JP2009155654A - Thermosetting resin composition, and prepreg, metal-clad laminate, and printed wiring board, using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that improves the heat resistance without deterioration of dielectric characteristics, and to provide prepregs, laminates and printed wiring boards, using the same. <P>SOLUTION: The thermosetting resin composition comprises a copolymerized resin (component A) containing a monomer unit (a) and another monomer unit (b), and a thermosetting resin (component B), wherein the component B contains a biphenylaralkyl type epoxy resin (component B1). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermosetting resin composition, a prepreg using the same, a metal-clad laminate, and a printed wiring board.

  As a printed wiring board for electronic equipment, a laminated board mainly using an epoxy resin is widely used. However, as the mounting density of electronic equipment increases, the finer pattern, the fixing of the surface mounting method, the higher signal propagation speed and the higher frequency of signals handled, the lower the dielectric loss and heat resistance of printed wiring board materials. There is a strong demand for improvement.

  As a specific example of a resin composition or laminate using an epoxy resin as a curing agent and a copolymer resin composed of styrene and maleic anhydride, for example, for the purpose of imparting flexibility, a reactive epoxy diluent and acrylonitrile-butadiene Examples thereof include a printed wiring board made of a flexible epoxy resin, a copolymer resin composed of styrene and maleic anhydride, which requires a copolymer (Patent Document 1). In addition, an epoxy resin, a copolymer resin having an acid value of 280 or more obtained from an aromatic vinyl compound and maleic anhydride, and an epoxy resin containing dicyanamide are mentioned (Patent Document 2).

  Furthermore, prepregs and laminates using epoxy resin compositions containing brominated epoxy resins, epoxy resin curing agents that are copolymer resins of styrene and maleic anhydride, styrene compounds, and solvents have been proposed. (Patent Document 3). In addition, epoxy resins, copolymer resins of aromatic vinyl compounds and maleic anhydride, prepregs and laminates using epoxy resin compositions containing phenolic compounds have been proposed (Patent Documents 4 and 5), and further, epoxy resins, A resin composition containing an acid anhydride type epoxy resin crosslinking agent, an allyl network-forming compound, a laminated board using the resin composition, and a printed wiring board have been proposed (Patent Document 6).

  However, these have insufficient performance in terms of low dielectric loss, high heat resistance, high moisture resistance, and high adhesion to copper foil, etc., all of which are required as patterns become finer and signal frequency increases. The performance is not satisfied.

  A thermosetting resin composition containing a copolymer resin of styrene and maleic anhydride, a cyanate, and a compound has also been proposed, and an epoxy resin may be included as a constituent component (Patent Document 7). However, a further improvement in heat resistance is required for prepregs and laminates using the thermosetting resin composition.

JP 49-109476 A JP-A-1-221413 Japanese Patent Laid-Open No. 9-25349 Japanese Patent Laid-Open No. 10-1785 Japanese Patent Laid-Open No. 10-17686 JP-A-10-505376 JP 2000-317085 A

  The object of the present invention is to provide a thermosetting resin composition that is excellent in all of dielectric properties, heat resistance, moisture resistance, and adhesiveness with copper foil in view of the above problems. It is providing the thermosetting resin composition which improved heat resistance, without making it. Moreover, the objective of this invention provides the member using such a thermosetting resin composition, for example, a prepreg, a laminated board, a printed wiring board, etc.

  In order to achieve the above object, the present inventors have conducted various studies, and when combining a copolymer resin containing styrene and maleic anhydride as a copolymer unit with a specific biphenylaralkyl type epoxy resin, dielectric properties are obtained. The present invention was completed by finding that the heat resistance could be improved without lowering the temperature.

That is, according to the present invention,
Component A General Formula (I):

(In the formula, R ₁ is a hydrogen atom, a halogen atom, or a C _{1 to} C ₅ hydrocarbon group, and R ₂ is independently a halogen atom or a C _{1 to} C ₅ aliphatic hydrocarbon. A monomer unit (a) represented by a group, an aromatic hydrocarbon group or a hydroxyl group, and x is an integer of 0 to 3, and a general formula (II):

A copolymer resin containing a monomer unit (b) represented by:
Component B A thermosetting resin composition containing a thermosetting resin, wherein the component B is a component B1 general formula (III):

A thermosetting resin composition containing a biphenyl aralkyl type epoxy resin (component B1) represented by (p is an integer of 1 or more) is provided.

  According to the present invention, in the above configuration, the component B further includes a cyanate compound (component B2) containing two or more cyanato groups in one molecule, and the component B2 is represented by the general formula (IV):

[Wherein R ₃ represents a halogen-substituted or unsubstituted C ₁ -C ₃ alkylene group, —S—,

(R ′ is a C ₁ -C ₃ alkylene group), and R ₄ and R ₅ are each independently a hydrogen atom or a C ₁ -C ₃ alkyl group.]
The thermosetting resin composition which is at least 1 type of the cyanate compound chosen from the compound shown by is provided.

  According to the present invention, in the above configuration, the component B contains the component B3, and this component B3 is a phenol-modified cyanate ester oligomer obtained by reacting the cyanate compound of the component B2 with a specific phenol compound. Certain thermosetting resin compositions are provided.

  According to this invention, the thermosetting resin composition whose compounding quantity of the said component B1 with respect to 100 mass parts of the said component A is 50-250 mass parts is provided. Moreover, according to this invention, the thermosetting resin composition whose compounding quantity of the said component B2 and B3 with respect to 100 mass parts of the said component A is 100-400 mass parts is provided.

  According to the present invention, each thermosetting resin composition described above is varnished, impregnated with the varnish on a base material, and then dried, and one or a plurality of the prepregs are stacked, and at least A metal-clad laminate obtained by laminating a metal foil on one surface and heating and pressing, and a printed wiring board using the same are also provided.

