JP5266685B2 - Thermosetting resin composition, prepreg and laminate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermosetting resin composition that is well-balanced among all of adhesion to a metal foil, heat resistance, moisture resistance, flame retardancy, heat resistance at the interface between the composition and a metal adherent to the composition, relative dielectric constant and dielectric dissipation factor and to provide a prepreg and a laminate using the thermosetting resin composition. <P>SOLUTION: The thermosetting resin composition comprises (A) a curing agent having an acid substituent and an unsaturated maleimide group, which is produced by a specific process, (B) a 6-substituted guanamine compound, (C) a copolymer resin containing a specific monomer unit and (D) an epoxy resin. The prepreg and the laminate using the thermosetting resin composition are provided. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention balances all of metal foil adhesion, heat resistance, moisture resistance, flame retardancy, heat resistance with metal and dielectric properties (relative permittivity, dielectric loss tangent), and has low toxicity and safety and work. The present invention relates to a thermosetting resin composition excellent in the environment and suitably used for electronic parts and the like, and a prepreg and a laminate using the same.

Thermosetting resins are widely used in fields that require high reliability, such as electronic parts, because their unique cross-linked structure exhibits high heat resistance and dimensional stability. In the interlayer insulating material, due to the recent demand for higher density, high copper foil adhesiveness for forming fine wiring and workability when drilling or punching is required.
Moreover, due to recent environmental problems, mounting of electronic parts using lead-free solder and flame resistance using halogen-free are required, and therefore higher heat resistance and flame resistance than conventional ones are required. Furthermore, in order to improve the safety of the product and the working environment, there is a demand for a thermosetting resin composition that is composed only of low-toxic components and does not generate toxic gases.

  Bismaleimide compounds are curing agents for thermosetting resins that have excellent dielectric properties, flame retardancy, and heat resistance, but since known bismaleimide compounds do not have curing reactivity with epoxy resins, epoxy curing systems When used as it is in the thermosetting resin, there is a problem that the heat resistance is insufficient. That is, although examples relating to thermosetting resins in which an adduct of a bismaleimide compound and an aminophenol is produced and used by heat-kneading without using an organic solvent (see, for example, Patent Document 1 and Patent Document 2) are disclosed. The yield of the adduct of bismaleimide compound and aminophenol is low, and when these are used as a copper clad laminate or an interlayer insulating material, heat resistance, workability and the like are insufficient.

  In addition, melamine resins and guanamine compounds, which are thermosetting resins, are excellent in adhesiveness, flame retardancy and heat resistance, but lack solubility in organic solvents and have high toxicity such as N, N-dimethylformamide. Unless a large amount of the nitrogen atom-containing organic solvent is used, it is difficult to produce a thermosetting resin composition, and storage stability is insufficient. In addition, copper clad laminates and interlayer insulating materials using these thermosetting resins have a problem of contaminating various chemicals such as plating solutions when manufacturing electronic parts and the like.

Many examples of thermosetting resins using melamine resins and guanamine compounds are known as solutions for solving these problems (see, for example, Patent Documents 3 to 7).
However, these are thermosetting resins obtained by condensing melamine resins and guanamine compounds with aldehydes such as formaldehyde, and although their solubility in organic solvents has been improved, the thermal decomposition temperature is low, and toxic decomposition Since it generates gas, the working environment is deteriorated, and the heat resistance to lead-free solder and the heat resistance with copper are insufficient in recent years. Also, in fine processing and wiring formation, copper foil adhesion, flexibility, and toughness are insufficient, circuit patterns are broken or peeled off, and cracks occur when drilling or punching is performed. Such problems occur.
Moreover, although the example (for example, refer patent document 8) regarding a methylolation guanamine resin is disclosed, these also have problems, such as heat resistance, adhesiveness, workability, like the above.
Furthermore, a case relating to a thermosetting resin using an adduct of a bismaleimide compound and an aminobenzoic acid produced without using an organic solvent, a benzoguanamine formaldehyde condensate, etc. (see, for example, Patent Document 9) is disclosed. However, the thermal decomposition temperature is low, and the heat resistance to lead-free solder and the heat resistance with copper are insufficient in recent years.

