JP2012153896A - Flame retardant resin compound, thermosetting resin composition using the same, prepreg, and laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a non-halogen flame retardant resin compound having a good balance between all of flame retardancy, metal foil adhesivity, heat resistance, moisture resistance and dielectric characteristics, and suitably usable for electronic parts or the like; a thermosetting resin composition and a prepreg and a laminate using the non-halogen flame retardant resin compound.SOLUTION: The flame retardant resin compound is produced by reacting a compound (a), which is obtained from an N-substituted maleimide compound and an amine compound having an acid substituent, with a phosphorus-containing epoxy resin (b) in an organic solvent. The thermosetting resin composition includes: a solution (A) of the flame retardant resin compound; a 6-substituted guanamine compound (B); a copolymer resin (C) from a styrene compound or a vinyl compound and a maleic anhydride; an epoxy resin (D); a hardener (E) for an epoxy resin having an acid substituent; and an inorganic filler (F). The prepreg and a laminate are produced using the thermosetting resin composition.

Description

  The present invention relates to a non-halogen flame retardant resin compound, and in particular, is well balanced in all of flame retardancy, metal foil adhesion, heat resistance, moisture resistance, and dielectric properties (dielectric constant, dielectric loss tangent), The present invention relates to a flame retardant resin compound suitably used for parts and the like, a thermosetting resin composition using the same, a prepreg and a laminate.

  Thermosetting resins are widely used in fields that require high reliability, such as electronic parts, because their unique cross-linked structure expresses high heat resistance and dimensional stability. The mounting of electronic components by lead-free solder and the flame resistance by halogen-free are required, and therefore higher heat resistance and flame retardance are required than conventional ones. Conventionally, addition of halogen compounds (chlorine, bromine), antimony trioxide, and the like, and a method of containing halogen in the resin have been used as methods for making the resin flame-retardant. However, these are required to be improved from the viewpoint of environmental protection.

As a technique for making a resin flame-retardant, a composition in which phenoxyphosphazene is added as a flame retardant for an epoxy resin has been reported (for example, see Patent Documents 1 and 2). However, in this case, in order to obtain sufficient flame retardancy, it is necessary to add a large amount of flame retardant, and there are problems such as a decrease in heat resistance.
In addition, a resin composition composed of a polycarbonate-based resin and a polystyrene-based resin, a phosphazene compound, a triazine skeleton-containing compound, and a fluoropolyolefin has been proposed (see, for example, Patent Document 3). However, this focuses on the flame retardancy of a resin comprising a polycarbonate resin and a polystyrene resin.
Furthermore, as a technique for flame retarding styrene-based resins, a technique of adding polyphenylene ether, an organic phosphorus compound, a triazine skeleton-containing compound, and a borate has been proposed (for example, see Patent Document 4). However, although this effect has been proposed to some extent with respect to the styrene resin, there is a problem that it is inferior in moisture absorption resistance and low smoke generation.

JP-A-10-259292 Japanese Patent Publication No. 6-53787 JP 2001-354844 A Japanese Patent Laid-Open No. 5-51510

  In view of the present situation, the object of the present invention is a non-halogen flame retardant resin that is balanced in all of flame retardancy, metal foil adhesion, heat resistance, moisture resistance and dielectric properties, and is suitably used for electronic parts and the like. It is providing a compound, a thermosetting resin composition using the same, a prepreg, and a laminate.

  As a result of intensive studies to achieve the above object, the present inventors reacted an acidic substituent obtained by a specific method, a curing agent having an unsaturated maleimide group, and an epoxy resin in an organic solvent. The flame retardant resin compound manufactured in accordance with the above objectives, and the thermosetting resin composition in which a solution of the flame retardant resin compound is blended with a 6-substituted guanamine compound has excellent characteristics. The present invention has been found to be advantageously used in the production of laminated plates and the like. The present invention has been completed based on such findings.

That is, the present invention provides the following flame retardant resin compound, thermosetting resin composition, prepreg and laminate.
1.1 A maleimide compound (a-1) having at least two N-substituted maleimide groups in the molecule and an amine compound (a-2) having an acidic substituent represented by the following general formula (1) in an organic solvent (a -3) reacting the compound (a) obtained by reaction in the phosphorus-containing epoxy resin (b) represented by the following general formula (2) in an organic solvent (c) at 100 to 150 ° C. Flame retardant resin compound produced by

（式中、Ｒ₁は、水酸基、カルボキシ基及びスルホン酸基から選ばれる酸性置換基、Ｒ₂は、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和が５である。）

(In the formula, R ₁ represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group; R ₂ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom; An integer of ˜5, y is an integer of 0 to 4, and the sum of x and y is 5.)

（式中、Ｒ'は、炭素数６〜１２の２価の芳香族炭化水素基であり、Ｒ"は、エポキシ基を有する有機基である。）

(In the formula, R ′ is a C 6-12 divalent aromatic hydrocarbon group, and R ″ is an organic group having an epoxy group.)