  The thermosetting resin composition of the present invention is excellent in dielectric properties, moisture and heat resistance, for example, solder heat resistance during moisture absorption, and adhesiveness with copper foil, and a prepreg obtained by impregnating or applying the present composition to a substrate and A laminate produced by laminating a prepreg is excellent in dielectric properties, moisture and heat resistance, and adhesiveness with copper foil, and is useful as a printed wiring board for electronic equipment.

  The thermosetting resin composition of the present invention comprises a copolymer resin (component A) containing a specific copolymer unit and a thermosetting resin (component B) containing a specific biphenyl aralkyl type epoxy resin (component B1) as essential components. , And other components blended as necessary.

    In the present invention, Component A is a copolymer resin containing a monomer unit (a) and a monomer unit (b).

  In component A, the monomer unit (a) has the general formula (I):

(In the formula, R ₁ is a hydrogen atom, a halogen atom, or a C _{1 to} C ₅ hydrocarbon group, and R ₂ is independently a halogen atom or a C _{1 to} C ₅ aliphatic hydrocarbon. A group, an aromatic hydrocarbon group or a hydroxyl group, and x is an integer of 0 to 3.

Examples of R ₁ include a hydrogen atom, a halogen atom, or a C _{1 to} C ₅ alkyl group. Examples of the halogen atom include chlorine, bromine, fluorine, and iodine. Examples of the C _{1 to} C ₅ alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. R ₁ is particularly preferably a hydrogen atom or a methyl group.

Examples of R ₂ include a halogen atom, a C _{1 to} C ₅ aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a hydroxyl group. Examples of the halogen atom include chlorine, bromine, fluorine, and iodine, and examples of the C _{1 to} C ₅ aliphatic hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. . Examples of the aromatic hydrocarbon group include a phenyl group. Further, R ₂ may be an aromatic hydrocarbon group including a group that forms a naphthalene ring together with the benzene ring portion of the monomer unit (a). R ₂ is particularly preferably a hydrogen atom or a methyl group.

Moreover, in general formula (I), x represents the integer of 0-3. When x is 2 or 3, R ₂ may be the same or different. A preferred value for x is zero.

  The monomer unit (a) can be obtained, for example, from a compound obtained by mixing one or more of styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, bromostyrene, and the like.

  If necessary, substituents such as allyl, methacryloyl, acryloyl and hydroxyl groups are introduced into the monomer unit (a) through a Friedel-Crafts reaction or a reaction using a metal catalyst such as lithium. can do.

  In component A, the monomer unit (b) has the general formula (II):

It is a maleic anhydride unit as shown by. In the present invention, a hydroxyl group-containing compound, an amino group-containing compound, a cyanate group-containing compound, an epoxy group-containing compound, and the like may be introduced into the monomer unit (b). Specifically, it is preferable to introduce these by a method in which the monomer unit (b) is modified with each of the above compounds.

  Component A is represented by the general formula (VII):

(Wherein, m and n are natural numbers, and R ₁ , R ₂ and x are as defined above), and more preferably, a general formula (X):

(Wherein R ₁ , m and n are as defined above). Here, m and n represent the number of each monomer unit in one molecule, and may be a block copolymer or a random copolymer.

  In the component A, the copolymer composition ratio m / n of the monomer unit (a) to the monomer unit (b) is a balance between the relative dielectric constant and the dielectric loss tangent, the glass transition temperature, the solder heat resistance, and the adhesiveness to the copper foil. Is considered to be 0.8 to 19. When m / n is less than 0.8, the dielectric properties tend to deteriorate. When m / n exceeds 19, the solder heat resistance and the adhesion to copper foil tend to deteriorate. A particularly preferred range of m / n is 1-5.

  As component A, in addition to the monomer unit (a) and monomer unit (b), the monomer unit (c) is represented by the general formula (VIII):

A copolymer resin (component A1) containing N-phenylmaleimide and / or a derivative thereof represented by the formula (wherein R ₁₀ and y are as defined above) is preferable.

In the general formula (VIII), R ₁₀ is a halogen atom, a C _{1 to} C ₅ aliphatic hydrocarbon group, an aromatic hydrocarbon group, a hydroxyl group, a thiol group, or a carboxyl group. The halogen atom chlorine, bromine, fluorine and the like, C ₁ -C ₅ aliphatic hydrocarbon C ₁ -C ₅ alkyl group as a group, for example, a methyl group, an ethyl group, a propyl group, butyl group and pentyl Groups. Examples of the aromatic hydrocarbon group include a phenyl group. R ₁₀ is preferably a hydrogen atom or a methyl group.

In the general formula (VIII), y is an integer of 0 to 3, and when y is 2 or 3, R ₁₀ may be the same or different. A preferred value for y is zero.

  As the monomer unit (c), a monomer unit obtained from N-phenylmaleimide or a derivative of N-phenylmaleimide having a phenolic hydroxyl group is preferable in terms of dielectric properties and glass transition temperature, and a monomer obtained from N-phenylmaleimide The unit is particularly preferable for improving heat resistance and moisture resistance.

  Examples of derivatives of N-phenylmaleimide include general formulas (XI) to (XVI):

(In the formula, w is each independently an integer of 1 to 3).

  Component A1 is represented by the general formula (IX):

(Wherein, r is a natural number, and R ₁ , R ₂ , R ₁₀ , m, n, x and y are as defined above), and more preferably, General formula (XVII):

(Wherein, r is a natural number, and R ₁ , m, and n are as defined above). Here, m, n, and r represent the number of each monomer in one molecule, and may be a block copolymer or a random copolymer. The values of m, n, and r are not particularly limited, but it is preferable that m is 1 to 5, n is 0.1 to 1, and r is 0.1 to 0.9.