As an example of a resin composition or laminate using an epoxy resin as a curing agent and a copolymer resin containing maleic anhydride, a flexible printed wiring board made of a copolymer resin composed of styrene and maleic anhydride (for example, Patent Document 10) is disclosed. Further, a copolymer resin having an acid value of 280 or more obtained from an epoxy resin, an aromatic vinyl compound and maleic anhydride, and an epoxy resin compound containing dicyandiamide (for example, see Patent Document 11) are disclosed. Further, brominated epoxy resin, copolymer resin of styrene and maleic anhydride (epoxy resin curing agent), prepreg containing styrene compound and solvent, electrical laminate material (for example, see Patent Document 12), epoxy resin , A copolymer resin of an aromatic vinyl compound and maleic anhydride, a prepreg containing a phenol compound, an electrical laminate material (for example, see Patent Document 13), an epoxy resin, a copolymer resin of an aromatic vinyl compound and maleic anhydride, A resin composition containing a phenol compound and a prepreg containing styrene or a styrene low polymer, an electrical laminate material (see, for example, Patent Document 14), an epoxy resin, a crosslinking agent for a carboxylic anhydride type epoxy resin, and an allyl network-forming compound. Articles, laminated boards, printed wiring boards (for example, see Patent Document 15), etc.
However, these have insufficient performance in terms of dielectric properties, high heat resistance, high moisture resistance, and high adhesion to copper foil, which are required with fine patterning, high frequency signals, and the like.

Japanese Patent Publication No. 63-34899 JP-A-6-32969 Japanese Examined Patent Publication No. 62-46584 Japanese Patent Laid-Open No. 10-67942 JP 2001-11672 A Japanese Patent Laid-Open No. 02-258820 Japanese Patent Laid-Open No. 03-145476 Japanese Examined Patent Publication No. 62-61051 Japanese Patent Publication No. 6-8342 JP 49-109476 A JP-A-1-221413 Japanese Patent Laid-Open No. 9-25349 Japanese Patent Laid-Open No. 10-1785 Japanese Patent Laid-Open No. 10-17686 Japanese National Patent Publication No. 10-505376

  In view of the present situation, the object of the present invention is a thermosetting resin composition balanced in all of metal foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with metal, relative dielectric constant and dielectric loss tangent. And providing a prepreg and a laminate using the same.

  As a result of intensive studies to achieve the above object, the present inventors have found that a curing agent having an acidic substituent and an unsaturated maleimide group produced by a specific method (hereinafter also simply referred to as a curing agent), 6 -A thermosetting resin composition containing a substituted guanamine compound, a copolymer resin containing a specific monomer unit, and an epoxy resin meets the above-mentioned purpose, and can be advantageously used as a thermosetting resin composition for a laminate. I found. The present invention has been completed based on such findings.

That is, the present invention provides the following thermosetting resin composition, prepreg and laminate.
1. (A) (a-1) A maleimide compound having at least two N-substituted maleimide groups in one molecule and (a-2) an amine compound having an acidic substituent represented by the following general formula (1) in an organic solvent A curing agent having an acidic substituent and an unsaturated maleimide group produced by reacting with a curing agent represented by the following general formula (5) or general formula (6) , (B) the following general formula (2) A copolymer resin containing a monomer unit represented by the following general formula (3) and (c-2) a monomer unit represented by the following general formula (4): (D) A thermosetting resin composition comprising an epoxy resin having at least two epoxy groups in one molecule.

（式中、Ｒ₁は各々独立に、水酸基、カルボキシ基およびスルホン酸基から選ばれる酸性置換基、Ｒ₂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、ｘは１〜５の整数、ｙは０〜４の整数で、且つｘとｙの和は５である。）

(In the formula, each R ₁ is independently an acidic substituent selected from a hydroxyl group, a carboxy group and a sulfonic acid group, and each R ₂ is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. 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.)

（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、それぞれ独立に、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。）

(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.)

（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).)

2 . A prepreg obtained by impregnating or coating the thermosetting resin composition according to the above 1 on a base material and then forming a B-stage.
3 . A laminate obtained by laminating the prepreg of 2 above.
4 . 4. The laminate of 3 above, which is a metal-clad laminate obtained by superposing metal foil on at least one of the prepregs, followed by heating and pressing.

The thermosetting resin composition of the present invention is balanced in all of metal foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with metal, relative dielectric constant and dielectric loss tangent, Low toxicity and excellent safety and work environment.
Therefore, according to the present invention, it is possible to provide a prepreg or a laminate having excellent performance using the thermosetting resin composition.

