JP6977241B2 - Thermosetting resin composition, prepreg, laminated board and printed wiring board - Google Patents

Description

The present invention relates to a thermosetting resin composition and a prepreg, a laminated board and a printed wiring board using the same.

Thermosetting resins are widely used in fields where high reliability is required, such as electronic components, because their unique crosslinked structure exhibits high heat resistance and dimensional stability. In particular, copper-clad laminates and interlayer insulating materials are required to have high copper foil adhesiveness for forming fine wiring and workability such as drilling or punching due to the recent demand for high density. To.

In recent years, in order to process a large amount of data at high speed, the frequency of signals has been increasing in computers, information equipment terminals, and the like. As the frequency increases, the transmission loss of the electric signal increases, so that the copper-clad laminate and the interlayer insulating material are required to have a low relative permittivity and a low dielectric loss tangent.

Furthermore, in recent years, due to the growing awareness of the environment, consideration for the environment has become indispensable for electronic devices and electronic components. Halogen-based flame retardants used in all plastic products including electronic parts are capable of producing toxic brominated dibenzodioxin and furan when decabromodiphenyl oxide, which is the most typical brominated flame retardant, is incinerated. Its safety has been questioned since it was reported. Therefore, from the viewpoint of consideration for environmental problems, the introduction of conventional halogen-free products that do not use brominated flame retardants containing halogens is being promoted.
Halogen-free means that the halogen atom is not contained at all, or the content thereof is extremely small. For example, in the Japan Electronic Circuit Industry Association, a copper-clad laminate for a halogen-free printed wiring board is used. The definition is that the content of chlorine (Cl) and bromine (Br) is 900 ppm or less, and the total content of chlorine (Cl) and bromine (Br) is 1500 ppm or less.

As a method for imparting flame retardancy without containing a halogen-based compound, a method in which a phosphorus-containing flame retardant and a relatively large amount of an inorganic filler are used in combination is usually applied. As the inorganic filler used here, aluminum hydroxide, silica and the like are often selected. However, according to this method, there is a problem that the resin layer is weakened and the copper foil adhesiveness is deteriorated in the desmear step of removing the smear generated after the drilling process. Therefore, it has been difficult to achieve both halogen-free and excellent flame retardancy, low relative permittivity, low dielectric loss tangent and excellent copper foil adhesiveness.

For example, Patent Document 1 describes in advance a specific ratio of an epoxy resin and a monofunctional acid anhydride as a resin composition capable of achieving a high glass transition temperature, lowering the dielectric constant, and increasing the peel strength. A resin composition comprising a reacted preliminary reaction product is disclosed.

JP-A-2015-13941

However, even in the resin composition disclosed in Patent Document 1, the copper foil adhesiveness is not sufficient and improvement is desired.
The present invention has been made in view of the above problems, and is a thermosetting resin composition having excellent copper foil adhesiveness, excellent relative permittivity and dielectric loss tangent, and a prepreg and a laminated board using the same. And to provide a printed wiring board.

As a result of studying to solve the above-mentioned problems, the present inventors have found that the following problems can be solved by the present invention.
That is, the present invention provides the following thermosetting resin compositions, prepregs, laminated boards and printed wiring boards.
[1] (A) Inorganic filler coupled with aminosilane, (B) Epoxy resin, (C) (c-1) Monomer unit represented by the following general formula (1) and (c-2) ) A thermosetting resin composition containing a copolymer resin containing a monomer unit represented by the following general formula (2).

(In the formula, R ₁ and R ₂ independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group.)

[2] The thermosetting resin composition according to the above [1], further comprising (D) a maleimide compound having an N-substituted maleimide group in the molecule.
[3] As a maleimide compound having an N-substituted maleimide group in (D) molecule, (d-1) a structural unit derived from a maleimide compound having at least two N-substituted maleimide groups in one molecule, and (d-1). -2) The thermosetting resin composition according to the above [2], which comprises a maleimide compound containing a structural unit derived from an amine compound having an acidic substituent represented by the following general formula (3).

(In the formula, R ₃ independently represents an acidic substituent selected from a hydroxyl group, a carboxy group and a sulfonic acid group, and R ₄ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)

[4] The above-mentioned [2], wherein the maleimide compound having an N-substituted maleimide group in the molecule (D) includes a compound represented by the following general formula (4) or a compound represented by the following general formula (5). Alternatively, the thermosetting resin composition according to [3].

(In the formula, R ₃ , R ₄ , x and y represent the same as those in the general formula (3), and R ₅ independently contains a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. show.)

(In the formula, R ₃ , R ₄ , x and y represent the same as those in the general formula (3), and R ₆ and R ₇ each independently have a hydrogen atom and an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Alternatively, it indicates a halogen atom, and A is an alkylene group, an alkylidene group, an ether group, a sulfonyl group or a divalent group represented by the following formula (6).)

[5] The thermosetting resin composition according to any one of the above [1] to [4], further comprising (E) dicyandiamide.
[6] A prepreg containing the thermosetting resin composition according to any one of the above [1] to [5].
[7] A laminated board containing a cured product of the prepreg according to the above [6].
[8] A printed wiring board including the laminated board according to the above [7].

