermosetting resin to obtain a thermosetting resin composition.
In step 3, (A) the thermosetting resin may be directly mixed with the dispersion of (B) the inorganic filler, and it is previously mixed in a solvent with a curing agent, a curing accelerator, (D) a silicone compound, etc. It may be mixed as a solution.
The mixing temperature in step 3 may be appropriately adjusted according to the type of the organic solvent and (A) thermosetting resin to be used, but from the viewpoint of productivity, preferably 10 to 100 ° C., more preferably 20 to 80 ° C. It is.
The mixing time in step 3 is preferably 5 to 240 minutes, more preferably 30 to 180 minutes, and still more preferably 60 to 150 minutes, from the same viewpoint.

  The mixing in the steps 1 to 3 may be performed using, for example, a conventionally known mixer such as a mixer, and from the viewpoint of improving the dispersibility of the (D) inorganic filler, a kneader, three rolls, ball mill, bead mill It may be processed by a dispersing machine such as a nanomizer, a homogenizer or the like.

  The varnish containing the thermosetting resin composition obtained by the above method may be used as it is for the production of a prepreg or the like, or may be dried and pulverized if necessary to obtain a powder.

[Prepreg]
The prepreg of the present invention is obtained by impregnating or coating the thermosetting resin composition of the present invention on a substrate.
Specifically, after the thermosetting resin composition of the present invention is applied to a substrate by a method such as impregnation, spraying or extrusion, heating and the like are performed to semi-cure the thermosetting resin (A). The prepreg of the present invention can be produced by (B-staging).
Hereinafter, the prepreg of the present invention will be described in detail.

As a base material of the prepreg of the present invention, known ones used for various electric insulating material laminates can be used.
Examples of the material of the substrate include inorganic fibers such as E glass, D glass, S glass and Q glass; organic fibers such as polyimide, polyester and tetrafluoroethylene; and mixtures thereof.
As a shape of a base material, shapes, such as a woven fabric, a nonwoven fabric, a rovinck, a chopped strand mat, and a surfacing mat, are mentioned, for example.
The material and shape of the substrate may be appropriately selected according to the intended use and performance of the molded article, and can be used singly or in combination of two or more kinds of materials and shapes.
The thickness of the substrate is not particularly limited, and, for example, one having a thickness of 0.01 to 0.5 mm can be used.
Moreover, as a base material, what was surface-treated with a silane coupling agent etc., and what performed opening processing mechanically are suitable from heat resistance, moisture resistance, and a surface of processing nature.
The impregnation or coating amount of the thermosetting resin composition to the substrate is such that the adhesion amount of the thermosetting resin composition after drying is the content of the thermosetting resin composition in the prepreg after drying, The amount which becomes mass% is preferable.
Moreover, the drying conditions after impregnating or coating the thermosetting resin composition are not particularly limited as long as the solvent can be removed while maintaining the thermosetting resin composition in a semi-cured state, for example, drying The temperature is 100 to 200 ° C., and the drying time is 1 to 30 minutes.

[Laminated board]
In the laminate of the present invention, the insulating resin layer is formed using the prepreg of the present invention, and the laminate of the present invention can be formed by laminating using the prepreg of the present invention described above. it can.
For example, a laminated board can be manufactured by laminating and forming the above-mentioned prepreg in a configuration in which 1 to 20 sheets of the above-described prepreg are stacked and metal foils such as copper and aluminum are disposed on one side or both sides thereof. The metal foil is not particularly limited as long as it is used in a laminate for an electrical insulating material. The forming conditions may be, for example, the method of laminates and multilayer plates for electrical insulating materials, for example, using multi-stage press, multi-stage vacuum press, continuous forming, autoclave forming machine, etc., temperature 100-250 ° C., pressure 0 It can be molded under the conditions of 2. Also, a multilayer board can be manufactured by combining the prepreg of the present invention and the wiring board for inner layer, and laminating and molding.

[Printed wiring board]
The printed wiring board of the present invention is one using the laminate of the present invention.
The printed wiring board of the present invention can be produced, for example, by processing a metal foil disposed on one side or both sides of the insulating resin layer in the laminate of the present invention. That is, the conductor layer of the laminate of the present invention is subjected to wiring processing by a known etching method, and a plurality of laminates subjected to wiring processing via the above-mentioned prepreg are laminated and heat-pressed collectively A printed wiring board can be manufactured through formation of through holes or blind via holes by drilling or laser processing and formation of interlayer wiring by plating or conductive paste.

