JP2012229363A - Thermosetting resin composition and prepreg, laminate board and circuit board using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition free of halogen, and small in fluctuation of relative permittivity and dielectric loss tangent; and to provide a prepreg, laminate board and circuit board each using the composition.SOLUTION: This thermosetting composition includes: (A) an aluminum salt of diethylphosphinic acid having a structure represented by general formula (1) and an average particle diameter of 0.5-3 μm; (B) a maleimide compound having an N-substituted maleimide group in the molecule; (C) a curing agent comprising a 6-substituted guanamine compound or dicyandiamide; and (D) an epoxy resin having at least two epoxy groups in one molecule (in formula, Rrepresents a phenyl, methyl, butyl, allyl, methoxy or benzyloxy group). The prepreg, laminate board and circuit board each using the composition are provided.

Description

  The present invention relates to a thermosetting resin composition suitably used for electronic parts and the like, and more specifically, is a halogen-free thermosetting resin composition having a small variation in relative dielectric constant and dielectric loss tangent, and a prepreg using the same. The present invention relates to a laminated board and a wiring board.

  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 adhesion for forming fine wiring and workability when performing drilling or punching by drilling or the like are also required.

  In recent years, environmental awareness has become indispensable for electronic devices and electronic components as environmental awareness increases. Halogen-based flame retardants used in plastic products, including electronic parts, can produce toxic brominated dibenzodioxins and furans when incinerated, the most typical brominated flame retardant, decabromodiphenyl oxide. Since being reported, its safety has been suspected. In consideration of environmental issues, the introduction of halogen-free products that do not use conventional brominated flame retardants containing halogen has been promoted (see, for example, Patent Document 1).

  In order to impart flame retardancy without containing a halogen compound, a method of adding a relatively large amount of an inorganic filler and a phosphorus-containing flame retardant in combination is generally used. Aluminum hydroxide is often selected as the inorganic filler used here. Similarly, lead-free solders that do not contain lead are also being introduced, and high heat resistance and low thermal expansion are required for wiring board materials in order to support lead-free solder processes that are performed at higher temperatures than before. Yes.

  In recent years, in order to process a large amount of data at high speed, the frequency of signals has been increased in computers and information equipment terminals. As the frequency used increases, the transfer loss of electrical signals increases. Therefore, it is necessary to suppress variations in characteristic impedance of the signal circuit. In order to suppress variations in the characteristic impedance of the signal circuit, it is necessary to reduce the three factors of variation in the insulating layer thickness, variation in the signal circuit width, and variation in the relative dielectric constant of the insulating material.

An example is disclosed in which a dielectric ceramic material is used for the filler, and the dielectric characteristics of the insulating layer can be adjusted according to the purpose of use, such as high dielectric constant and low dielectric loss (see, for example, Patent Document 2). However, these do not reduce variations in dielectric characteristics (relative permittivity and dielectric loss tangent) of the insulating layer.
In addition, as a resin composition balanced in all of metal foil adhesion, heat resistance, moisture resistance, flame retardancy and dielectric properties, compounds containing metal salts of phosphinic acid, maleimide compounds, guanamine compounds and epoxy resins are included. Although known (for example, refer to Patent Document 3), further improvement is required for the dielectric characteristics.

JP 2007-182544 A JP 2004-207320 A JP 2009-155399 A

  In view of the current situation, an object of the present invention is to provide a thermosetting resin composition that is halogen-free and has small variations in relative permittivity and dielectric loss tangent, and a prepreg, laminate, and wiring board using the same. is there.

  As a result of intensive studies to achieve the above object, the present inventors have found that a resin composition comprising a finely divided aluminum salt of diethylphosphinic acid, a maleimide compound, a curing agent and an epoxy resin meets the above object. I found out. The present invention has been completed based on such findings.

That is, the present invention provides the following thermosetting resin composition, prepreg, laminate and wiring board.
1. An aluminum salt of diethylphosphinic acid (A) having a structure represented by the following general formula (1) and having an average particle diameter of 0.5 to 3 μm, and a maleimide compound (B) having an N-substituted maleimide group in the molecule A curing agent (C) composed of a 6-substituted guanamine compound or dicyandiamide represented by the following general formula (2), and an epoxy resin (D) having at least two epoxy groups in one molecule. Thermosetting resin composition.

（式中、Ｒ₁はフェニル基、メチル基、ブチル基、アリル基、メトキシ基又はベンジルオキシ基を示す。）

(In the formula, R ₁ represents a phenyl group, a methyl group, a butyl group, an allyl group, a methoxy group, or a benzyloxy group.)