2. The flame retardant resin compound solution (A) of 1 above, the 6-substituted guanamine compound (B) shown in the following general formula (2b), the monomer unit (C-1) shown in the following general formula (3) and the following general formula Copolymer resin (C) having monomer unit (C-2) shown in (4), selected from epoxy resin (D) having at least two epoxy groups in one molecule, hydroxyl group, carboxy group and sulfonic acid group A thermosetting resin composition comprising an epoxy resin curing agent (E) having at least two acidic substituents in one molecule, and an inorganic filler (F).

（式中、Ｒ₃は、フェニル基、メチル基、アリル基、ブチル基、メトキシ基又はベンジルオキシ基を示す）

(Wherein R ₃ represents a phenyl group, a methyl group, an allyl group, a butyl group, a methoxy group or a benzyloxy group)

（式中、Ｒ₄、Ｒ₅は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜５個の炭化水素基、フェニル基又は置換フェニル基である。）

(In the formula, R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group.)

3. A prepreg obtained by impregnating or coating the thermosetting resin composition of 2 above on a base material and then forming a B-stage.
4). A laminate obtained by laminating the prepreg described in 3 above.
5. 4. The laminate of 4 above, which is a metal-clad laminate obtained by heating and pressing after a metal foil is laminated on at least one of the prepregs.

Since the flame retardant resin compound of the present invention is a non-halogen flame retardant resin compound, it is excellent from the viewpoint of environmental protection.
The thermosetting resin composition of the present invention is well balanced in all of flame retardancy, metal foil adhesion, heat resistance, moisture resistance and dielectric properties (relative dielectric constant, dielectric loss tangent), and has excellent performance. A laminated board etc. can be provided and used suitably for an electronic component etc.

Hereinafter, the present invention will be described in detail.
First, the flame retardant resin compound of the present invention includes a maleimide compound (a-1) having at least two N-substituted maleimide groups in one molecule and an amine compound having an acidic substituent represented by the following general formula (1). A compound (a) obtained by reacting (a-2) in an organic solvent (a-3) and a phosphorus-containing epoxy resin (b) represented by the following general formula (2) are combined with an organic solvent (c). It is produced by reacting in, and has an acidic substituent and an unsaturated maleimide group.

（式中、Ｒ₁は、水酸基、カルボキシ基及び、スルホン酸基から選ばれる酸性置換基、Ｒ₂は、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和が５である。）

(In the formula, R ₁ represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group; R ₂ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom; (An integer of 1 to 5, y is an integer of 0 to 4, and the sum of x and y is 5.)

（式中、Ｒ'は、炭素数６〜１２の２価の芳香族炭化水素基であり、Ｒ"は、エポキシ基を有する有機基である。）

(In the formula, R ′ is a C 6-12 divalent aromatic hydrocarbon group, and R ″ is an organic group having an epoxy group.)

  Examples of the maleimide compound (hereinafter also referred to as “maleimide compound”) having at least two N-substituted maleimide groups in one molecule of (a-1) include bis (4-maleimidophenyl) methane and polymaleimidephenyl. Methane, bis (4-maleimidophenyl) ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebis Maleimide, m-phenylene bismaleimide, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, and the like. Among these, bis (4- Maleimidophenyl) methane, m-phenylenebismaleimide and bis (4-maleimidophenyl) s Hong is preferable, from the viewpoint is inexpensive, m- phenylene bismaleimide and bis (4-maleimide phenyl), more preferably methane, bis (4-maleimide phenyl) methane in terms of solubility in a solvent particularly preferred.

Examples of the amine compound having an acidic substituent represented by the general formula (1) of (a-2) (hereinafter also referred to as “amine compound”) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, o-aminobenzoic acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5- Among them, m-aminophenol, p-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and 3,5-dihydroxy are mentioned in terms of solubility and synthesis yield. Aniline is preferable, m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance, and m-aminophenol is preferable because of low toxicity. Phenol is particularly preferred.

The maleimide compound (a-1) and the amine compound (a-2) are used in an amount equivalent to the maleimide group equivalent of the maleimide compound (a-1) and the equivalent amount of the amine compound (a-2) in terms of —NH ₂ group. The equivalent ratio of:
1.0 ≦ (maleimide group equivalent) / (- equivalent of NH ₂ groups in terms) ≦ 10.0
It is preferable that it is the range shown to, and it is still more preferable that the applicable amount ratio is 2.0-10.0. By setting the corresponding amount ratio within the above range, the solubility in the solvent is not insufficient, gelation occurs, and the heat resistance of the thermosetting resin is not lowered.