According to the present invention, it is possible to provide a thermosetting resin composition having excellent copper foil adhesiveness, excellent relative permittivity and dielectric loss tangent, and prepregs, laminated boards and printed wiring boards using the same.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises (A) an inorganic filler coupled with an aminosilane (hereinafter, also referred to as “(A) component”) and (B) an epoxy resin (hereinafter, “(B)). A copolymer resin containing (C) (c-1) a monomer unit represented by the following general formula (1) and (c-2) a monomer unit represented by the following general formula (2). (Hereinafter, also simply referred to as "(C) copolymer resin" or "(C) component").

(In the formula, R ₁ and R ₂ independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group.)

By adopting the above structure, the thermosetting resin composition of the present invention has excellent copper foil adhesiveness, excellent relative permittivity and dielectric loss tangent. The reason why such an effect is obtained is not clear, but it is considered as follows.
That is, in the thermosetting resin composition of the present invention, by using an inorganic filler coupled with aminosilane, the adhesive force between the inorganic filler and the organic resin component is improved, and plated copper or laminated copper foil is used. Since the resin portion as the base material of the above is tougher than that of the conventional one, it is considered that the copper foil adhesiveness can be improved without deteriorating the general characteristics. In the present specification, the copper foil adhesiveness means both the adhesiveness to the copper foil formed by plating and the adhesiveness to the laminated copper foil.

<(A) Inorganic filler treated with aminosilane>
The inorganic filler contained in the thermosetting resin composition of the present invention is coupled with aminosilane. By treating the inorganic filler with aminosilane, the affinity with the thermosetting resin is improved, and the thermosetting resin composition containing the inorganic filler has excellent copper foil adhesiveness, flame retardancy and dielectric properties. Become.
On the other hand, in the case of the inorganic filler not treated with aminosilane, the interfacial treatment effect cannot be obtained, so that the distance between the particles becomes short and the inorganic filler particles tend to aggregate. This aggregation causes a decrease in heat resistance, poor insulation, and the like in the printed wiring board. In addition, since the affinity with the epoxy resin is low, the resin layer becomes fragile in the desmear process for removing the smear generated after the drilling process, and excellent copper foil adhesiveness cannot be obtained.

Examples of the inorganic filler include silica, mica, talc, short fiber or fine powder of glass, hollow glass, antimony trioxide, calcium carbonate, quartz powder, aluminum hydroxide, magnesium hydroxide and the like. These may be used alone or in admixture of two or more. Among these, silica, aluminum hydroxide and magnesium hydroxide are preferable, and silica is more preferable, from the viewpoint of dielectric properties, heat resistance and flame retardancy.
Examples of silica include precipitated silica manufactured by a wet method and having a high water content, and dry silica manufactured by a dry method and containing almost no bound water or the like. Examples thereof include crushed silica, fumed silica, and fused spherical silica. Among these, fused spherical silica is preferable because of its low thermal expansion and high fluidity when filled in a resin.

The average particle size of the inorganic filler is preferably 0.01 to 30 μm. Within this range, the obtained thermosetting resin composition has good moldability (inner layer circuit filling property). From the same viewpoint, the average particle size of the inorganic filler is more preferably 0.1 to 10 μm, and further preferably 0.3 to 2 μm.
The average particle size of the inorganic filler means the volume average particle size. The volume average particle size is the particle size at a point corresponding to 50% of the volume when the cumulative frequency distribution curve by the particle size is obtained with the total volume of the particles as 100%, and the particle size using the laser diffraction scattering method. It can be measured with a distribution measuring device or the like.

The component (A) is not particularly limited as long as it is an inorganic filler treated with aminosilane, but an inorganic filler previously treated with aminosilane before being blended with the resin is preferable. That is, the method of coupling the inorganic filler with aminosilane is directly applied to the inorganic filler from the so-called integral blend treatment method in which the inorganic filler is mixed in the resin and then the aminosilane is added to the resin composition. A method of coupling the aminosilane by a dry method or a wet method is preferable. The coupling-treated inorganic filler may be blended as it is, or may be blended after being made into a slurry.

The aminosilane means a compound having a group containing a silicon atom to which a hydrolyzable group is bonded and a substituted or unsubstituted amino group.
Examples of the substituent of the substituted amino group include an alkyl group and an aryl group.
The alkyl group may be, for example, an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 3 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like.
The aryl group may be, for example, an aryl group having 6 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms. Specific examples of the aryl group include a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group and the like. Examples of the substituent of the aryl group include an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group are the same as described above.
Among these, from the viewpoint of adhesiveness to the organic resin, it is preferable to have an amino group substituted with an aryl group, and it is more preferable to have an amino group substituted with a phenyl group.
The amino group may be either a primary amino group, a secondary amino group or a tertiary amino group, but is preferably a secondary amino group from the viewpoint of reactivity with the resin.
Examples of the hydrolyzable group include an alkoxy group having 1 to 5 carbon atoms, an acyloxy group having 1 to 5 carbon atoms, and an alkenyloxy group having 1 to 5 carbon atoms. Among these, an alkoxy group is preferable from the viewpoint of versatility and hydrolyzability. Examples of the alkoxy group include a methoxy group and an ethoxy group.
The number of hydrolyzable groups bonded to the silicon atom in the aminosilane is preferably 1 to 3, more preferably 2 or 3, and even more preferably 3 from the viewpoint of resistance in the chemical solution treatment step of the printed wiring board.