Hereinafter, the present invention will be described in detail.
First, the curing agent of the component (A) of the thermosetting resin composition of the present invention includes (a-1) a maleimide compound having at least two N-substituted maleimide groups in one molecule and (a-2) A curing agent having an acidic substituent and an unsaturated maleimide group, produced by reacting an amine compound having an acidic substituent represented by the general formula (1) in an organic solvent.

（式中、Ｒ₁は各々独立に、水酸基、カルボキシ基およ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の和は５である。）

(In the formula, each R ₁ independently 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; Is an integer from 1 to 5, y is an integer from 0 to 4, and the sum of x and y is 5.)

  (A-1) Examples of maleimide compounds having at least two N-substituted maleimide groups in one molecule include bis (4-maleimidophenyl) methane, poly (maleimidophenyl) methane, and bis (4-maleimidophenyl). Ether, bis (4-maleimidophenyl) sulfone, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, 4-methyl-1,3-phenylenebismaleimide, m-phenylenebismaleimide, 2 , 2-bis [4- (4-maleimidophenoxy) phenyl] propane, etc. Among them, bis (4-maleimidophenyl) methane, m-phenylenebis, which has a high reaction rate and can have higher heat resistance. Maleimide and bis (4-maleimidophenyl) sulfone are preferred and inexpensive because - phenylene bismaleimide and bis (4-maleimide phenyl) methane are more preferred, bis terms of solubility in a solvent (4-maleimide phenyl) methane are particularly preferred.

  (A-2) Examples of the amine compound represented by the general formula (1) include m-aminophenol, p-aminophenol, o-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid, and o-aminobenzoic acid. Acid, o-aminobenzenesulfonic acid, m-aminobenzenesulfonic acid, p-aminobenzenesulfonic acid, 3,5-dihydroxyaniline, 3,5-dicarboxyaniline, and the like. Among these, solubility and M-aminophenol, p-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline are preferred from the viewpoint of synthesis yield, and m-aminophenol and p- from the viewpoint of heat resistance. Aminophenol is more preferred, and m-aminophenol is particularly preferred from the viewpoint of low toxicity.

The amount ratio of the maleimide compound (a-1) and the amine compound (a-2) is equivalent to the maleimide group equivalent of the maleimide compound (a-1) and —NH ₂ group equivalent of the amine compound (a-2). The equivalent ratio with the equivalent 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 the range of 2.0-10.0. By setting the corresponding ratio within the above range, the solubility in the solvent is not insufficient, gelation occurs, and the heat resistance of the thermosetting resin does not decrease.

The organic solvent used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. And ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, and mesitylene, nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, and sulfur-containing solvents such as dimethylsulfoxide. 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 used is preferably 10 to 1000 parts by mass, preferably 100 to 500 parts by mass, per 100 parts by mass of the sum of the amine compound (a-1) and the maleimide compound (a-2). Is more preferable, and 200 to 500 parts by mass is particularly preferable.

The reaction temperature is preferably 50 to 200 ° C, more preferably 100 to 160 ° C. The reaction time is preferably 0.1 to 10 hours, and more preferably 1 to 8 hours.
In this 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-1) and reacting with the amine compound of (a-2), 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 component (B) of the thermosetting resin composition of the present invention is a 6-substituted guanamine compound represented by the following general formula (2). Examples of the 6-substituted guanamine compound represented by the general formula (2) 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, which have a high reaction rate and can have higher heat resistance, are included. -Vinyl-s-triazine is more preferred, and benzoguanamine is particularly preferred from the viewpoint of 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ルオキシ基を示す。）

(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、それぞれ独立に、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 comprises (c-1) a monomer unit represented by the following general formula (3) and (c-2) a monomer unit represented by the following general formula (4). It is a copolymer 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.)

Examples of the monomer unit represented by the general formula (3) in (c-1) include styrene compounds such as styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, bromostyrene, ethylene, propylene, isobutylene, and the like. It is obtained from the above vinyl compound, and if necessary, two or more monomers may be mixed and used.
Further, the monomer unit represented by the general formula (4) of (c-2) is obtained from maleic anhydride.
In addition to the above monomer units, the copolymer resin of component (C) may further contain various polymerizable monomer units. As monomers for obtaining these various monomer units (c-3), Examples thereof include maleimide compounds such as N-phenylmaleimide, N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide, and N-cyclohexylmaleimide, compounds having a methacryloyl group or acryloyl group such as methyl methacrylate and methyl acrylate, and the like. A maleimide compound is preferable from the viewpoint of characteristics and flame retardancy, and N-phenylmaleimide and N-hydroxyphenylmaleimide are more preferable from the viewpoint of moisture and heat resistance and adhesiveness.