The organic solvent (a-3) is not particularly limited. Ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen-containing solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone, sulfur atoms such as dimethylsulfoxide A containing solvent etc. are mentioned, 1 type (s) or 2 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 remain at the time of production of the prepreg. Particularly preferred is propylene glycol monomethyl ether which hardly remains as a solvent.
The amount of the organic solvent (a-3) used is preferably 10 to 1000 parts by mass, and 100 to 500 parts by mass per 100 parts by mass of the total of the amine compound (a-1) and the maleimide compound (a-2). It is more preferable to set it as 200 to 500 mass parts.

The reaction temperature when the amine compound (a-1) and the maleimide compound (a-2) are reacted in the organic solvent (a-3) is preferably 50 to 200 ° C, and preferably 100 to 160 ° C. Further preferred. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 8 hours.
In the reaction, a reaction catalyst can be optionally used as necessary. 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. Can be used in combination.

  By this reaction, for example, by using a bis (4-maleimidophenyl) compound as the maleimide compound of (a-2) and reacting with the amine compound of (a-1), the following general formula (5) or general formula ( A curing agent having an acidic substituent and an unsaturated maleimide group shown in 6) is synthesized.

（式中、Ｒ₁、Ｒ₂、ｘ及びｙは一般式（１）におけると同じものを示し、Ｒ₆は各々独立に、水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示す。）

Wherein R ₁ , R ₂ , x and y are the same as in general formula (1), and R ₆ is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Is shown.)

（式中、Ｒ₁、Ｒ₂、ｘ及びｙは一般式（１）におけると同じものを示し、Ｒ₇及びＲ₈は各々独立に水素原子、炭素数１〜５の脂肪族炭化水素基又はハロゲン原子を示し、Aはアルキレン基、アルキリデン基、エーテル基、スルフォニル基又は下記式（７）に示す基である。）

(Wherein R ₁ , R ₂ , x and y are the same as in general formula (1), R ₇ and R ₈ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or Represents a halogen atom, and A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group, or a group represented by the following formula (7).)

The flame-retardant resin compound is obtained by reacting the above compound (a) with a phosphorus-containing epoxy resin (b) in an organic solvent (c). 2), specifically, an organic cyclic phosphorus compound (for example, 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide [hereinafter abbreviated as HCA]). ) Is directly introduced into the molecule of the epoxy resin, and a branched phosphorus-containing epoxy resin obtained.
The organic solvent (c) used for the production of the flame retardant resin compound is not particularly limited as long as it dissolves the compound (a) and the phosphorus-containing epoxy resin (b) produced as described above.
The reaction temperature is preferably 100 to 150 ° C, more preferably 120 to 140 ° C. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 4 hours.
The flame retardant resin compound of the present invention is produced by the above reaction and can be separated by a known method. In the thermosetting resin composition of the present invention, this flame retardant resin compound is not separated. And used as a solution (A) of a flame retardant resin compound. Thereby, since the compound which has the outstanding flame retardance containing nitrogen and phosphorus is obtained in a solution state, the mixing | blending to a thermosetting resin composition becomes easy, and the characteristic can be introduce | transduced.

  The component (B) of the thermosetting resin composition of the present invention is a 6-substituted guanamine compound represented by the following general formula (2b). Examples of the 6-substituted guanamine compound represented by the general formula (2b) include 2,4-diamino-6-phenyl-s-triazine called benzoguanamine and 2,4-diamino-6-methyl called acetoguanamine. -S-triazine, 2,4-diamino-6-vinyl-s-triazine, and the like. Among them, benzoguanamine and 2,4-diamino-6-vinyl having a high reaction rate and higher heat resistance -S-Triazine is more preferred, and benzoguanamine is particularly preferred because of its low toxicity and low cost.

（式中、Ｒ₃は、フェニル基、メチル基、アリル基、ブチル基、メトキシ基又はベンジロキシ基を示す。）

(In the formula, R ₃ represents a phenyl group, a methyl group, an allyl group, a butyl group, a methoxy group or a benzyloxy group.)

（式中、Ｒ₄、Ｒ₅は、それぞれ独立して、水素原子、ハロゲン原子、炭素数１〜５個の炭化水素基、フェニル基又は置換フェニル基を示す。） The component (C) of the thermosetting resin composition of the present invention includes a monomer unit (C-1) represented by the following general formula (3) and a monomer unit (C-2) represented by the following general formula (4). Polymeric resin.

(In the formula, R ₄ and R ₅ each 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 monomer unit (C-1) represented by the general formula (3) includes, for example, styrene compounds such as styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, bromostyrene, and vinyl such as ethylene, propylene, and isobutylene. It is obtained from a compound, and if necessary, two or more monomers may be mixed and used.
Further, the monomer unit (C-2) represented by the general formula (4) is obtained from maleic anhydride.
In addition to the above monomer units, the copolymer resin (C) may further contain various polymerizable monomer units. As these various copolymerizable monomer units (C-3), Examples thereof include maleimide compounds such as N-phenylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide and N-cyclohexylmaleimide, and compounds having a methacryloyl group or acryloyl group such as methyl methacrylate and methyl acrylate.