The aminosilane is not particularly limited, and is, for example, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltri. Methoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, 3 -Trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, etc. Will be. These may be used alone or in admixture of two or more. Among these, N-phenyl-3-aminopropyltrimethoxysilane is preferable from the viewpoint of dispersibility of the inorganic filler, reactivity with the resin, and adhesiveness.
By coupling treatment with aminosilane, not only the aggregation of the inorganic filler can be suppressed, but also the curability of the resin can be improved, and the reactivity and adhesiveness between the inorganic filler and the resin can be improved, and the copper foil adhesiveness can be improved. It can exhibit high chemical resistance to various acidic or basic aqueous solutions used in the printed wiring board manufacturing process while improving high frequency characteristics, thermal expansion characteristics, etc. and high heat resistance.

The component (A) is also commercially available, for example, "SC2050-KNK" (manufactured by Admatex Co., Ltd.), which is silica coupled with N-phenyl-3-aminopropyltrimethoxysilane. And so on.

The content of the component (A) in the thermosetting resin composition of the present invention is 10 to 300 parts by mass with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A). It is preferably 10 to 250 parts by mass, more preferably 10 to 200 parts by mass, particularly preferably 15 to 150 parts by mass, and extremely preferably 15 to 115 parts by mass. preferable. When the content of the component (A) is 10 parts by mass or more, low dielectric loss tangent, low thermal expansion, high heat resistance, and high plating peel strength can be obtained, and when it is 300 parts by mass or less, excellent moldability can be obtained. ..
Here, the "solid content conversion" in the present invention means that only the non-volatile content excluding volatile components such as organic solvents is used as a reference. That is, 100 parts by mass in terms of solid content means equivalent to 100 parts by mass of non-volatile content.

<(B) Epoxy resin>
(B) The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. Here, the (B) epoxy resin is classified into a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, and the like, and these can be used alone or in combination of two or more. can.
Epoxy resins are classified into various epoxy resins according to the difference in the main skeleton, and in each of the above types of epoxy resins, bisphenol A type, bisphenol F type, biphenyl type, novolak type, polyfunctional phenol type, and naphthalene type are further classified. , Alicyclic type, alcohol type epoxy resin, etc.
Among these, bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene ring-containing epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, from the viewpoint of dielectric properties, heat resistance, moisture resistance and copper foil adhesiveness, Phenol novolak type epoxy resin and cresol novolak type epoxy resin are preferable, and dicyclopentadiene type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl type epoxy resin and phenol novolac type epoxy have excellent dielectric properties and high glass transition temperature. The resin is more preferable, and the cresol novolac type epoxy resin and the dicyclopentadiene type epoxy resin are further preferable from the viewpoint of moisture resistance and heat resistance.

<(C) Copolymer resin>
The (C) copolymer resin contains (c-1) a monomer unit represented by the following general formula (1) and (c-2) a monomer unit represented by the following general formula (2).

(In the formula, R ₁ and R ₂ independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group.)

Examples of the hydrocarbon group having 1 to 5 carbon atoms represented by R ₁ and R ₂ include an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and an alkynyl group having 1 to 5 carbon atoms. Can be mentioned.
Examples of the halogen atom represented by R ₁ and R ₂ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among the groups represented by R ₁ and R ₂ , from the viewpoint of solubility in a solvent and compatibility with a resin, an alkyl group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group is preferable, and phenyl. It is more preferable that it is a group.
Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group and the like.
Examples of the substituent in the substituted phenyl group include groups similar to the hydrocarbon group having 1 to 5 carbon atoms represented by _{R 1} and R _2.

(C) The total content of the monomer unit represented by the general formula (1) and the monomer unit represented by the general formula (2) in the copolymer resin is preferably 50% by mass or more, more preferably 50% by mass or more. It is 70% by mass or more, more preferably 90% by mass or more, and particularly preferably substantially 100% by mass.
(C) The ratio (m: n) of the number of moles m of the monomer unit represented by the general formula (1) to the number n of the number of moles of the monomer unit represented by the general formula (2) in the copolymer resin is , Preferably 2: 1 to 8: 1, more preferably 2: 1 to 7: 1, still more preferably 3: 1 to 6: 1, and particularly preferably 3: 1 to 5: 1.