  In component A1, the copolymer composition ratio m / (n + r) of the monomer unit (a) to the monomer units (b) and (c) is the relative dielectric constant and dielectric loss tangent, the glass transition temperature, the solder heat resistance, and the copper foil. In consideration of the balance with adhesiveness, 0.8 to 19 is preferable, and 1 to 5 is more preferable.

  In the component A1 of the present invention, the copolymer composition ratio n / r of the monomer unit (b) to the monomer unit (c) is the relative dielectric constant and dielectric loss tangent, the glass transition temperature, the solder heat resistance, and the adhesiveness to the copper foil. In view of the balance, 1/49 to 49 is preferable, and 1/9 to 9 is more preferable.

  Component A can be prepared by a known method. For example, a copolymer resin solution of component A can be prepared by dissolving a copolymer resin of styrene and maleic anhydride in a predetermined solvent. In addition, aniline or a derivative thereof is added to the solution of component A thus obtained, and a reaction is performed at a predetermined temperature, whereby component A1 composed of styrene, maleic anhydride, N-phenylmaleimide or a derivative thereof is performed. A copolymer resin solution can be prepared. Furthermore, component A such as component A1 may be copolymerized with various polymerizable components other than the above monomer units. Examples of these various polymerizable components include ethylene, propylene, butadiene, isobutylene, Examples thereof include compounds having a methacryloyl group or an acryloyl group such as acrylonitrile, vinyl compounds such as vinyl chloride and fluoroethylene, methacrylates such as methyl methacrylate, and acrylate compounds such as methyl acrylate.

  Moreover, the form of copolymerization of each monomer unit of component A such as component A1 is not particularly limited, and any form such as a block copolymer or a random copolymer may be used.

  Furthermore, the weight average molecular weight of component A is preferably 1,000 to 300,000, more preferably 5,000, considering the balance between heat resistance and mechanical strength and moldability at 200 ° C. or lower. ~ 150,000. The weight average molecular weight used in the present invention is a value measured by gel permeation chromatography using tetrahydrofuran as an eluent and converted by a standard polystyrene calibration curve.

  The thermosetting resin of component B in the present invention has the general formula (III):

A biphenylaralkyl epoxy resin (component B1) represented by (p is an integer of 1 or more) is an essential component.

  The weight average molecular weight of the component B1 is preferably in the range of 550 to 900, more preferably in the range of 570 to 870, considering the balance of heat resistance, dielectric properties, and adhesiveness.

  Component B preferably contains a cyanate compound (component B2) having two or more cyanato groups in one molecule in addition to component B1, from the viewpoint of improving dielectric properties and heat resistance.

  Component B2 is not particularly limited, but the general formula (IV):

Wherein R ₃ is a halogen-substituted or unsubstituted C ₁ -C ₃ alkylene group, —S—,

(R ′ is a C ₁ -C ₃ alkylene group) and R ₄ and R ₅ are each independently a hydrogen atom or a C ₁ -C ₃ alkyl group). It is preferable.

When R ₃ is a C ₁ -C ₃ alkylene group, a methylene group, an ethylene group, a propylene group, and an isopropylene group are exemplified. These may be substituted with a halogen atom. Examples of the halogen atom include chlorine, bromine, fluorine, and iodine. R ₃ is

In this case, examples of R ′ include a methylene group, an ethylene group, a propylene group, and an isopropylene group.

R ₄ and R ₅ may be the same or different and are a hydrogen atom, a methyl group, an ethyl group, or a propyl group. Particularly preferred are a hydrogen atom and a methyl group.

  Specific examples of the compound of the general formula (IV) include 2,2-di (cyanatophenyl) propane, di (4-cyanato-3,5-dimethylphenyl) methane, di (4-cyanatophenyl) thioether, 2,2-di (4-cyanatophenyl) hexafluoropropane, di (cyanatophenyl) ethane, a cyanate compound of phenol and dicyclopentadiene copolymer may be mentioned, and these compounds may be used alone or in combination. Can be used as a mixture.

  In addition to component B1, component B includes component B2 and general formula (V):

(Wherein R ₆ and R ₇ represent a hydrogen atom or a methyl group, and may be the same or different, and s is an integer of 1 to 3) and the general formula (VI):

(In the formula, R ₈ represents a hydrogen atom or a methyl group, and R ₉ represents

And t is 1 or 2), the equivalent ratio of the cyanate group of the cyanate compound of component B2 to the phenolic hydroxyl group of the phenol compound (hydroxyl group / cyanato group) is 0. It is preferable to contain a phenol-modified cyanate ester oligomer (component B3) obtained by reacting in the range of 0.01 to 0.3 from the viewpoint of improving heat resistance, particularly solder heat resistance during moisture absorption.

In the general formula (V), R ₆ and R ₇ may be the same or different and each represents a hydrogen atom or a methyl group. Moreover, s is an integer of 1-3. Specific examples of the phenol compound represented by the general formula (V) include p- (α-cumyl) phenol, mono (or tri) (α-methylbenzyl) phenol, and particularly p- (α-cumyl). Phenol is preferred.

In the general formula (VI), each R ₈ independently represents a hydrogen atom or a methyl group, and R ₉ represents a methyl group, an ethyl group, or

And R ₈ is preferably a methyl group. Further, t is 1 or 2, and a particularly preferable value of t is 1.

  Specific examples of the phenol compound of the general formula (VI) include p-tert-butylphenol, 2,4 (or 2,6) di-tert-butylphenol, p-tert-pentylphenol and p-tert-octylphenol. . Moreover, you may mix 1 type of these phenolic compounds individually and 2 or more types.