When the number of monomer units of (C-1) in the copolymer resin (C) is m, the number of monomer units of (C-2) is n, and the number of copolymerizable monomer units of (C-3) is r, The monomer ratio (m / n) in the copolymer resin (C) is preferably 0.8 to 19.0 considering the balance between dielectric properties, glass transition temperature, moisture and heat resistance, and adhesiveness, and is preferably 1.0 to 1.0. -6.0 is more preferable.
In addition, the monomer ratio [m / (n + r)] in the case of containing the monomer unit (C-3) is 0.1 to 9 in consideration of the balance between dielectric properties, glass transition temperature, moisture and heat resistance, and adhesiveness. 0.0 is preferable, and 1.0 to 6.0 is more preferable.
The weight average molecular weight of the copolymer resin (C) is preferably 1,000 to 200,000 in consideration of the balance between heat resistance and mechanical strength and moldability. The weight average molecular weight is a value measured by GPC using tetrahydrofuran as an eluent and converted by a standard polystyrene calibration curve.

The component (D) of the thermosetting resin composition of the present invention is an epoxy resin having two or more epoxy groups in one molecule, such as bisphenol A, bisphenol F, biphenyl, novolac, Examples thereof include epoxy resins such as glycidyl ethers such as functional phenols, naphthalenes, alicyclics, and alcohols, glycidylamines, and glycidyl esters, which can be used alone or in combination.
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 in terms of dielectric properties, heat resistance, moisture resistance and metal foil adhesion Phenol novolac type epoxy resin and cresol novolac type epoxy resin are preferable, and dicyclopentadiene type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl type epoxy resin and phenol novolac type epoxy resin are preferable because they have dielectric properties and high glass transition temperature. More preferred are phenol novolac type epoxy resins and dicyclopentadiene type epoxy resins from the viewpoint of moisture and heat resistance.

  (E) component of the thermosetting resin composition of this invention is a hardening | curing agent for epoxy resins which has at least two acidic substituents chosen from a hydroxyl group, a carboxy group, and a sulfonic acid group in 1 molecule. Examples of such epoxy resin curing agents include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as dicyanodiamide, phenol compounds such as phenol novolac and cresol novolac, and the like. Of these, phenol compounds such as phenol novolak and cresol novolak that have good heat resistance are preferred, and cresol novolak type phenol resins are particularly preferred because of their improved flame retardancy and adhesion.

The content of each component in the thermosetting resin composition of the present invention is preferably as follows as the mass in 100 parts by mass of the total mass of the components (A) to (E).
The component (A) is preferably 1 to 96 parts by mass, more preferably 20 to 49 parts by mass, and particularly preferably 20 to 44 parts by mass. When the content of the component (A) is 1 part by mass or more, flame retardancy, adhesiveness, and flexibility are improved, and when it is 96 parts by mass or less, heat resistance is not lowered.
The component (B) is preferably 1 to 96 parts by mass, more preferably 20 to 49 parts by mass, and particularly preferably 20 to 44 parts by mass. By setting the content of the component (B) to 1 part by mass or more, flame retardancy, adhesiveness, and dielectric properties are improved, and heat resistance is not lowered even when the content exceeds 96 parts by mass.
The component (C) is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass. By setting the content of component (C) to 1 part by mass or more, solubility and dielectric properties are improved, and by setting it to 50 parts by mass or less, flame retardancy does not decrease.
Component (D) is preferably 1 to 96 parts by mass, more preferably 20 to 49 parts by mass, and particularly preferably 20 to 44 parts by mass.
The component (E) is preferably 1 to 96 parts by mass, more preferably 10 to 39 parts by mass, and particularly preferably 15 to 39 parts by mass.
By setting the content of the components (D) and (E) to 1 part by mass or more, flame retardancy, adhesion, and heat resistance are improved, and by setting the content to 96 parts by mass or less, the low dielectric loss property is reduced. There is nothing to do.

The thermosetting resin composition of the present invention can optionally contain an inorganic filler. Examples of inorganic fillers include silica, mica, talc, short glass fiber or fine powder and hollow glass, antimony trioxide, calcium carbonate, quartz powder, aluminum hydroxide, magnesium hydroxide, and the like. Silica, aluminum hydroxide and magnesium hydroxide are preferable from the viewpoint of dielectric properties, heat resistance and flame retardancy, and silica and aluminum hydroxide are more preferable from the viewpoint of low cost.
The content of the inorganic filler is preferably 0 to 300 parts by mass, more preferably 20 to 200 parts by mass, with respect to 100 parts by mass of the total mass of the components (A) to (E). It is especially preferable to set it as 20-150 mass parts. By setting the content of the inorganic filler to 300 parts by mass or less, moldability and adhesiveness are not lowered.