The (C) copolymer resin can be produced, for example, by copolymerizing a vinyl compound and maleic anhydride.
(C) Examples of the vinyl compound used as the raw material monomer of the copolymerized resin include vinyl compounds such as ethylene, propylene, butadiene, isobutylene and acrylonitrile; methacrylates such as methylmethacrylate and methacryloyl groups such as acrylates such as methylacrylate or acryloyl. Compounds having a group; styrene-based compounds such as styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene and the like can be mentioned. These may be used alone or in admixture of two or more. Among these, a copolymer resin of styrene and maleic anhydride and a copolymer resin of isobutylene and maleic anhydride are preferable from the viewpoint of solubility in a solvent and compatibility with a resin.
Further, a substituent such as an allyl group, a methacryloyl group, an acryloyl group or a hydroxy group may be arbitrarily introduced into the monomer through a Friedel-Crafts reaction, a reaction using a metal-based catalyst such as lithium, or the like.

<(D) Maleimide compound having an N-substituted maleimide group in the molecule>
The thermosetting resin composition of the present invention preferably further contains a maleimide compound having an N-substituted maleimide group in the molecule (D) (hereinafter, also referred to as “component (D)”).
As the component (D), any maleimide compound having an N-substituted maleimide group in the molecule can be used without particular limitation. For example, a maleimide compound having one N-substituted maleimide group in one molecule, Examples thereof include maleimide compounds having two N-substituted maleimide groups in one molecule.

Examples of the maleimide compound having one N-substituted maleimide group in one molecule include N-phenylmaleimide and N-hydroxyphenylmaleimide.
Examples of the maleimide compound having two N-substituted maleimide groups in one molecule include bis (4-maleimidephenyl) methane, poly (maleimidephenyl) methane, bis (4-maleimidephenyl) ether, and bis (4-maleimidephenyl) ether. Maleimidephenyl) sulfone, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2,2- Examples thereof include bis [4- (4-maleimidephenoxy) phenyl] propane. These may be used alone or in admixture of two or more.
Among these, bis (4-maleimidephenyl) methane, m-phenylene bismaleimide and bis (4-maleimidephenyl) sulfone are preferable from the viewpoint of high reaction rate and higher heat resistance, and are inexpensive. M-Phenylene bismaleimide and bis (4-maleimidephenyl) methane are more preferable, and bis (4-maleimidephenyl) methane is further preferable from the viewpoint of solubility in a solvent.

The component (D) is a structural unit derived from (d-1) a maleimide compound having at least two N-substituted maleimide groups in the one molecule (hereinafter, also referred to as “(d-1) maleimide compound”). (D-2) A maleimide compound containing a structural unit derived from an amine compound having an acidic substituent represented by the following general formula (3) (hereinafter, also referred to as “(d-2) amine compound”) (hereinafter, simply referred to as “simply”). It is also preferable to be "a compound having an acidic substituent and an unsaturated maleimide group").

(In the formula, R ₃ independently represents an acidic substituent selected from a hydroxyl group, a carboxy group and a sulfonic acid group, and R ₄ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)

Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R _4, for example, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an alkynyl group having 1 to 5 carbon atoms Can be mentioned. Among these, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like.

Examples of the (d-2) amine compound include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, and o-aminobenzenesulfon. Examples thereof include acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline and the like. These may be used alone or in admixture of two or more. Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline are preferable from the viewpoint of solubility and synthetic yield, and point of heat resistance. Therefore, aminophenols such as o-aminophenol, m-aminophenol, and p-aminophenol are more preferable, and p-aminophenol is further preferable from the viewpoint of dielectric properties.

The ratio of the amount of the (d-1) maleimide compound to the (d-2) amine compound used is the same as the maleimide group equivalent of the (d-1) maleimide compound and the -NH ₂ group equivalent of the (d-2) amine compound. Equivalent ratio is:
1.0 <(maleimide group equivalent) / (-NH ₂ group equivalent) ≤ 10.0
The range shown in is preferable, and the corresponding amount ratio is more preferably in the range of 2.0 to 10.0. By setting the equivalent ratio within the above range, gelation does not occur, and the solubility in a solvent and the heat resistance of the thermosetting resin are excellent.

A compound having an acidic substituent and an unsaturated maleimide group can be obtained by reacting a (d-1) maleimide compound with a (d-2) amine compound.
The reaction between the (d-1) maleimide compound and the (d-2) amine compound may be carried out in an organic solvent. The organic solvent is not particularly limited, and is, for example, an alcohol solvent such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, and propylene glycol monomethyl ether; a ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; tetrahydrofuran and the like. Ether-based solvents; aromatic solvents such as toluene, xylene, mesitylen, etc .; nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; sulfur-containing solvents such as dimethylsulfoxide, etc., which may be used alone or. Two or more types can be mixed and used.
Among these organic solvents, cyclohexanone, propylene glycol monomethyl ether and methyl cellosolve are preferable from the viewpoint of solubility, and cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity, and they are highly volatile and during the production of prepreg. Propylene glycol monomethyl ether is more preferable because it does not easily remain as a residual solvent.
The amount of the organic solvent used is preferably 10 to 1000 parts by mass, more preferably 30 to 500 parts by mass, based on 100 parts by mass of the total of the (d-1) maleimide compound and the (d-2) amine compound. It is preferably 50 to 200 parts by mass, and more preferably 50 to 200 parts by mass. When the amount of the organic solvent used is 10 parts by mass or more, the solubility becomes sufficient, and when it is 1000 parts by mass or less, a sufficient reaction rate can be obtained.