  Component B3 is a cyanate ester oligomer in which a cyanate compound containing two or more cyanate groups in one molecule (component B2) alone forms a triazine ring by a cyclization reaction (mainly 3, 5, 7, cyanate compounds). 9 and 11-mers), an imidocarbonate-modified oligomer in which the phenolic hydroxyl group of the phenol compound is added to the cyanate group of component B2, and one or two of the phenol compounds in the structure constituting the triazine ring Oligomer generated by introduction (in this case, one or two of the three chains extending from the triazine ring are replaced with a molecule derived from a phenol compound, resulting in a modified oligomer having fewer crosslinking points than a single oligomer of a cyanate compound) It is a mixed oligomer.

  The phenol-modified cyanate ester oligomer (component B3) is obtained by converting part or all of a cyanate compound (component B2) containing two or more cyanato groups in one molecule with a phenol compound. Considering prevention of recrystallization of the cyanate compound into the solvent when the curable resin composition is varnished, varnish viscosity, coating stability, storage stability, etc., the conversion rate of this component B2 is 10 to 70. %, And as a result, it is preferable that component B3 and unconverted component B2 coexist. More preferably, the conversion rate of component B2 is 20 to 70%.

  In addition, the component B3 takes into consideration prevention of recrystallization of the cyanate compound in the solvent, varnish viscosity, coating stability, storage stability, etc. when the thermosetting resin composition is varnished. The number average molecular weight is preferably obtained by reacting so as to be 380 to 2500. In particular, the number average molecular weight of the phenol-modified cyanate ester oligomer is preferably 800 to 2000.

  In preparing component B3, it is also effective to mix and dissolve component A together with component B2 in advance to form a semi-IPN (Interpenetrating Polymer Network) structure composed of component A and component B2. By adopting this semi-IPN structure, the glass transition temperature, copper foil adhesion, and dielectric properties of the finally obtained thermosetting resin composition can be improved.

  Furthermore, in order to improve the dielectric properties of the cured product of the thermosetting resin composition finally obtained and the heat resistance during moisture absorption, the above-mentioned phenol compound is reacted with the component B2 in a predetermined blending amount with the component B3. Thereafter, at least one selected from the phenol compounds represented by the general formula (V) and the general formula (VI) is added to the component B3, and the compounding equivalent ratio of the cyanate group and the phenol compound in the component B2 before the reaction ( It is preferable to blend so that (hydroxyl group / cyanato group) is less than 0.29. When this hydroxyl group / cyanato group is 0.29 or more, there is a possibility that the dielectric properties are lowered and the heat resistance during moisture absorption is lowered.

  In this way, when the phenol compound is blended after preparing component B3, the phenol compound reacted at the time of preparing B3 and the phenol compound blended after preparing component B3 may be the same or different. Good.

  Furthermore, Component B is one or more selected from phenol novolac type epoxy resins, cresol novolac type epoxy resins, phenol salicylaldehyde novolac type epoxy resins, biphenyl type epoxy resins and dicyclopentadiene type epoxy resins (component B4). May be contained.

  In the thermosetting resin composition of the present invention, the blending amounts of Component A and Component B are preferably determined as follows.

  In consideration of the balance between the glass transition temperature, the solder heat resistance, the adhesiveness to the copper foil, the relative dielectric constant, and the dielectric loss tangent, the component B1 is 50 to 250 parts by mass with respect to 100 parts by mass of the component A. preferable. More preferably, it is 80-200 mass parts.

  When the component B is further contained as the component B, the component B2 is preferably 100 to 400 parts by mass, particularly preferably 150 to 250 parts by mass with respect to 100 parts by mass of the component A. Moreover, it is preferable that the sum total of component B1 and component B2 shall be 200-400 mass parts with respect to 100 mass parts of component A.

  Moreover, when component B contains component B3 further, it is preferable to make component B3 into 100-400 mass parts with respect to 100 mass parts of component A, More preferably, it is 150-250 mass parts. . Moreover, it is preferable that the sum total of component B1, B2 and B3 shall be 200-400 mass parts with respect to 100 mass parts of component A.

  Furthermore, when component B contains component B4, it is preferable to make component B4 into 20-100 mass parts with respect to 100 mass parts of component A1, More preferably, it is 30-80 mass parts. Moreover, it is preferable that the sum total of component B1-B4 shall be 200-400 mass parts with respect to 100 mass parts of component A. FIG.

  In addition, in the thermosetting resin composition of the present invention, in addition to the above components, additives such as a curing accelerator, a filler, other thermoplastic resins, an elastomer, and a flame retardant are blended as necessary. can do.

  As this hardening accelerator, the compound which has a catalyst function which accelerates | stimulates hardening reaction of the glycidyl group of component B1 can be used.

  Examples of such a curing accelerator include alkali metal compounds, alkaline earth metal compounds, imidazole compounds, organic phosphorus compounds, secondary amines, tertiary amines, quaternary ammonium salts, and the like. An imidazole compound is preferred. The blending amount is preferably 0.05 to 3 parts by mass with respect to 100 parts by mass of component B1 in consideration of the catalyst function, storage stability of varnish and prepreg, and the like.

  When Component B contains Component B2, it is preferable to use a curing accelerator having a catalytic function for promoting the self-polymerization reaction of Component B2 and the reaction between Component B2 and the phenol compound. Examples of such curing accelerators include organometallic salts of iron, copper, zinc, cobalt, nickel, manganese, tin (eg, 2-ethylhexane salt, naphthenate) and organometallic complexes (acetylacetone complex, etc.). Can be mentioned. It is preferable that the compounding quantity shall be 0.01-3 mass parts with respect to 100 mass parts of component B2. Furthermore, a part or all thereof may be blended when the component B2 and the component B3 are synthesized, or may be blended after the synthesis.

  Moreover, when using both hardening accelerator together, when a catalyst function and the storage stability of a varnish or a prepreg are considered, it is preferable to set it as 0.1-5 mass parts in total with respect to 100 mass parts of component B2.