Furthermore, the thermosetting resin composition of the present invention includes any known curing accelerator for epoxy resins, thermoplastic resins, elastomers, flame retardants, organic compounds, as long as the thermosetting properties of the resin composition are not impaired. Fillers can be included.
Examples of the curing accelerator for epoxy resins include imidazoles and derivatives thereof, tertiary amines, and quaternary ammonium salts.
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, silicone resin, 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 flame retardants include halogen-containing flame retardants containing bromine and chlorine, triphenyl phosphate, tricresyl phosphate, trisdichloropropyl phosphate, phosphazenes, red phosphorus and other phosphorus flame retardants, antimony trioxide, hydroxylation Examples include inorganic flame retardants such as aluminum and magnesium hydroxide.
Examples of the organic filler include organic powders such as silicone powder, polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, and polyphenylene ether.

  Moreover, an organic solvent can be arbitrarily used as a dilution solvent in the thermosetting resin composition of the present invention. The organic solvent is not particularly limited. For example, 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. Examples of the solvent include one type or a mixture of two or more types.

  Furthermore, the thermosetting resin composition can optionally contain an ultraviolet absorber, an antioxidant, a photopolymerization initiator, a fluorescent whitening agent, an adhesion improver, and the like, and is not particularly limited. For example, UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, and thioxanthones, and fluorescent whitening such as stilbene derivatives Agents, urea compounds such as urea silane, and adhesion improvers such as silane coupling agents.

  The prepreg of the present invention is formed by impregnating or coating the thermosetting resin composition of the present invention on a base material and then forming a B-stage. That is, after impregnating or coating the thermosetting resin composition of the present invention on a substrate, it is semi-cured (B-staged) by heating or the like to produce the prepreg of the present invention. Hereinafter, the prepreg of the present invention will be described in detail.

As the base material used for the prepreg of the present invention, known materials used for various types of laminates 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, for example, shapes such as woven fabric, non-woven fabric, robink, chopped strand mat, and surfacing mat, but the material and shape are selected depending on the intended use and performance of the molded product, and if necessary, A single material or two or more materials and shapes can be combined.
The thickness of the substrate is not particularly limited. For example, a substrate having a thickness of about 0.03 to 0.5 mm can be used, and the substrate is surface-treated with a silane coupling agent or the like, or mechanically opened. Is suitable from the viewpoints of heat resistance, moisture resistance and processability. After impregnating or coating the base material so that the amount of the resin composition attached to the base material is 20 to 90% by mass in terms of the resin content of the prepreg after drying, the temperature is usually 100 to 200 ° C. Can be heated and dried for 1 to 30 minutes and semi-cured (B-stage) to obtain the prepreg of the present invention.

  The laminate of the present invention is obtained by laminating the prepreg of the present invention. That is, for example, the prepreg of the present invention is laminated and molded in a configuration in which, for example, 1 to 20 sheets are stacked and a metal foil such as copper and aluminum is disposed on one side or both sides thereof. As the molding conditions, for example, a method of a laminated plate for an electrical insulating material and a multilayer plate can be applied. For example, a multistage press, a multistage vacuum press, a continuous molding, an autoclave molding machine or the like is used, a temperature of 100 to 250 ° C., a pressure of 0.2 It can shape | mold in the range of 10-10 MPa and heating time 0.1-5 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.
The copper clad laminate obtained in the following examples was measured and evaluated for performance by the following method.

(1) Evaluation of copper foil adhesiveness (copper foil peel strength) By immersing a copper-clad laminate in a copper etching solution, an evaluation board was prepared by removing the copper foil while leaving a 1 cm wide band portion. The peel strength of the belt portion was measured using [AG-100C manufactured by Shimadzu Corporation].
(2) Measurement of glass transition temperature (Tg) A 5 mm square evaluation substrate from which copper foil was removed by immersing a copper clad laminate in a copper etching solution was prepared, and a TMA test apparatus [TMA2940 manufactured by DuPont Co., Ltd.] was used. Used and evaluated by observing the thermal expansion characteristics of the evaluation substrate.

(3) Evaluation of solder heat resistance A 5 cm square evaluation board from which the copper foil has been removed is prepared by immersing a copper clad laminate in a copper etching solution, and a pressure cooker test apparatus (manufactured by Hirayama Manufacturing Co., Ltd.) is used. Then, it was left for 4 hours under conditions of 121 ° C. and 0.2 MPa, and then immersed in a solder bath at a temperature of 288 ° C. for 20 seconds, and then the solder heat resistance was evaluated by observing the appearance of the evaluation substrate.
(4) Evaluation of hygroscopicity (water absorption rate) A copper-clad laminate was immersed in a copper etching solution to prepare an evaluation board from which the copper foil was removed, and a pressure / cooker test apparatus (manufactured by Hirayama Manufacturing Co., Ltd.) was used. Then, after leaving for 4 hours under the conditions of 121 ° C. and 0.2 MPa, the water absorption rate of the evaluation substrate was measured.