The reaction temperature between the (d-1) maleimide compound and the (d-2) amine compound is preferably 50 to 200 ° C, more preferably 100 to 160 ° C. The reaction time is preferably 0.1 to 10 hours, more preferably 1 to 8 hours.
A reaction catalyst can be optionally used for this reaction. The reaction catalyst is not particularly limited, and examples thereof include amines such as triethylamine, pyridine, and tributylamine; imidazoles such as methylimidazole and phenylimidazole; and phosphorus-based catalysts such as triphenylphosphine, which may be used alone or 2 Can be used by mixing seeds or more.

Examples of the component (D) obtained by reacting the (d-1) maleimide compound with the (d-2) amine compound include a compound represented by the following general formula (4) and the following general formula (5). One or more selected from the represented compounds may be mentioned.

(In the formula, R ₃ , R ₄ , x and y represent the same as those in the general formula (3), and R ₅ independently contains a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. show.)

(In the formula, R ₃ , R ₄ , x and y represent the same as those in the general formula (3), and R ₆ and R ₇ are independently hydrogen atoms, aliphatic hydrocarbon groups having 1 to 5 carbon atoms or groups. It represents a halogen atom, and A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group or a divalent group represented by the following formula (6).)

_{Examples of the aliphatic hydrocarbon group having 1 to 5 carbon atoms represented by R 5} , R ₆ and R ₇ in the general formulas (4) and (5) include an alkyl group having 1 to 5 carbon atoms and a carbon number of carbon atoms. Examples thereof include an alkenyl group having 1 to 5 and an alkynyl group having 1 to 5 carbon atoms. Among these, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like.
Examples of the halogen atom represented by R ₅ , R ₆ and R ₇ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

<(E) dicyandiamide>
The thermosetting resin composition of the present invention preferably further contains (E) dicyandiamide (hereinafter, also referred to as “component (E)”). By containing (E) dicyandiamide, heat resistance, dielectric properties, moldability and flame retardancy are excellent.

The content of the components (B) to (E) in the thermosetting resin composition of the present invention is preferably as follows.
The content of the component (B) is preferably 1 to 80 parts by mass, preferably 10 to 70 parts by mass with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A). More preferably, it is more preferably 20 to 60 parts by mass. By setting the content of the component (B) to 1 part by mass or more, excellent heat resistance and flame retardancy can be obtained, and the moldability when used as a prepreg is improved, and by setting the content to 80 parts by mass or less. , Good dielectric properties can be obtained.
The content of the component (C) is preferably 2 to 50 parts by mass, preferably 5 to 40 parts by mass with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A). More preferably, it is more preferably 5 to 30 parts by mass. When the content of the component (C) is 2 parts by mass or more, the dielectric constant becomes low, and when it is 50 parts by mass or less, excellent moldability, adhesiveness and flame retardancy can be obtained.
When the thermosetting resin composition of the present invention contains the component (D), the content thereof is 1 to 98 with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A). It is preferably 9.9 parts by mass, more preferably 20 to 98.9 parts by mass, and even more preferably 20 to 90 parts by mass. When the content of the component (D) is 1 part by mass or more, flame retardancy, adhesiveness and dielectric properties are improved, and when it is 98.9 parts by mass or less, good heat resistance can be obtained.
When the thermosetting resin composition of the present invention contains the component (E), the content thereof is 0.1 with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A). It is preferably ~ 50 parts by mass, more preferably 0.5 to 50 parts by mass, and even more preferably 0.5 to 30 parts by mass. When the content of the component (E) is 0.1 parts by mass or more, the solubility and the dielectric property are improved, and when the content is 50 parts by mass or less, good flame retardancy can be obtained.

<Other ingredients>
Further, the thermosetting resin composition of the present invention is optionally known as a thermoplastic resin, a curing agent, a curing accelerator, an elastomer, a flame retardant, an organic filler, an organic solvent, as long as the effect of the present invention is not impaired. It may contain additives and the like.

Examples of the thermoplastic resin include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin other than the component (D), xylene resin, and petroleum resin. Examples include silicon resin.

Examples of the curing agent include acid anhydrides other than the component (C); amine compounds such as diaminodiphenylmethane; phenol compounds such as phenol novolac and cresol novolac; 6-substituted guanamine compounds represented by the following general formula (7) and the like. Can be mentioned.

(In the formula, R ₈ represents a phenyl group, a methyl group, a butyl group, an allyl group, a methoxy group or a benzyloxy group.)

Examples of the 6-substituted guanamine compound represented by the general formula (7) include 2,4-diamino-6-phenyl-s-triazine called benzoguanamine and 2,4-diamino-called acetoguanamine. Examples thereof include 6-methyl-s-triazine and 2,4-diamino-6-vinyl-s-triazine, among which benzoguanamine having a high reaction rate and capable of higher heat resistance and lower dielectric constant and 2 , 4-Diamino-6-vinyl-s-triazine is more preferred, and benzoguanamine is even more preferred because of its low cost and solubility in solvents.