  Examples of the filler include fused silica, glass, alumina, zircon, calcium silicate, calcium carbonate, silicon nitride, boron nitride, beryllia, zirconia, potassium titanate, aluminum silicate, magnesium silicate and the like. These can be used as powders or spherical beads. In addition, whiskers, single crystal fibers, glass fibers, hollow fillers, and the like can be used. Examples of the organic type include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

  Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, and silicone resin.

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

  Examples of the flame retardant include halogenated flame retardants such as hexabromobenzene, polycarbonate bromide, brominated epoxy resin and brominated phenol resin, phosphate ester flame retardants such as tricresyl phosphate and trisdichloropropyl phosphate, red phosphorus, Examples include inorganic flame retardants such as antimony trioxide, aluminum hydroxide, and magnesium hydroxide.

  The thermosetting resin composition of the present invention is used for the production of metal-clad laminates and printed wiring boards that are excellent in dielectric properties, heat resistance, insulation reliability, and flame resistance by heat curing and have low water absorption. Is done. Specifically, a prepreg can be produced by dissolving the thermosetting resin composition of the present invention in a solvent to form a varnish, impregnating a base material such as a glass cloth and drying. Next, a metal-clad laminate can be produced by stacking one or a plurality of the prepregs, stacking a metal foil on one surface or upper and lower surfaces, and heating and pressing. Furthermore, a printed wiring board can be produced by a known method using this metal-clad laminate.

  When the thermosetting resin composition of the present invention is varnished, the solvent is not particularly limited, but ketones, aromatic hydrocarbons, esters, amides, alcohols, and the like are used. Specifically, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbon solvents such as toluene and xylene, ester systems such as methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, and ethyl acetate Solvent, amide solvents such as N-methylpyrrolidone, formamide, N-methylformamide, N, N-dimethylacetamide, methanol, ethanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol, triethylene glycol monomethyl Ether, triethylene glycol monoethyl ether, triethylene glycol, propylene glycol monomethyl ether, dipropylene glycol Monomethyl ether, propylene glycol monopropyl ether, alcohol solvents such as dipropylene glycol monopropyl ether. These solvents may be used alone or in combination of two or more.

  The prepreg of the present invention can be produced, for example, by impregnating or coating the thermosetting resin composition of the present invention on a substrate and then semi-curing (B-stage) by heating or the like. As said base material, the well-known thing used for the laminated board for various electrical insulation materials can be used. Specific examples include inorganic fibers such as E glass, D glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and polytetrafluoroethylene, and mixtures thereof.

  These base materials can be used in various forms such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat. The material and shape can be selected according to the intended use and performance of the molded product, and can be used alone or in combination of two or more materials and shapes, and the thickness of the substrate in that case Is not particularly limited, and can be, for example, about 0.03 to 0.5 mm. Those subjected to surface treatment with a silane coupling agent or the like, or those subjected to mechanical opening treatment are suitable from the viewpoints of heat resistance, moisture resistance and processability. The base material was impregnated or coated with the heat-crosslinking resin composition of the present invention so that the amount of the resin composition attached to the base material was 20 to 90% by weight in terms of the resin content of the prepreg after drying. Thereafter, the prepreg of the present invention can be usually obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-stage).

The laminate of the present invention can be produced, for example, by laminating 1 to 20 sheets of the prepreg of the present invention and laminating and forming a metal foil such as copper and aluminum on one or both sides thereof. The metal foil is not particularly limited as long as it is used for electrical insulating materials. In addition, as the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. It can be molded in a range of ˜100 kg / cm ² and a heating time of 0.1 to 5 hours. Further, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.

  Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention in any way.

Synthesis Example 1: Preparation of copolymer resin solution (a-1) of component A In a 2 liter reaction vessel equipped with a thermometer, a stirrer, and a reflux condenser, heated and cooled, from styrene and maleic anhydride. A copolymer resin (manufactured by Elf Atchem, trade name SMA1000, in formula (X), R ₁ is a hydrogen atom, m / n = 1.3, weight average molecular weight 8,000) 410 g, and cyclohexanone 273 g, The temperature was raised to 150 to 160 ° C. and refluxed for 24 hours. Then, it cooled to about 100 degreeC, toluene 398g was added, and the copolymer resin solution (solid content 38 mass%) (a-1) was obtained.

Synthesis Example 2: Preparation of copolymer resin solution (a-2) of component A In a 2 liter reaction vessel equipped with a thermometer, a stirrer and a reflux condenser, heated and cooled to a reaction vessel of styrene and maleic anhydride Copolymer resin (manufactured by Elf Atchem, trade name EF-40), in the formula (X), R ₁ is a hydrogen atom, m / n = 4.0, weight average molecular weight 10,000) 410 g, and cyclohexanone 273 g The mixture was heated to 150 to 160 ° C. and refluxed for 24 hours. Then, it cooled to about 100 degreeC, 398g of toluene was added, and the copolymer resin solution (solid content 38 mass%) (a-2) was obtained.

Synthesis Example 3: Preparation of copolymer resin solution (a-3) of component A1 In a 1 liter reaction vessel equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, which can be heated and cooled, styrene and 202 g of maleic anhydride copolymer resin (manufactured by Elf Atchem, trade name: SMA1000) and 134 g of cyclohexanone were added, the temperature was raised to 100 ° C., and 46.5 g of aniline was added dropwise little by little while maintaining at 97 to 103 ° C. After dropping, the reaction was carried out at 100 ° C. for 4 hours, and then the temperature was raised to 155 to 160 ° C. and the reaction was carried out by refluxing for 12 hours. Thereafter, it is cooled to about 100 ° C., 159 g of toluene is added, and a copolymer resin composed of styrene, maleic anhydride and N-phenylmaleimide (in formula (XVII), R ₁ is a hydrogen atom, m / (n + r) = 1. , N / r = 1, weight average molecular weight 9,000) solution (solid content 45 wt%) (a-3) was obtained.