(5) Flame Retardancy Evaluation An evaluation board cut out to 127 mm in length and 12.7 mm in width was prepared from an evaluation board in which a copper foil was removed by immersing a copper clad laminate in a copper etching solution, and a UL94 test was performed. Evaluation was made according to the method (Method V).
(6) Measurement of relative dielectric constant and dielectric loss tangent An evaluation board from which the copper foil was removed by immersing the obtained copper-clad laminate in a copper etching solution was prepared, and a relative dielectric constant measuring device (manufactured by Hewlett-Packard Company, The relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured using HP4291B).

Production Example 1: Production of Compound (aa) Bis (4-maleimidophenyl) methane was placed in a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 358.0 g, m-aminophenol: 54.5 g and propylene glycol monomethyl ether: 412.5 g were added and reacted for 5 hours while refluxing to obtain a solution of the compound (aa).

Production Example 2: Production of Compound (ab) Bis (4-maleimidophenyl) methane was added to a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 358.0 g, p-aminophenol: 54.5 g and propylene glycol monomethyl ether: 412.5 g were added and reacted for 5 hours while refluxing to obtain a solution of compound (ab).

Production Example 3: Production of Compound (ac) Bis (4-maleimidophenyl) sulfone was added to a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 408.0 g, p-aminophenol: 54.5 g and N, N-dimethylacetamide: 462.5 g were added and reacted for 5 hours while refluxing to obtain a solution of compound (ac).

Production Example 4: Production of Compound (ad) A bis (4-maleimidophenyl) ether was added to a reaction vessel having a volume of 2 liters capable of being heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 360.0 g, p-aminophenol: 54.5 g and N, N-dimethylacetamide: 414.5 g were added and reacted for 5 hours under reflux to obtain a solution of compound (ad).

Production Example 5 Production of Compound (ae) Heated and cooled reaction vessel equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser was charged with 2,2′-bis [4- (4-Maleimidophenoxy) phenyl] propane: 570.0 g, p-aminophenol: 54.5 g and propylene glycol monomethyl ether: 624.5 g were added and reacted for 5 hours while refluxing to obtain a solution of compound (ae) Got.

Production Example 6: Production of Compound (af) 4-methyl-1,3-phenylene was added to a reaction vessel having a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Bismaleimide: 282.0 g, p-aminophenol: 54.5 g and propylene glycol monomethyl ether: 336.5 g were added and reacted for 5 hours while refluxing to obtain a solution of the compound (af).

Production Example 7: Production of phosphorus-containing epoxy resin (b1) Mantle heater, temperature control device, electric stirrer, thermocouple, water-cooled cooling device,
In a five-necked glass reaction vessel having a capacity of 3000 ml equipped with a dropping funnel, the dried 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (hereinafter referred to as “organocyclic phosphorus compound HCA”) 216 g) was added and dissolved by heating. The temperature was raised while stirring, and when the temperature reached 110 ° C., 112 g of 4-hydroxybenzaldehyde and 940 g of phenol were added, and the reaction was carried out for 3 hours or more. Excess phenol was recovered, the reaction product was washed out with methanol and cooled to room temperature, and then the reaction product was filtered and dried (9,10-dihydro-9-oxa-10-phosphophenanthrene). -10-oxide-10-yl)-(4-hydroxyphenyl) methanol (hereinafter referred to as “phosphorus-containing compound HPP”) was obtained.

  Bisphenol A diglycidyl ether [Dainippon] in a 3000 ml five-neck glass reaction vessel equipped with a mantle heater, temperature control device, electric stirrer, nitrogen inlet, thermocouple, water-cooled cooler, and dropping funnel Ink Chemical Industries, Ltd., trade name: Ep850] and 1000 g of the phosphorus-containing compound HPP obtained above were added and heated to 120 ° C. while introducing nitrogen gas. After the bisphenol A diglycidyl ether and the phosphorus-containing compound HPP were completely dissolved, the reaction product was dried under vacuum, nitrogen gas was introduced again, and then dried under vacuum. After repeating such drying treatment twice, when the temperature of the reaction system dropped to 85 to 90 ° C., 6.0 g of triphenylphosphine was added, and nitrogen gas was introduced with stirring. The mixture was heated to 160 ° C. and maintained for 10 minutes, and the reaction system gradually generated heat to rise to 180 ° C. and then maintained at that temperature for 3 hours to obtain a phosphorus-containing epoxy resin. The theoretical value of phosphorus content is 2.66% by mass. The phosphorus-containing epoxy resin was dissolved in 1035 g of propylene glycol monomethyl ether to prepare a phosphorus-containing epoxy resin (b1) having a solid content of 60% by mass.