Examples of the curing accelerator include imidazoles and derivatives thereof, tertiary amines, quaternary ammonium salts and the like.

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

Examples of the flame retardant include halogen-containing flame retardants containing bromine, chlorine and the like; phosphorus-based flame retardants such as triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphazene and red phosphorus; antimony trioxide and water. Examples thereof include flame retardants of inorganic substances such as aluminum oxide and magnesium hydroxide. Among these flame retardants, phosphorus-based flame retardants, which are non-halogen flame retardants, inorganic flame retardants, and the like are preferable from the viewpoint of reducing the environmental load. Further, it is preferable to use a phosphorus-based flame retardant and an inorganic flame retardant such as aluminum hydroxide in combination from the viewpoint of compatibility with other properties such as economy and heat resistance.

Examples of the organic filler include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; alcohol solvents such as methyl cellosolve; ether solvents such as tetrahydrofuran; aromatic solvents such as toluene, xylene and mesitylene. Can be mentioned.

Examples of the additive include ultraviolet absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals and thioxanthones, and stilbene derivatives. Examples thereof include a fluorescent whitening agent, a urea compound such as urea silane, and an adhesion improving agent such as a silane coupling agent.

[Prepreg]
The prepreg of the present invention contains the thermosetting resin composition of the present invention.
The prepreg of the present invention is, for example, impregnated or coated on a substrate with the thermosetting resin composition of the present invention and then heat-dried to semi-cure the thermosetting resin composition of the present invention (B stage). ) Can be manufactured. Hereinafter, the prepreg of the present invention will be described in detail.

As the base material used for the prepreg of the present invention, well-known materials used for various laminated boards for electrical insulating materials can be used. Examples of the material 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 have the shape of, for example, woven fabric, non-woven fabric, robink, chopped strand mat, surfaced mat, etc., but the material and shape are selected according to the intended use and performance of the molded product, and if necessary. It can be used alone or in combination of two or more materials and shapes.
The thickness of the base material is not particularly limited, but for example, a material having a thickness of about 0.01 to 0.5 mm can be used, and a material surface-treated with a silane coupling agent or the like or mechanically opened. Is suitable from the viewpoint of heat resistance, moisture resistance and processability. After impregnating or coating the substrate so that the amount of the thermosetting resin composition adhered to the substrate is 20 to 90% by mass in the prepreg after drying. Usually, the prepreg of the present invention can be obtained by heating and drying at a temperature of 100 to 200 ° C. for 1 to 30 minutes and semi-curing (B-staged).

[Laminate board]
The laminated board of the present invention contains a cured product of the prepreg of the present invention.
The laminated board of the present invention is obtained by laminating and molding the prepreg of the present invention. For example, the prepreg of the present invention is laminated and molded in a configuration in which 1 to 20 sheets of the prepreg of the present invention are laminated and copper foils are arranged on one side or both sides thereof. It can be manufactured by doing.
As the molding conditions, the laminating conditions for the electrically insulating material laminated plate and the multilayer plate can be applied. For example, a multi-stage press, a multi-stage vacuum press, continuous forming, an autoclave forming machine, etc. are used, and the temperature is 100 to 250 ° C. and the pressure is 0.2. It can be molded under the conditions of 10 MPa and a heating time of 0.1 to 5 hours. Further, the laminated board of the present invention can be manufactured by combining the prepreg of the present invention and the wiring board for the inner layer and laminating and molding.

[Printed circuit board]
The printed wiring board of the present invention includes the laminated board of the present invention.
The printed wiring board of the present invention can be manufactured, for example, by circuit processing the laminated board of the present invention. The circuit processing can be performed by processing the conductor layer of the laminated board of the present invention by an etching method. After that, a plurality of laminated plates circuit-processed via the above-mentioned prepreg may be laminated and heat-pressed to form multiple layers at once. Further, through-holes or blind via holes may be formed by drilling or laser processing. Interlayer wiring may be formed by plating or conductive paste.

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.
The performance of the copper-clad laminates obtained in Examples and Comparative Examples was measured and evaluated by the following methods.