In the copolymer resin of component (C), the number of monomer units of (c-1) is m, the number of monomer units of (c-2) is n, and the copolymerizable component of (c-3) is r In this case, the monomer ratio (m / n) in the copolymer resin of component (C) is 0.8 to 19.0 in consideration of the balance between dielectric properties, glass transition temperature, moisture and heat resistance, and adhesiveness. Is preferable, and 1.0 to 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 0.1 considering the balance between dielectric properties, glass transition temperature, moisture and heat resistance, and adhesiveness. 9.0 is preferable, and 1.0 to 6.0 is more preferable.
The weight average molecular weight of the (C) component copolymer resin 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 not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule. For example, bisphenol A-based, bisphenol F-based, biphenyl-based And glycidyl ethers such as novolacs, polyfunctional phenols, naphthalenes, alicyclics, and alcohols, glycidylamines, glycidyl esters, and the like. One type or a mixture of two or more types may be used. it can.
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.

The thermosetting resin composition of the present invention may be used in combination with an epoxy resin curing agent or curing accelerator. Examples of epoxy resin curing agents include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as dicyanodiamide, and phenolic compounds such as phenol novolac and cresol novolac. 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.
Examples of epoxy resin curing accelerators include imidazoles and derivatives thereof, tertiary amines, and quaternary ammonium salts.

The content of each component in the thermosetting resin composition of the present invention is the mass in terms of solid content of the curing agent having an acidic substituent and an unsaturated maleimide group of component (A) and components (B) to (D). As a mass in a total of 100 parts by mass, the following is preferable.
The component (A) is preferably 1 to 95 parts by mass, more preferably 20 to 95 parts by mass, and particularly preferably 20 to 90 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 the content is 95 parts by mass or less, the heat resistance is not lowered.
(B) It is preferable to set it as 1-95 mass parts, It is more preferable to set it as 20-95 mass parts, It is especially preferable to set it as 20-90 mass parts. By setting the content of the component (B) to 1 part by mass or more, flame retardancy, adhesiveness, and dielectric characteristics are improved, and by setting the content to 95 parts by mass or less, heat resistance does not decrease.
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.
(D) It is preferable to set it as 1-95 mass parts, It is more preferable to set it as 20-95 mass parts, It is especially preferable to set it as 20-90 mass parts. By setting the content of the component (D) to 1 part by mass or more, flame retardancy, adhesiveness, and heat resistance are improved, and by setting the content to 95 parts by mass or less, the dielectric characteristics are not deteriorated.

The thermosetting resin of the present invention can optionally contain an inorganic filler as the component (E). 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 because they are inexpensive.
The content of the component (E) may be 0 to 300 parts by mass with respect to 100 parts by mass of the total mass of the components (A) and the mass of the components (B) to (D). It is preferably 20 to 200 parts by mass, more preferably 20 to 150 parts by mass. (E) By making content of a component into 300 mass parts or less, a moldability and adhesiveness do not fall.

Furthermore, the thermosetting resin composition of the present invention may contain a known thermoplastic resin, elastomer, flame retardant, organic filler, etc. as long as the resin composition does not impair the properties of the thermosetting resin. Can do.
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. Among these flame retardants, phosphorus-based flame retardants that are non-halogen flame retardants, inorganic flame retardants, and the like are preferable from the viewpoint of the environment. In addition, it is particularly preferable to use a phosphorus-based flame retardant in combination with an inorganic flame retardant such as aluminum hydroxide from the viewpoint of compatibility with other characteristics such as flame retardancy and heat resistance.

  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. 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 heat resistance with copper (T-288) An evaluation board of 5 mm square was prepared from a copper clad laminate, and the evaluation board was swollen at 288 ° C. using a TMA test apparatus (TMA2940 manufactured by DuPont). It was evaluated by measuring the time until it occurred.

(5) 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 Seisakusho 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.
(6) Flame Retardancy Evaluation An evaluation board cut out to a length of 127 mm and a width of 12.7 mm was prepared from an evaluation board obtained by removing a copper foil by immersing a copper-clad laminate in a copper etching solution, and tested for UL94. Evaluation was made according to the method (Method V).
(7) Measurement of relative dielectric constant and dielectric loss tangent An evaluation substrate 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 Curing Agent (A-1) 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, 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 curing agent (A-1).