EXAMPLES The present invention will next be described in detail by way of examples, which should not be construed as limiting the scope of the present invention.
Analysis and evaluation in Examples and Comparative Examples were performed by the methods described below.

[Reaction rate of cyanate resin]
Each of the solution before the reaction in which the cyanate resin was blended and the solution after the reaction were subjected to GPC measurement under the following conditions, and the reduction rate of the area of the peak derived from the cyanate resin was calculated by the following equation to obtain the reaction rate.
Reaction rate (%) = [(peak area before reaction) − (peak area after reaction)] / (peak area before reaction) × 100
<GPC measurement conditions>
-Measuring device: "AS-8020" (trade name) manufactured by Tosoh Corp.
・ Column: Tosoh Co., Ltd. product "HZ2000", "HZ3000" (brand name)
Eluent: Tetrahydrofuran Sample concentration: 10 mg / ml
Injection volume: 20 μL
Flow rate: 0.5 mL / min Measurement temperature: 30 ° C.

[Minimum melt viscosity]
The minimum melt viscosity was measured by the following method about the thermosetting resin composition obtained by each Example and the comparative example.
First, resin powder obtained in each Example and Comparative Example was molded into a thickness of 1 mm (20 mmφ) by uniaxial molding. Next, this sample was measured using “ARES-2 KSTD” manufactured by Rheometric Co., using a plate and a cup under the following conditions.
<Measurement conditions>
・ Measurement temperature range: 30 to 200 ° C
· Heating rate: 4 ° C / minute · Pressure: 0.5 N
-Gap: 0.5 to 1.5 mm
Distortion: 0.5%
Frequency: 6.283 rad / sec

Example 1
In a 1 L flask, (b) 192 g of silica (trade name: SO-G1 manufactured by Admatex Co., Ltd.) as an untreated inorganic filler, (C) a titanate coupling agent (Ajinomoto Fine Techno Co., Ltd.) , Brand name: 2 g of Prenact (registered trademark) KR-TTS was added, and stirred at 25 ° C. for 1 hour. Subsequently, 149 g of methyl ethyl ketone was blended as a solvent, and the mixture was further stirred at 25 ° C. for 1 hour to disperse the (B) inorganic filler in the solvent.
After that (A) as a thermosetting resin, 100 g of bisphenol A novolac epoxy resin (manufactured by DIC Corporation, trade name: EPICLON (registered trademark) N865), phenol novolac resin (manufactured by Meiwa Kasei Co., Ltd., trade name: HF) -4) 54 g and 0.2 g of 2-ethyl -4- methyl imidazole were added as a hardening accelerator, and it stirred at 25 degreeC for 2 hours, and obtained the varnish of 70 mass% of solid content.
Thereafter, the varnish obtained above was applied to a PET film at a gap of 150 μm and dried by heating at 140 ° C. for 10 minutes, and then the resin was taken out as powder from the PET film to obtain resin powder.

Examples 2 to 4
Resin powder was obtained in the same manner as in Example 1 except that the raw material composition was changed as shown in Table 1 in Example 1.

Comparative Example 1
(A) As a thermosetting resin, 100 g of bisphenol A novolac type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON (registered trademark) N865), phenol novolac resin (Meiwa Kasei Co., Ltd.) as a thermosetting resin (Trade name: HF-4) 54 g, (b) as an untreated inorganic filler, silica (made by Admatex Co., Ltd., trade name: SO-G1) 192 g, (C) titanate coupling agent (Ajinomoto fine techno Made by Co., Ltd., trade name: Prenact (registered trademark) KR-TTS 2 g, 0.2 g of 2-ethyl-4-methylimidazole as a curing accelerator, 149 g of methyl ethyl ketone as a solvent, 2 hours at 25 ° C. Stirring was performed to obtain a varnish having a solid content of 70% by mass.
Thereafter, the varnish obtained above was applied to a PET film at a gap of 200 μm and dried by heating at 140 ° C. for 10 minutes, and then the resin was taken out as powder from the PET film to obtain resin powder.

Comparative example 2
In Comparative Example 1, after (b) an untreated inorganic filler is dispersed in methyl ethyl ketone, (C) a titanate coupling agent is blended and stirred at 25 ° C. for 1 hour, (A) a thermosetting resin, and A resin powder was obtained in the same manner as in Comparative Example 1 except that a curing accelerator was added and stirring was performed at 25 ° C. for 2 hours.