Production Example 8: Production of Flame Retardant Resin Compound Solution (A1) Obtained in Production Example 1 in a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser. The compound (aa) obtained: 277.9 g, the phosphorus-containing epoxy resin (b1) obtained in Production Example 7: 300.0 g and N, N-dimethylacetamide: 50.0 g were added, and the mixture was kept at 120 ° C. for 5 hours. Reaction was performed to obtain a flame retardant resin compound solution (A1).

Production Example 9: Production of Flame Retardant Resin Compound Solution (A2) Obtained in Production Example 2 in a 2 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling. The compound (ab) obtained: 277.9 g, the phosphorus-containing epoxy resin (b1) obtained in Production Example 7: 300.0 g and N, N-dimethylacetamide: 50.0 g were added, and the mixture was kept at 120 ° C. for 5 hours. Reaction was carried out to obtain a flame retardant resin compound solution (A2).

Production Example 10 Production of Flame Retardant Resin Compound (A3) Obtained in Production Example 3 in a reaction vessel with a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Compound (ac): 277.88 g, phosphorus-containing epoxy resin (b1) obtained in Production Example 7: 300.00 g and N, N-dimethylacetamide: 50.00 g were added and reacted at 120 ° C. for 5 hours. Thus, a solution of the flame retardant resin compound (A3) was obtained.

Production Example 11 Production of Flame Retardant Resin Compound (A4) Obtained in Production Example 3 in a reaction vessel with a volume of 2 liters that can be heated and cooled equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Compound (ad): 277.88 g, phosphorus-containing epoxy resin (b1) obtained in Production Example 7: 300.00 g and N, N-dimethylacetamide: 50.00 g were added and reacted at 120 ° C. for 5 hours. Thus, a solution of the flame retardant resin compound (A4) was obtained.

Production Example 12 Production of Flame Retardant Resin Compound (A5) Obtained in Production Example 3 in a reaction vessel with a volume of 2 liters that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Compound (ae): 277.88 g, phosphorus-containing epoxy resin (b1) obtained in Production Example 7: 300.00 g and N, N-dimethylacetamide: 50.00 g were added and reacted at 120 ° C. for 5 hours. Thus, a solution of the flame retardant resin compound (A5) was obtained.

Production Example 13 Production of Flame Retardant Resin Compound (A6) Obtained in Production Example 3 in a reaction vessel having a volume of 2 liters that can be heated and cooled with a thermometer, a stirrer, and a moisture meter with a reflux condenser. Compound (af): 277.88 g, phosphorus-containing epoxy resin (b1) obtained in Production Example 7: 300.00 g, and N, N-dimethylacetamide: 50.00 g were added and reacted at 120 ° C. for 5 hours. To obtain a solution of the flame retardant resin compound (A6).

Production Example 14 Production of Copolymer Resin (C1) Styrene (m) and maleic anhydride (maleic anhydride (with a thermometer, a stirrer, a moisture quantifier with a reflux condenser and a volume of 2 liter capable of heating and cooling) n) copolymer resin (manufactured by Elf Atchem, trade name EF-40, monomer ratio (m / n) = 4.0, weight average molecular weight: 10,000): 514.0 g and cyclohexanone: 462.6 g, Toluene: 51.4 g was added, heated to 70 ° C. and dissolved uniformly, and then aniline: 46.5 g was added dropwise in small portions. Next, the temperature was raised to the reflux temperature, and the reaction was performed for 5 hours while removing the generated condensed water to obtain a solution of a copolymer resin (C1) composed of styrene, maleic anhydride, and N-phenylmaleimide. The monomer ratio of styrene (m), maleic anhydride (n) and N-phenylmaleimide (r) in (C1) was m / (n + r) = 4.0, and the weight average molecular weight was 11,000.

Production Example 15 Production of Copolymer Resin (C2) Isobutylene (m) and maleic anhydride (maleic anhydride (m) were added to a 1 liter reaction vessel with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser. n) copolymer resin (trade name Isoban-600, m / n = 1.0, weight average molecular weight: 6,000, manufactured by Kuraray Co., Ltd.): 154.0 g and N.I. N-dimethylacetamide: 308.0 g and toluene: 30.8 g were added, and the mixture was heated to 70 ° C. and dissolved uniformly. Then, 54.5 g of p-aminophenol was added little by little. Next, the temperature was raised to the reflux temperature, and the reaction was performed for 5 hours while removing the generated condensed water to obtain a solution of a copolymer resin (C2) composed of isobutylene, maleic anhydride, and N-hydroxyphenylmaleimide. The monomer ratio of (C2) isobutylene (m), maleic anhydride (n), and p-hydroxyphenylmaleimide (r) was m / (n + r) = 1.0, and the weight average molecular weight was 7,000.