Production Example 2: Production of curing agent (A-2) Bis (4-maleimidophenyl) methane 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. : 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 the curing agent (A-2).

Production Example 3: Production of Curing Agent (A-3) Bis (4-maleimidophenyl) methane was placed 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. : 358.0 g, p-aminobenzoic acid: 68.5 g, and N, N-dimethylacetamide: 426.5 g were added and reacted at 140 ° C. for 5 hours to obtain a solution of the curing agent (A-3).

Production Example 4: Production of Curing Agent (A-4) m-phenylene bismaleimide: 268. in a reaction vessel with a volume of 1 liter that can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. 0 g, m-aminophenol: 54.5 g, and N, N-dimethylacetamide: 322.5 g were added and reacted at 140 ° C. for 5 hours to obtain a solution of a curing agent (A-4).

Production Example 5: Production of curing agent (A-5) Bis (4-maleimidophenyl) sulfone 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. : 408.0 g, p-aminophenol: 54.5 g, and N, N-dimethylacetamide: 462.5 g were allowed to react at 100 ° C. for 2 hours to obtain a solution of the curing agent (A-5).

Production Example 6: Production of curing agent (A-6) Bis (4-maleimidophenyl) ether was added to a 2 liter reaction vessel with a thermometer, a stirrer, and a moisture meter with a reflux condenser and capable of heating and cooling. : 360.0 g, p-aminophenol: 54.5 g and N, N-dimethylacetamide: 414.5 g were added and reacted at 100 ° C. for 2 hours to obtain a solution of the curing agent (A-6).

Production Example 7: Production of curing agent (A-7) 2,2′-bis [4] was placed in a reaction vessel having a thermometer, a stirrer, and a water quantifier with a reflux condenser and a capacity of 2 liters capable of heating and cooling. -(4-Maleimidophenoxy) phenyl] propane: 570.0 g, p-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 624.5 g were added and reacted at 120 ° C. for 2 hours to cure the curing agent (A-7 ) Was obtained.

Production Example 8 Production of Curing Agent (A-8) In 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, 4-methyl-1,3- Phenylene bismaleimide: 282.0 g, p-aminophenol: 54.5 g, and propylene glycol monomethyl ether: 336.5 g were added and reacted at 120 ° C. for 2 hours to obtain a solution of a curing agent (A-8).

Production Example 9 Production of Copolymer Resin (C-1) Styrene (m) and anhydrous maleate were placed 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. Copolymer resin of acid (n) (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 and toluene: 51.4 g were added, and the mixture was heated to 70 ° C. and dissolved uniformly. Then, 46.5 g of aniline was added dropwise little by little. Next, the temperature was raised to the reflux temperature, and the reaction was carried out for 5 hours while removing the generated condensed water to obtain a copolymer resin solution (C-1) comprising styrene, maleic anhydride and N-phenylmaleimide. The monomer ratio of (C-1) styrene (m), maleic anhydride (n) and N-phenylmaleimide (r) was m / (n + r) = 4.0, and the weight average molecular weight was 11,000. .

Production Example 10 Production of Copolymer Resin (C-2) Isobutylene (m) and anhydrous maleate were added to a reaction vessel having a volume of 1 liter which can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture meter with a reflux condenser. A copolymer resin of acid (n) (manufactured by Kuraray Co., Ltd., trade name: Isoban-600, m / n = 1.0, weight average molecular weight: 6,000): 154.0 g; 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 carried out for 5 hours while removing the generated condensed water to obtain a copolymer resin solution (C-2) composed of isobutylene, maleic anhydride and N-hydroxyphenylmaleimide. The monomer ratio of (C-2) isobutylene (m), maleic anhydride (n) and p-hydroxyphenylmaleimide (r) was m / (n + r) = 1.0, and the weight average molecular weight was 7,000. It was.

Comparative Production Example 1: Production of Curing Agent (A-9) With reference to the example of Patent Document 1, a kneader having a volume of 1 liter equipped with a steam heating device and bis (4-maleimidophenyl) methane: 358.0 g m-Aminophenol: 54.5 g was added, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled, and pulverized to obtain a hardener (A-9) powder.