Synthesis Example 4: Preparation of copolymer resin solution (a-4) of component A1 In a 1 liter reaction vessel equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser, which can be heated and cooled, styrene and 493 g of maleic anhydride copolymer resin (trade name EF-40, manufactured by Elf Atchem Co.) and 329 g of toluene were added, the temperature was raised to 80 ° C., and 17.9 g of aniline was added dropwise little by little while maintaining at 77 to 83 ° C. . After dropping, 49 g of cyclohexanone and 10.5 g of p-tert-pentylphenol were added and reacted at 80 ° C. for 1 hour, and then heated to 120 to 130 ° C. and reacted by refluxing for 5 hours. Thereafter, the mixture is cooled to about 80 ° C., 42 g of methyl ethyl ketone is added, and a copolymer resin composed of styrene, maleic anhydride, N-phenylmaleimide and N-phenylmaleimide having a phenolic hydroxyl group (in the formula (IX), R ₁ is hydrogen). Atom, R ₁₀ is hydroxyl group, x = 0, y = 1, m / (n + r) = 4.0, n / r = 2.3, weight average molecular weight 10,000) solution (solid content 55% by mass) (a -4) was obtained.

Synthesis Example 5: Preparation of component B3 phenol-modified cyanate ester oligomer (b-1) In a 3-liter reaction vessel equipped with a thermometer, a condenser, and a stirrer, 652.5 g of toluene, 2,2-bis (4- Sianatophenyl) propane (trade name Arocy B-10, manufactured by Asahi Ciba Co., Ltd.) 1500 g, p- (α-cumyl) phenol (manufactured by Tokyo Chemical Industry Co., Ltd.) 22.5 g, and the liquid temperature at 120 ° C. After maintaining, 0.3 g of zinc naphthenate (manufactured by Wako Pure Chemical Industries, Ltd.) was added as a reaction accelerator and heated for 4 hours (reaction concentration: 70% by mass), so that the conversion of cyanate compound was about 55%. A phenol-modified cyanate ester oligomer was synthesized. The conversion rate of the cyanate compound is liquid chromatography (model: pump; L-6200 manufactured by Hitachi, Ltd., RI detector; L-3300, column: TSKgel-G4000H, G2000H manufactured by Tosoh Corporation, solvent: THF, Concentration: 1%). The number average molecular weight (Mn) of the obtained phenol-modified cyanate ester oligomer was 1430. At the same time, it was confirmed that the elution peak of p- (α-cumyl) phenol disappeared.

Comparative Synthesis Example 1: Preparation of Styrene Resin (a-5) 277 g of styrene, 4.0 g of ronitrile, 0.4 g of dodecanethiol, 216 g of methyl ethyl ketone and 200 g of toluene were added, and the polymerization reaction was carried out at 70 ° C. for 4 hours in a nitrogen atmosphere. A styrene resin solution (solid content 41 mass%, weight average molecular weight 20,000) ) (A-5) was obtained.

Example 1
As component A, copolymer resin solution (a-2) of Synthesis Example 2 and as component B, biphenyl aralkyl type epoxy resin of component B1 (trade name NC-3000-H, manufactured by Nippon Kayaku Co., Ltd., weight average molecular weight 72, The same applies hereinafter) in the amounts shown in Table 1 and dissolved in methyl ethyl ketone. Then, 2-methylimidazole (trade name 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) is blended according to Table 1 as a curing accelerator, and has a nonvolatile content of 70%. A varnish was obtained.

Example 2
As component A, the copolymer resin solution (a-1) of Synthesis Example 1, as component B, the phenol-modified cyanate ester oligomer (b-1) of Component B3 obtained in Synthesis Example 5, and the biphenylaralkyl type epoxy resin of Component B1 (Trade name NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.), p- (α-cumyl) phenol as a phenol compound to be added later to Component B3 in the blending amount shown in Table 1 and dissolved in methyl ethyl ketone, Zinc naphthenate and 2-methylimidazole (trade name 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) were blended as curing accelerators according to Table 1 to obtain a varnish having a nonvolatile content of 70%.

Example 3
As component A, copolymer resin solution (a-2) of synthesis example 2, as component B, phenol-modified cyanate ester oligomer (b-1) of component B3 obtained in synthesis example 5, and biphenylaralkyl type epoxy resin of component B1 (Trade name NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.), phenol novolac type epoxy resin of component B4 (trade name N-770, manufactured by Dainippon Ink & Chemicals, Inc.), phenol added to component B3 later After compounding p- (α-cumyl) phenol as a compound in the amount shown in Table 1 and dissolving in methyl ethyl ketone, zinc naphthenate and 2-methylimidazole (trade name 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) are used as curing accelerators. Blended according to Table 1, a varnish having a nonvolatile content of 65% was obtained.

Example 4
As component A, the copolymer resin solution (a-4) of Synthesis Example 4, as component B, the phenol-modified cyanate ester oligomer (b-1) of Component B3 obtained in Synthesis Example 5, and the biphenylaralkyl type epoxy resin of Component B1 (Trade name NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.), component B4 cresol novolac type epoxy resin (trade name ESCN-190, manufactured by Sumitomo Chemical Co., Ltd.), and a phenol compound added later to component B3 After blending p- (α-cumyl) phenol in the blending amounts shown in Table 1 and dissolving in methyl ethyl ketone, zinc naphthenate and 2-methylimidazole (trade name 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) are used as curing accelerators. The varnish having a nonvolatile content of 65% was obtained.