(1) Evaluation of Adhesiveness (Plating Peel Strength) with Plated Copper A 10 cm × 10 cm laminated plate from which the copper foil was removed was produced by etching the entire surface of the copper foil of the copper-clad laminated plate obtained in each example. Then, in a swelling solution at 80 ± 5 ° C. (a mixture of Circuposit Hall Prep 4125 and Cuposit Z, manufactured by Dow Chemical Japan Co., Ltd.) for 2 minutes, a permanganic acid solution at 80 ± 5 ° C. (Circuposit MLB Promoter 213A) -1 and Circuposit MLB Promoter 213B mixed solution, Dow Chemical Japan Co., Ltd. for 3 minutes in a reducing solution at 40 ± 5 ° C (Circuposit MLB Neutralizer 216-5, Dow Chemical Japan Co., Ltd.) Soaked for 2 minutes. Then, electroless plating and electroplating were performed to form plated copper having a thickness of 20 μm. Then, by immersing it in an etching solution, an evaluation substrate in which plated copper was formed to a width of 1 cm was produced, and plated copper was produced using a tensile tester (manufactured by Shimadzu Corporation, trade name: Shimadzu Autograph AG-IS 10kN). Adhesion with and (90 ° peel strength) was measured.
(2) Evaluation of Adhesion to Laminated Copper Foil (Copper Foil Peel Strength) A 1 cm wide copper foil was formed by immersing the copper-clad laminate obtained in each example in a copper etching solution to prepare an evaluation substrate. , The adhesiveness (90 ° peel strength) to the laminated copper foil was measured using a tensile tester (manufactured by Shimadzu Corporation, trade name: Shimadzu Autograph AG-IS 10 kN).
(3) Measurement of glass transition temperature (Tg) A 5 mm × 5 mm evaluation substrate from which the copper foil was removed was prepared by immersing the copper-clad laminate obtained in each example in a copper etching solution, and TMA (thermomechanical analysis) was performed. Thermomechanical analysis was performed by a compression method using a test device (manufactured by DuPont, trade name: TMA2940). After the evaluation substrate was mounted on the apparatus in the Z direction, the measurement was carried out twice in succession under the measurement conditions of a load of 5 g and a heating rate of 10 ° C./min. The Tg indicated by the intersection of the different tangents of the thermal expansion curve in the second measurement was obtained.
(4) Evaluation of solder heat resistance A 5 cm × 5 cm evaluation board from which the copper foil was removed was produced by immersing the copper-clad laminate obtained in each example in a copper etching solution, and a pressure cooker manufactured by Hirayama Seisakusho Co., Ltd. Using the test device, the pressure cooker treatment was performed at 121 ° C. and 2 atm (about 203 kPa) for 4 hours. Then, after immersing the evaluation substrate in a solder bath having a temperature of 288 ° C. for 20 seconds, the appearance was visually observed to confirm the presence or absence of abnormalities such as swelling.
(5) Evaluation of heat resistance with copper (T-288) A 5 mm × 5 mm evaluation substrate was prepared from the copper-clad laminates obtained in each example, and a TMA test device (TMA test device) was prepared according to the test method specified by IPC TM650. Evaluation was performed by measuring the time until swelling of the evaluation substrate occurred at 288 ° C. using Dupont Co., Ltd., trade name: TMA2940).
(6) Measurement of Dielectric Characteristics (Relative Permittivity and Dissipation Factor) Using the copper-clad laminate obtained in each example, a network analyzer (manufactured by Hulett Packard, trade name: 8722C) is used to perform a triplate structure linear line resonator method. The relative permittivity and the dielectric loss tangent were measured at 1 to 10 GHz. The size of the test piece is 0.8 mm thick x 200 mm long x 50 mm wide, and a straight line (line length 200 mm) with a width of 1.0 mm is formed by etching at the center of one side of one copper-clad laminate, and the back side is Copper was left on the entire surface to form a ground layer. The other was etched on one side and the back side was a ground layer. Next, the ground layer of the two copper-clad laminates was turned to the outside to form a laminated strip line. The measurement was performed at 25 ° C.
(7) Evaluation of flame retardancy The copper foil was removed by immersing the copper-clad laminate obtained in each example in a copper etching solution, and a test piece cut out to a length of 127 mm and a width of 12.7 mm was prepared. The evaluation was made according to the UL94 test method (V method).
(8) Evaluation of Appearance of Substrate After Etching A 50 cm × 50 cm evaluation substrate from which the copper foil was removed was prepared by immersing the copper-clad laminate obtained in each example in a copper etching solution, and a 10x magnifying glass was formed. The presence or absence of voids (voids), foreign substances, and aggregates was confirmed.

(Production Example 1: Production of Maleimide Compound (D-1))
1000 g of bis (4-maleimidephenyl) ether, 80 g of p-aminophenol and N, N-dimethyl in a reaction vessel with a volume of 2 liters capable of heating and cooling equipped with a thermometer, a stirrer and a water meter with a reflux cooling tube. 850 g of acetamide was added [(maleimide group equivalent) / (-NH ₂ group equivalent) = 4.0] and reacted at 100 ° C. for 2 hours to obtain a solution of the maleimide compound (D-1).

(Examples 1 to 3 and Comparative Examples 1 to 3)
Each component shown in Table 1 was mixed at the blending ratio (part by mass) shown in Table 1, and methyl ethyl ketone (manufactured by TonenGeneral Sekiyu Co., Ltd.) was used as a diluting solvent to obtain a uniform varnish having a solid content of 45% by mass. .. The prepared varnish was impregnated into an E glass cloth having a thickness of 0.1 mm and then heated and dried at 160 ° C. for 5 minutes to obtain a prepreg having a thermosetting resin composition content of 45% by mass. Eight prepregs were stacked, electrolytic copper foils having a thickness of 18 μm were placed one above the other, and pressed at a pressure of 4.0 MPa and a temperature of 185 ° C. for 60 minutes to obtain a copper-clad laminate.