Comparative Production Example 2: Production of Curing Agent (A-10) Referring to the example of Patent Document 9, with a 1 liter kneader equipped with a steam heating device, bis (4-maleimidophenyl) methane: 358.0 g m-Aminobenzoic acid: 68.5 g was added, heated and kneaded at 135 to 140 ° C. for 15 minutes, cooled and pulverized to obtain a hardener (A-10) powder.

Examples 1-10, Comparative Examples 1-6
(A) Curing agent (A-1 to 8) obtained in Production Examples 1 to 8 above or a curing agent obtained in Comparative Production Example (A) as a curing agent having an acidic substituent and an unsaturated maleimide group of component (A) -9, 10), benzoguanamine [manufactured by Nippon Shokubai Co., Ltd.] as the 6-substituted guanamine compound of component (B), and the copolymer obtained in Production Examples 9-10 as a copolymer resin of component (C) Resin (C-1, 2), copolymer resin of styrene and maleic anhydride (C-3: manufactured by Elf Atchem, trade name: EF-40, m / n = 4.0, weight average molecular weight: 10,000 ) Or a copolymer resin of isobutylene and maleic anhydride (C-4: manufactured by Kuraray Co., Ltd., trade name: Isoban-600, m / n = 1.0, weight average molecular weight: 6,000), (D) component epoxy resin Phenol novolac epoxy resin [D-1 : Dainippon Ink & Chemicals, Inc., trade name: Epicron N-770] or dicyclopentadiene type epoxy resin [D-2: Dainippon Ink & Chemicals, trade name: HP-7200H], epoxy Cresol novolak type phenolic resin (Dainippon Ink Chemical Co., Ltd., trade name: KA-1165) as a curing agent, crushed silica [E-1: Fukushima Ceramics Co., Ltd., Product name: F05-30, average particle size 10 μm] and aluminum hydroxide [E-2: Showa Denko Co., Ltd., product name: HD-360, average particle size 3 μm], and methyl ethyl ketone as a diluent solvent It mixed by the mixture ratio (mass part) shown to Table 1-Table 3, and obtained the uniform varnish with a resin content of 70 mass%.
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 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), solder heat resistance (T-288), hygroscopicity (water absorption), difficulty Flammability, relative dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) were measured and evaluated by the above methods. The evaluation results are shown in Tables 1 to 3.

In Comparative Examples 5 and 6, a varnish in which the thermosetting resin was uniformly dissolved was not obtained, and a prepreg could not be produced.
As apparent from Tables 1 and 2, in the examples of the present invention, copper foil adhesion (copper foil peel strength), glass transition temperature (Tg), solder heat resistance (T-288), hygroscopicity ( Water absorption), flame retardancy, relative dielectric constant (1 GHz) and dielectric loss tangent (1 GHz) are all balanced.
On the other hand, as is apparent from Table 3, in the comparative example, the prepreg could not be produced, and copper foil adhesion, glass transition temperature, solder heat resistance, hygroscopicity, flame retardancy, relative dielectric constant and dielectric loss tangent None of these are balanced and inferior to any of the properties.
A prepreg obtained by impregnating or coating a base material with the thermosetting resin composition of the present invention, and a laminate produced by laminating the prepreg, have copper foil adhesion, glass transition temperature, solder heat resistance. Are balanced in all of properties, hygroscopicity, flame retardancy, relative dielectric constant and dielectric loss tangent, and are useful as printed wiring boards for electronic devices.

Claims (4)

(A) (a-1) A maleimide compound having at least two N-substituted maleimide groups in one molecule and (a-2) an amine compound having an acidic substituent represented by the following general formula (1) in an organic solvent A curing agent having an acidic substituent and an unsaturated maleimide group produced by reacting with a curing agent represented by the following general formula (5) or general formula (6), (B) the following general formula (2) A copolymer resin containing a monomer unit represented by the following general formula (3) and (c-2) a monomer unit represented by the following general formula (4): (D) A thermosetting resin composition comprising an epoxy resin having at least two epoxy groups in one molecule.

(In the formula, each R ₁ is independently an acidic substituent selected from a hydroxyl group, a carboxy group and a sulfonic acid group, and each R ₂ is independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms, or a halogen atom. 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.)

(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 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.)

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.)

(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).)

A prepreg obtained by impregnating or coating the base material with the thermosetting resin composition according to claim 1, and then forming a B-stage. A laminate obtained by laminating the prepreg according to claim 2 . The laminate according to claim 3 , 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.