Comparative Examples 3 to 6
Resin powder was obtained in the same manner as in Example 1 except that the raw material composition was changed as shown in Table 1 in Example 1.

Example 5
In a 1 L flask, (b) 192 g of silica (trade name: SO-G1 manufactured by Admatex Co., Ltd.) as an untreated inorganic filler, (C) a titanate coupling agent (Ajinomoto Fine Techno Co., Ltd.) Brand name: 2 g of Prenact (registered trademark) KR-TTS was added, and the mixture was stirred at 25 ° C. for 1 hour. Next, 149 g of propylene glycol monomethyl ether was blended as a solvent, and the mixture was further stirred at 25 ° C. for 1 hour to disperse the (B) inorganic filler in the solvent.
After that, bis (4-maleimidophenyl) methane (manufactured by Kaiai Kasei Co., Ltd.), which is a maleimide compound having two or more N-substituted maleimide groups in one molecule as (A) thermosetting resin, trade name: BMI 8) 3 g, and 3,3'-diethyl-4,4'-diaminodiphenylmethane (Nippon Kayaku Co., Ltd. product, trade name: KAYAHARD A-), which is a compound having two or more amino groups in one molecule. A) 54.1 g and (D) 15.4 g of a silicone oil having amino groups at both ends as a silicone compound (manufactured by Toray Dow Corning Co., Ltd., trade name: BY-16-853 B) are added, Stirring was performed for 2 hours to obtain a varnish having a solid content of 70% by mass.
Thereafter, the varnish obtained above was applied to a PET film at a gap of 150 μm and dried by heating at 140 ° C. for 10 minutes, and then the resin was taken out as powder from the PET film to obtain resin powder.

Example 6
Resin powder was obtained in the same manner as in Example 5 except that the raw material composition was changed as shown in Table 2 in Example 5.

Comparative example 7
Bis (4-maleimidophenyl) methane (Kaiai Kasei Co., Ltd.) which is a maleimide compound having two or more N-substituted maleimide groups in one molecule as a thermosetting resin (A) in a 1 L flask (Trade name: BMI) 84.7 g, and 3,3'-diethyl-4,4'-diaminodiphenylmethane (Nippon Kayaku Co., Ltd. product, a product having two or more amino groups in one molecule) Name: 54.1 g of KAYAHARD A-A, (b) Untreated inorganic filler, silica (Admatex Co., Ltd., trade name: SO-G1) 192 g, (C) Titanate coupling agent (Ajinomoto fine techno Made by Co., Ltd., trade name: Prenact (registered trademark) KR-TTS 2 g, (D) As a silicone compound, silicone oil having amino groups at both ends (Toray Dow Co., Ltd. Manufactured by RING CO., LTD., Trade name: BY-16-853B, 149 g of propylene glycol monomethyl ether as a solvent, and stirred at 70 ° C. for 2 hours to obtain a varnish having a solid content of 70% by mass .
Thereafter, the varnish obtained above was applied to a PET film at a gap of 150 μm and dried by heating at 140 ° C. for 10 minutes, and then the resin was taken out as powder from the PET film to obtain resin powder.

Comparative Example 8
In Comparative Example 7, after (b) an untreated inorganic filler is dispersed in propylene glycol monomethyl ether, (C) a titanate coupling agent is blended, and after being stirred at 25 ° C. for 1 hour, (A) thermosetting A resin powder was obtained in the same manner as in Comparative Example 7 except that the resin and (D) the silicone compound were blended and stirring was performed at 25 ° C. for 2 hours.

Comparative Examples 9 to 11
Resin powder was obtained in the same manner as in Example 5 except that the raw material composition was changed as shown in Table 2 in Example 5.