Example 5
As component A, copolymer resin solution (a-2) of Synthesis Example 4, as component B, phenol-modified cyanate ester oligomer (b-1) of Component B3 obtained in Synthesis Example 5, and biphenylaralkyl type epoxy resin of Component B1 (Trade name NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.), component B4 phenol salicylaldehyde novolak type epoxy resin (trade name TMH-574, manufactured by Sumitomo Chemical Co., Ltd.), p- (α- Cumyl) phenol is blended in the blending amounts shown in Table 1 and dissolved in methyl ethyl ketone. Then, zinc naphthenate and 2-methylimidazole (trade name 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) are blended as a curing accelerator according to Table 1, and nonvolatile A varnish of 65% min was obtained.

Example 6
As component A, copolymer resin solution (a-2) of synthesis example 2, as component B, phenol-modified cyanate ester oligomer (b-1) of component B3 obtained in synthesis example 5, and biphenylaralkyl type epoxy as component B1 Resin (trade name NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy resin (trade name YX-4000H, manufactured by Japan Epoxy Resin Co., Ltd.) which is component B4, and p- (α-cumyl) as a phenol compound ) After blending phenol in the blending amount shown in Table 1 and dissolving it in methyl ethyl ketone, zinc naphthenate and 2-methylimidazole (2MZ, trade name of Shikoku Kasei Kogyo Co., Ltd.) are blended as curing accelerators according to Table 1, and the nonvolatile content 65% varnish was obtained.

Example 7
As component A, copolymer resin solution (a-2) of synthesis example 2, as component B, phenol-modified cyanate ester oligomer (b-1) of component B3 obtained in synthesis example 5, and biphenylaralkyl type epoxy resin of component B1 (Trade name NC-3000-H, manufactured by Nippon Kayaku Co., Ltd.), dicyclopentadiene type epoxy resin of component B1 (trade name YX-4000H, manufactured by Japan Epoxy Resin Co., Ltd.), p- (α-cumyl as a phenol compound) ) After blending phenol in the blending amount shown in Table 1 and dissolving in methyl ethyl ketone, zinc naphthenate and 2-methylimidazole (trade name 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) are blended as a curing accelerator according to Table 1, and the non-volatile content 65% varnish was obtained.

Comparative Example 1
As component A, a copolymer resin solution (a-2) of Synthesis Example 2 and as component B, a cresol novolac type epoxy resin (trade name ESCN-190, manufactured by Sumitomo Chemical Co., Ltd.) is blended in the blending amounts shown in Table 1. After being dissolved in methyl ethyl ketone, 2-methylimidazole (trade name: 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was blended as a curing accelerator according to Table 1 to obtain a varnish having a nonvolatile content of 70%.

Comparative Example 2
As component A, the copolymer resin solution (a-1) of Synthesis Example 1 and as component B, the phenol-modified cyanate ester oligomer (b-1) of Component B3 obtained in Synthesis Example 5 and a phenol novolac epoxy resin (trade name) N-770, manufactured by Dainippon Ink and Chemicals, Inc.), p- (α-cumyl) phenol as a phenol compound was blended in the blending amounts shown in Table 1, dissolved in methyl ethyl ketone, and then zinc naphthenate and 2- Methylimidazole (trade name 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) was blended according to Table 1 to obtain a varnish having a nonvolatile content of 70%.

Comparative Example 3
As component A, the copolymer resin solution (a-3) of Synthesis Example 3, and as Component B, the phenol-modified cyanate ester oligomer (b-1) of Component B3 obtained in Synthesis Example 5, a phenol novolac epoxy resin (trade name) N-770, manufactured by Dainippon Ink Chemical Co., Ltd.), biphenyl type epoxy resin (trade name YX-4000H, manufactured by Japan Epoxy Resin Co., Ltd.), and p- (α-cumyl) phenol as a phenol compound shown in Table 1. After mixing in an amount and dissolving in methyl ethyl ketone, zinc naphthenate and 2-methylimidazole (trade name 2MZ, manufactured by Shikoku Kasei Kogyo Co., Ltd.) were blended according to Table 1 as a curing accelerator to obtain a varnish having a nonvolatile content of 65%.

Comparative Example 4
As component A, copolymer resin solution (a-5) of comparative synthesis example 1, as component B, phenol-modified cyanate ester oligomer (b-1) of component B3 obtained in synthesis example 5, biphenylaralkyl type epoxy resin (product) NC-3000-H (manufactured by Nippon Kayaku Co., Ltd.), p- (α-cumyl) phenol as a phenol compound in the blending amounts shown in Table 1, dissolved in methyl ethyl ketone, and zinc naphthenate as a curing accelerator and 2 -Methylimidazole (trade name 2MZ, manufactured by Shikoku Chemicals Co., Ltd.) was blended according to Table 1 to obtain a varnish having a nonvolatile content of 65%.

Evaluation test The varnish obtained in Examples 1 to 7 and Comparative Examples 1 to 4 was impregnated into a 0.2 mm thick glass cloth (basis weight 210 g / m ² ) and dried at 160 ° C. for 5 minutes to obtain a prepreg. It was. Four prepregs were laminated, and copper foils each having a thickness of 18 μm were laminated on the top and bottom, and press-molded at 230 ° C. and 2.45 MPa for 2 hours to prepare a copper-clad laminate. Subsequently, after removing copper of the copper-clad laminate by etching, a test piece of the laminate was obtained. Each test piece was evaluated for dielectric properties, glass transition temperature (Tg), solder heat resistance, water absorption, and outer layer peel strength. The evaluation method is as follows.