The details of each component shown in Table 1 are as follows.
[(A) component]
(A-1) Silica coupled with aminosilane (manufactured by Admatex Co., Ltd., trade name: SC2050-KNK, average particle size: 0.5 μm)
[Comparison ingredients]
(A'-2) Untreated silica (silica not coupled with aminosilane) (manufactured by Admatex Co., Ltd., trade name: SO-C2, average particle size: 0.5 μm)
(A'-3) Silica coupled with silicon oligomer (trade name: SO-2050-KC, manufactured by Admatex Co., Ltd., average particle size: 0.5 μm)
[(B) component]
-Cresol novolac type epoxy resin (manufactured by DIC Corporation, product name: N-695)
-Dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, trade name: HP-7200H)
[(C) component]
-Copolymerized resin of styrene and maleic anhydride (manufactured by Sartmer, trade name: SMA-EF-40)
[(D) component]
Maleimide compound (D-1): A compound having an acidic substituent and an unsaturated maleimide group produced in Production Example 1 [component (E)].
・ Dicyandiamide (manufactured by Kanto Chemical Co., Inc.)
[Flame retardants]
-Phosphoric acid ester (manufactured by Daihachi Chemical Industry Co., Ltd., product name: PX-200)

As is clear from Table 1, the thermosetting resin compositions of Examples 1 to 3 using the inorganic filler coupled with aminosilane are more excellent in the balance of various properties than the comparative examples, and in particular, plating. It had excellent peel strength.
As described above, the thermosetting resin composition of the present invention has excellent copper foil adhesiveness, excellent relative permittivity and dielectric loss tangent, and by using the thermosetting resin composition of the present invention, It is possible to provide a printed wiring board which is particularly excellent in adhesiveness to plated copper as compared with conventional halogen-free products.

Claims (8)

(A) Inorganic filler coupled with aminosilane, (B) Epoxy resin, (C) (c-1) Monomer unit represented by the following general formula (1) and (c-2) The following general It contains a copolymer resin containing a monomer unit represented by the formula (2), a maleimide compound having an N-substituted maleimide group in the molecule (D), and (E) disyandiamide, and the aminosilane is N-phenyl. A thermosetting resin composition which is -3-aminopropyltrimethoxysilane.
The content of the inorganic filler coupled with (A) aminosilane is 10 to 250 parts by mass with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A).
The content of the epoxy resin (B) is 1 to 60 parts by mass with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A).
(C) The content of the copolymer resin containing the monomer unit represented by the following general formula (1) and (c-2) the monomer unit represented by the following general formula (2) is (A). ) Is 5 to 30 parts by mass with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component.
(D) The content of the maleimide compound having an N-substituted maleimide group in the molecule is 20 to 90 parts by mass with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A). can be,
(E) A thermosetting resin composition having a content of dicyandiamide of 0.5 to 30 parts by mass with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A).

(In the formula, R ₁ and R ₂ independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a phenyl group, or a substituted phenyl group.)

The content of the inorganic filler coupled with (A) aminosilane is 15 to 150 parts by mass with respect to 100 parts by mass in terms of solid content of the thermosetting resin composition excluding the component (A). The thermosetting resin composition according to claim 1. (D) As the maleimide compound having an N-substituted maleimide group in the molecule, (d-1) a structural unit derived from the maleimide compound having at least two N-substituted maleimide groups in one molecule, and (d-2). The thermosetting resin composition according to claim 1 or 2, which comprises a maleimide compound containing a structural unit derived from an amine compound having an acidic substituent represented by the following general formula (3).

(In the formula, R ₃ independently represents an acidic substituent selected from a hydroxyl group, a carboxy group and a sulfonic acid group, and R ₄ independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms. x is an integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.) (D) The heat according to claim 3, wherein the maleimide compound having an N-substituted maleimide group in the molecule includes a compound represented by the following general formula (4) or a compound represented by the following general formula (5). Curable resin composition.

(In the formula, R ₃ , R ₄ , x and y represent the same as those in the general formula (3), and R ₅ independently contains a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. show.)

(In the formula, R ₃ , R ₄ , x and y represent the same as those in the general formula (3), and R ₆ and R ₇ each independently have a hydrogen atom and an aliphatic hydrocarbon group having 1 to 5 carbon atoms. Alternatively, it indicates a halogen atom, and A is an alkylene group, an alkylidene group, an ether group, a sulfonyl group or a divalent group represented by the following formula (6).)

(A) The inorganic filler coupled with aminosilane is obtained by coupling silica having an average particle diameter of 0.3 to 2 μm with N-phenyl-3-aminopropyltrimethoxysilane, claims 1 to 1. 4. The thermosetting resin composition according to any one of 4. A prepreg containing the thermosetting resin composition according to any one of claims 1 to 5. A laminated board containing a cured product of the prepreg according to claim 6. A printed wiring board including the laminated board according to claim 7.