Example 7
In a 500 mL flask, (b) 192 g of silica (trade name: SO-G1 manufactured by Admatex Co., Ltd.) as an untreated inorganic filler, (C) titanate coupling agent (manufactured by Ajinomoto Fine Techno Co., Ltd.) , And trade name: 2 g of Prenact (registered trademark) KR-TTS is added and stirred for 1 hour at 25 ° C. Then, 82.3 g of cyclohexanone is blended as a solvent and further stirred for 1 hour at 25 ° C. (B) Inorganic A dispersion of filler (I) was prepared.
Next, in a 1-liter heatable and coolable reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, as a thermosetting resin (A) having two or more cyanate groups in one molecule 138.6 g of a bisphenol A-type cyanate resin (trade name: Primaset (registered trademark) BADCy) which is a compound, (D) a silicone oil having a silicone oil having amino groups at both ends (Toray Dow Corning A trade name: BY-16-853B, 15.4 g, and 66.7 g of toluene as a solvent were added. Then, the temperature is raised to 120 ° C. with stirring, and resin solid content is dissolved, and after confirming that it is a solution, 0.002 g of 8 wt% mineral spirit solution of zinc naphthenate is added, and 4 at 110 ° C. The reaction was timed. A small amount of the reaction solution was taken out and subjected to GPC measurement, and it was found that the reaction rate calculated from the peak of the bisphenol A-type cyanate resin of the synthetic raw material in which the elution time appeared around 12.4 minutes was 50 mol%. Moreover, the peak of the product of the thermosetting resin which appears in about 10.9 minutes vicinity, and 8.0 to about 10.0 minutes was confirmed.
Then, the dispersion liquid (I) was added to the said reaction solution, and it stirred at 25 degreeC for 2 hours, and obtained the varnish of 70 mass% of solid content.
Thereafter, the varnish obtained above was applied to a PET film at a gap of 150 μm and dried by heating at 170 ° C. for 15 minutes, and then the resin was taken out as a powder from the PET film to obtain a resin powder.

Example 8
A resin powder was obtained in the same manner as in Example 7 except that the raw material composition was changed as shown in Table 3 in Example 7.

Comparative Example 12
(A) A compound having two or more cyanate groups in one molecule as a thermosetting resin in a 1-liter heatable and coolable reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser 138.6 g of bisphenol A type cyanate resin (Lonza Japan Co., Ltd., trade name: Primaset (registered trademark) BADCy), (D) Silicone oil having an amino group at both ends as a silicone compound (manufactured by Toray Dow Corning Co., Ltd.) Brand name: 15.4 g of BY-16-853 B) and 66.7 g of toluene as a solvent were charged. Then, the temperature is raised to 120 ° C. with stirring, and resin solid content is dissolved, and after confirming that it is a solution, 0.002 g of 8 wt% mineral spirit solution of zinc naphthenate is added, and at about 110 ° C. The reaction was performed for 4 hours. A small amount of the reaction solution was taken out and subjected to GPC measurement, and it was found that the reaction rate calculated from the peak of the bisphenol A-type cyanate resin of the synthetic raw material in which the elution time appeared around 12.4 minutes was 50 mol%. Moreover, the peak of the product of the thermosetting resin which appears in about 10.9 minutes vicinity, and 8.0 to about 10.0 minutes was confirmed.
Next, (b) 192 g of silica (trade name: SO-G1 manufactured by Admatex Co., Ltd.) as an untreated inorganic filler, (C) a titanate coupling agent (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name: 2 g of Prenact (registered trademark) KR-TTS, 82.3 g of cyclohexanone as a solvent were added, and the mixture was stirred at 25 ° C. for 2 hours to obtain a varnish having a solid content of 70% by mass.
Thereafter, the varnish obtained above was applied to a PET film at a gap of 150 μm and dried by heating at 170 ° C. for 15 minutes, and then the resin was taken out as a powder from the PET film to obtain a resin powder.

Comparative Example 13
A reaction solution was obtained in the same manner as in Comparative Example 12. Next, (b) 192 g of silica (manufactured by Admatex Co., Ltd., trade name: SO-G1) as an untreated inorganic filler is dispersed in 82.3 g of cyclohexanone, and then (C) a titanate coupling agent (Ajinomoto fine Techno G. K., trade name: Prenact (registered trademark) KR-TTS 2 g was added, and the mixture was stirred at 25 ° C. for 1 hour to obtain a dispersion liquid (II).
Thereafter, the dispersion liquid (II) was added to the above reaction solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain a varnish having a solid content of 70% by mass.
Thereafter, the varnish obtained above was applied to a PET film at a gap of 150 μm and dried by heating at 170 ° C. for 15 minutes, and then the resin was taken out as a powder from the PET film to obtain a resin powder.

Comparative Examples 14 to 16
A resin powder was obtained in the same manner as in Example 7 except that the raw material composition was changed as shown in Table 3 in Example 7.

The minimum melt viscosity of the thermosetting resin composition obtained by each Example and the comparative example is shown to Tables 1-3.
The details of each material in Tables 1 to 3 are as follows.