(1) Dielectric property: A dielectric property of 1 GHz was measured by a triplate structure linear line resonator method.
(2) Glass transition temperature (Tg): measured by a thermomechanical analysis method (TMA method).
(3) Solder heat resistance during moisture absorption: A test piece cut to 50 mm × 50 mm was subjected to moisture absorption treatment at 121 ° C. and 0.22 MPa for 5 hours with a pressure cooker, and then immersed in a solder bath at 260 ° C. for 20 seconds. The state of the test piece was visually observed. In the evaluation, the case where the occurrence of blistering and mesling was 0 was marked with ◯, the occurrence of messing was 21 or more, or the occurrence of blistering was 11 or more, and x was otherwise.
(4) Water absorption: A test piece cut to 50 mm × 50 mm was subjected to moisture absorption treatment at 121 ° C. and 0.22 MPa for 5 hours with a pressure cooker, and the water absorption was calculated from the weight difference before and after the moisture absorption treatment.
(5) Copper foil peel strength: A 1 cm wide copper line was formed by etching, and the copper foil peel strength in the 90 ° C. direction was measured by an autograph.

  As is apparent from Table 1, the examples of the present invention are excellent in all of dielectric characteristics, moisture and heat resistance, and adhesiveness (copper foil peel strength). In particular, the component B containing the phenol-modified cyanate ester oligomer (b-1) which is the component B3 (Examples 2 to 7) has a high glass transition temperature, and the moisture-absorbing solder heat resistance is further improved. confirmed. On the other hand, it was confirmed that none of the comparative examples were excellent in all of dielectric properties, moisture heat resistance, and adhesive properties, and in particular, the solder heat resistance was inferior.

Claims (18)

Component A General Formula (I):

(In the formula, R ₁ is a hydrogen atom, a halogen atom, or a C _{1 to} C ₅ hydrocarbon group, and R ₂ is independently a halogen atom or a C _{1 to} C ₅ aliphatic hydrocarbon. A monomer unit (a) represented by a group, an aromatic hydrocarbon group or a hydroxyl group, and x is an integer of 0 to 3, and a general formula (II):

A copolymer resin (component A) containing a monomer unit (b) represented by:
Component B A thermosetting resin composition containing a thermosetting resin, wherein the component B is a component B1 general formula (III):

(P is an integer greater than or equal to 1) The thermosetting resin composition characterized by containing the biphenyl aralkyl type epoxy resin shown. The thermosetting resin composition according to claim 1, wherein Component B further comprises a cyanate compound containing two or more cyanato groups in one molecule as Component B2. The component B2 has the general formula (IV):

[Wherein R ₃ represents a halogen-substituted or unsubstituted C ₁ -C ₃ alkylene group, —S—,

(R ′ is a C ₁ -C ₃ alkylene group), and R ₄ and R ₅ are each independently a hydrogen atom or a C ₁ -C ₃ alkyl group]. The thermosetting resin composition according to claim 1 or 2, wherein The component B contains the component B3, and the component B3 includes the cyanate compound of the component B2,
Formula (V):

(Wherein R ₆ and R ₇ represent a hydrogen atom or a methyl group, and may be the same or different, and s is an integer of 1 to 3) and the general formula (VI):

(In the formula, R ₈ represents a hydrogen atom or a methyl group, and R ₉ represents

And at least one selected from phenol compounds represented by t is 1 or 2, and the equivalent ratio of the phenolic hydroxyl group of the phenol compound to the cyanate group of the cyanate compound of Component B2 (hydroxyl group / cyanato group) ) Is a phenol-modified cyanate ester oligomer obtained by reacting in the range of 0.01 to 0.3. The thermosetting resin composition according to claim 1 or 2. The thermosetting resin composition of any one of Claims 1-4 whose compounding quantity of the said component B1 with respect to 100 mass parts of the said component A is 50-250 mass parts. The thermosetting resin composition of Claim 2 or 3 whose compounding quantity of the said component B2 with respect to 100 mass parts of the said component A is 100-400 mass parts. The thermosetting resin composition of Claim 4 whose compounding quantity of the said component B3 with respect to 100 mass parts of the said component A is 100-400 mass parts. The component A is represented by the general formula (VII):

8. In any one of claims 1 to 7, wherein m and n are integers of 1 or more, and R ₁ , R ₂ , and x are as defined above. The thermosetting resin composition as described. The thermosetting resin composition of Claim 8 whose copolymer composition ratio m / n of the monomer unit (a) with respect to a monomer unit (b) is 0.8-19 in the said component A. The thermosetting resin composition according to claim 9, wherein x is 0 in the monomer unit (a) of the component A. Component A is
Component A1 In addition to the monomer units (a) and (b), the general formula (VIII):

(In the formula, R ₁₀ is a halogen atom, a C ₁ -C ₅ aliphatic hydrocarbon group, an aromatic hydrocarbon group, a hydroxyl group, a thiol group, or a carboxyl group, and y is an integer of 0-3. The thermosetting resin composition of any one of Claims 1-7 which is a copolymer resin containing the monomer unit (c) shown by this. The component A1 is represented by the general formula (IX):

12. In the formula, r is an integer of 1 or more, and R ₁ , R ₂ , R ₁₀ , m, n, x, and y are as defined above. Thermosetting resin composition. The thermosetting resin composition according to claim 12, wherein a copolymer composition ratio m / (n + r) of the monomer unit (a) to the monomer units (b) and (c) is 0.8 to 19 in the component A1. object. The thermosetting resin composition according to claim 12, wherein in the component A1, the copolymer composition ratio n / r of the monomer unit (b) to the monomer unit (c) is from 1/49 to 49. The component B further contains at least one selected from a phenol novolac epoxy resin, a cresol novolac epoxy resin, a phenol salicylaldehyde novolac epoxy resin, a biphenyl epoxy resin, and a dicyclopentadiene epoxy resin. The thermosetting resin composition according to any one of 1 to 14. A prepreg obtained by varnishing the thermosetting resin composition according to any one of claims 1 to 15 and impregnating the varnish into a base material, followed by drying. A metal-clad laminate obtained by stacking one or more prepregs according to claim 16, laminating a metal foil on at least one surface thereof, and heating and pressing. A printed wiring board using the metal laminate according to claim 17.