Examples 1-10, Comparative Examples 1-4
In Examples, the flame retardant resin compound solutions (A1 to A6) obtained in Production Examples 8 to 13 as the component (A) were used, and in the comparative examples, bis (4-maleimidophenyl) methane instead of the component (A). [Daiwa Kasei Kogyo Co., Ltd., trade name: BMI1000] and flame retardant triphenyl phosphate [Eighth Chemical Industry Co., Ltd., trade name: TPP], Aromatic condensed phosphate [Eighth Chemical Industry ( Co., Ltd., trade name: PX200] or non-halogen phosphorus-containing flame retardant [Clariant, trade name: OP930], and (B) component 6-substituted guanamine compound as benzoguanamine [manufactured by Nippon Shokubai Co., Ltd.] As the copolymer resin of component (C), the copolymer resins (C1, C2) obtained in Production Examples 6 to 7 above, the copolymer resin of styrene and maleic anhydride (manufactured by Elf Atchem, trade name: EF-4 , M / n = 4.0, weight average molecular weight: 10,000) or a copolymer resin of isobutylene and maleic anhydride [manufactured by Kuraray Co., Ltd., trade name: ISOBAN-600, m / n = 1.0, weight average As a component (D) epoxy resin, a phenol novolac type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: Epicron N-770) or a dicyclopentadiene type epoxy resin (large Nippon Ink Chemical Co., Ltd., trade name: HP-7200H) as a curing agent for epoxy resin of component (E), cresol novolac type phenol resin [Dainippon Ink Chemical Co., Ltd., trade name: KA- 1165] as an inorganic filler, crushed silica [manufactured by Fukushima Ceramics Co., Ltd., trade name: F05-30, average particle size 10 μm] and aluminum hydroxide [Showa Denko Co., Ltd. ), Trade name: HD-360, average particle size 3 μm], and methyl ethyl ketone as a diluent solvent, respectively, and mixed at a blending ratio (parts by mass) shown in Tables 1 and 2 to obtain a resin content of 70 mass % Uniform varnish.
Next, the obtained varnish was impregnated and applied to an E glass cloth having a thickness of 0.2 mm and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg having a resin content of 55% by mass. Four prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 2.45 MPa (25 kgf / cm ² ) and a temperature of 185 ° C. for 90 minutes to obtain a copper-clad laminate.
Using the copper-clad laminate thus obtained, copper foil adhesion (copper foil peel strength), glass transition temperature (Tg), hygroscopicity (water absorption), flame retardancy, relative dielectric constant (1 GHz) In addition, the dielectric loss tangent (1 GHz) was measured and evaluated by the method described above. The results are shown in Tables 1 to 3.

As is apparent from Tables 1 to 3, when the thermosetting resin composition using the solution of the flame retardant resin compound of the present invention is used for a laminate, the flame retardancy is UL-94V-0. Good results are obtained.
In Examples of the present invention, all of copper foil adhesion (copper foil peel strength), glass transition temperature (Tg), hygroscopicity (water absorption), flame retardancy, relative dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) The prepreg obtained by impregnating or coating the base material with the thermosetting resin composition using the solution of the flame retardant resin compound of the present invention and the prepreg were produced by laminate molding. The laminate is excellent in flame retardancy and is useful as a printed wiring board for electronic equipment.

Claims (5)

A maleimide compound (a-1) having at least two N-substituted maleimide groups in one molecule and an amine compound (a-2) having an acidic substituent represented by the following general formula (1) are mixed with an organic solvent (a-3). ) And the phosphorus-containing epoxy resin (b) represented by the following general formula (2) is reacted at 100 to 150 ° C. in an organic solvent (c). Flame retardant resin compound.

(In the formula, R ₁ represents an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group; R ₂ represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom; An integer of ˜5, y is an integer of 0 to 4, and the sum of x and y is 5.)

(In the formula, R ′ is a C 6-12 divalent aromatic hydrocarbon group, and R ″ is an organic group having an epoxy group.) A solution (A) of the flame retardant resin compound according to claim 1, a 6-substituted guanamine compound (B) represented by the following general formula (2b), a monomer unit (C-1) represented by the following general formula (3), and Copolymer resin (C) having monomer unit (C-2) represented by the following general formula (4), epoxy resin (D) having at least two epoxy groups in one molecule, hydroxyl group, carboxy group and sulfonic acid group A thermosetting resin composition comprising: an epoxy resin curing agent (E) having at least two acidic substituents selected from 1) and an inorganic filler (F).

(Wherein R ₃ represents a phenyl group, a methyl group, an allyl group, a butyl group, a methoxy group or a benzyloxy group)

(In the formula, R ₄ and R ₅ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 5 carbon atoms, a phenyl group or a substituted phenyl group.)

  A prepreg obtained by impregnating or coating the base material with the thermosetting resin composition according to claim 2 and then forming a B-stage.   A laminate obtained by laminating the prepreg according to claim 3.   The laminate according to claim 4, wherein the laminate is a metal-clad laminate obtained by heating and pressing after a metal foil is laminated on at least one of the prepregs.