(A) Thermosetting resin-BisA-N-Ep: Bisphenol A novolac type epoxy resin (manufactured by DIC Corporation, trade name: EPICLON (registered trademark) N865)
-PN: Phenolic novolak resin (manufactured by Meiwa Kasei Co., Ltd., trade name: HF-4)
BMI: bis (4-maleimidophenyl) methane (manufactured by Kaiai Kasei Co., Ltd., trade name: BMI)
KH-AA: 3,3'-diethyl-4,4'-diaminodiphenylmethane (manufactured by Nippon Kayaku Co., Ltd., trade name: KAYAHARD A-A)

Hardening accelerator 2E4MZ: 2-ethyl-4-methylimidazole

Coupling agent TTS: isopropyl triisostearoyl titanate (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name: Prenact (registered trademark) KR-TTS)
9SA: isopropyl tridodecyl benzene sulfonyl titanate (manufactured by Ajinomoto Fine Techno Co., Ltd., trade name: Prenact (registered trademark) KR-9SA)
KBE-9103: 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (Shin-Etsu Chemical Co., Ltd. product name: KBE-9103)
· KBM-573: N-phenyl-3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. product, trade name: KBM-573)
KBM-1003: vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. product name: KBM-1003)

(D) Silicone compound · Silicone oil having amino groups at both ends (Toray · Dow Corning Co., Ltd., trade name: BY-16-853B)

Solvents · MEK: methyl ethyl ketone · PGMME: propylene glycol monomethyl ether

  From Tables 1 to 3, the thermosetting resin compositions of the present invention of Examples 1 to 8 have lower minimum melt viscosity and excellent formability as compared with the thermosetting resin compositions of Comparative Examples 1 to 16. I understand that.

Claims (12)

A prepreg formed by impregnating or coating a thermosetting resin composition containing (A) a thermosetting resin and (B) an inorganic filler on a substrate, wherein (B) the inorganic filler is solvent-free The prepreg which is surface-treated by (C) titanate coupling agent represented with following General formula (1) below .
(R) _4-n- Ti-(X) _n (1)
(Wherein, X is an alkoxy group having 1 to 8 carbon atoms, R is an isostearoyl group, and n is an integer of 1 to 4).   The prepreg according to claim 1, wherein an amount of the (C) titanate coupling agent used in the surface treatment is 0.2 to 10 parts by mass with respect to 100 parts by mass of the (b) untreated inorganic filler.   The prepreg according to claim 2, wherein (b) the untreated inorganic filler is silica.   The content of the (B) inorganic filler in the thermosetting resin composition is 10 to 400 parts by mass with respect to 100 parts by mass of the (A) thermosetting resin. The prepreg as described in a paragraph.   (A) A thermosetting resin is (A1) epoxy resin, (A2) a maleimide compound having two or more N-substituted maleimide groups in one molecule, and a compound having two or more amino groups in one molecule The prepreg according to any one of claims 1 to 4, which is one or more selected from a mixture of (A3) and (A3) a compound having two or more cyanate groups in one molecule.   The prepreg according to any one of claims 1 to 5, further comprising (D) a silicone compound.   The prepreg according to claim 6, wherein the silicone compound (D) has one or more reactive functional groups.   The prepreg according to claim 7, wherein the reactive functional group is one or more selected from an amino group and a hydroxyl group.   The prepreg according to any one of claims 1 to 8, wherein (C) the titanate coupling agent is isopropyl triisostearoyl titanate.   The laminated board formed by laminating-forming the prepreg of any one of Claims 1-9.   The printed wiring board using the laminated board of Claim 10. A method for producing a thermosetting resin composition comprising (A) a thermosetting resin and (B) an inorganic filler, wherein (B) the inorganic filler has the following general formula (1) in the absence of a solvent: has been surface-treated with represented (C) a titanate coupling agent,
(R) _4-n- Ti-(X) _n (1)
(Wherein, X is an alkoxy group having 1 to 8 carbon atoms, R is an isostearoyl group, and n is an integer of 1 to 4).
The manufacturing method of the thermosetting resin composition which has the following processes 1-3.
Step 1: (b) mixing the untreated inorganic filler and (C) a titanate coupling agent in the absence of solvent, (b) surface treating the untreated inorganic filler, (B) the inorganic filler Step 2: Obtain an organic solvent by adding the organic solvent to the (B) inorganic filler obtained in Step 1 and mixing to obtain a dispersion liquid of (B) inorganic filler Step 3: Obtained in Step 2 (B) A step of mixing a dispersion of an inorganic filler and (A) a thermosetting resin to obtain a thermosetting resin composition