2. The maleimide compound (B) having an N-substituted maleimide group in the molecule and the maleimide compound (b-1) having at least two N-substituted maleimide groups in one molecule and the acidity represented by the following general formula (3) Said 1 thermosetting resin composition which is a compound which has the unsaturated maleimide group obtained by making the amine compound (b-2) which has a substituent react.

（式中、Ｒ₂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、Ｒ₃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。）

Wherein R ₂ is independently an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and R ₃ 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、Ｒ₂、Ｒ₃、ｘ及びｙは一般式（３）と同じものを示し、Ｒ₄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。） 3. The thermosetting resin composition according to 1 or 2 above, wherein the maleimide compound (B) having an N-substituted maleimide group in the molecule contains a compound represented by the following general formula (4) or general formula (5).

(Wherein R ₂ , R ₃ , x and y are the same as those in the general formula (3), and each R ₄ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Show.)

（式中、Ｒ₂、Ｒ₃、ｘ及びｙは一般式（３）と同じものを示し、Ｒ₅及び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（６）に示す基である。）

(Wherein R ₂ , R ₃ , x and y are the same as those in the general formula (3), and R ₅ and R ₆ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom) A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group, or a group represented by the following formula (6).

4). The thermosetting resin composition according to any one of the above 1 to 3, wherein the curing agent (C) is dicyandiamide.
5. A prepreg characterized in that the resin composition according to any one of 1 to 4 is impregnated or coated in a sheet-like reinforcing base material and then B-staged.
6). A laminated board, wherein the insulating resin layer is formed using any one of the resin compositions 1 to 4 or 5 prepregs.
7). A wiring board obtained by subjecting a metal foil arranged on one or both sides of an insulating resin layer in the laminated board of 6 to a circuit process.

  The thermosetting resin composition of the present invention is halogen-free and has characteristics with small variations in relative permittivity and dielectric loss tangent, and is used for computers and information equipment terminals that process a large amount of data at high speed. It is suitably used as an insulating resin for wiring boards of electronic devices.

4 is a graph for evaluating variations in relative dielectric constant and dielectric loss tangent of copper-clad laminates obtained in Example 1 and Example 2. 5 is a graph for evaluating variations in relative dielectric constant and dielectric loss tangent of copper-clad laminates obtained in Comparative Examples 1 and 2.

Hereinafter, the present invention will be described in detail.
The thermosetting resin composition of the present invention has a structure represented by the following general formula (1), an aluminum salt of diethylphosphinic acid (A) having an average particle diameter of 0.5 to 3 μm, and N in the molecule. -A maleimide compound (B) having a substituted maleimide group, a curing agent (C), and an epoxy resin (D) having at least two epoxy groups in one molecule.

First, the aluminum salt of diethylphosphinic acid as component (A) is a particulate flame retardant having a structure represented by the general formula (1) and an average particle size of 0.5 to 3 μm. Such a metal salt of disubstituted phosphinic acid is produced by the method described in JP-A No. 2001-2686, and is obtained by pulverizing one having an average particle diameter of 3 to 5 μm commercially available from Clariant, Germany. be able to.
The thermosetting resin composition of the present invention can impart excellent flame retardancy, low dielectric properties, and heat and humidity resistance by using the metal salt of the disubstituted phosphinic acid as an essential component. That is, the phosphorus content in the compound can be increased by using an aluminum salt of diethylphosphinic acid. Further, by using a finely divided aluminum salt of diethylphosphinic acid having an average particle diameter of 0.5 to 3 μm, it is possible to reduce variation in electrical characteristics (relative permittivity and dielectric loss tangent) of the material.

Examples of the maleimide compound having an N-substituted maleimide group in the component (B) molecule include N-phenylmaleimide and N-hydroxyphenylmaleimide as maleimide compounds having one N-substituted maleimide group in one molecule. However, maleimide compounds having two N-substituted maleimide groups in one molecule are preferred.
Examples of maleimide compounds having two N-substituted maleimide groups in one molecule include bis (4-maleimidophenyl) methane, poly (maleimidophenyl) methane, bis (4-maleimidophenyl) ether, and 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 and the like.
Among these, bis (4-maleimidophenyl) methane, m-phenylenebismaleimide, and bis (4-maleimidophenyl) sulfone, which have a high reaction rate and can have higher heat resistance, are preferable, and m- Phenylene bismaleimide and bis (4-maleimidophenyl) methane are more preferred, and bis (4-maleimidophenyl) methane is particularly preferred from the viewpoint of solubility in a solvent.

（式中、Ｒ₂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、Ｒ₃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 addition, as component (B), a maleimide compound (b-1) having at least two N-substituted maleimide groups in one molecule as described above, and an amine compound having an acidic substituent represented by the following general formula (3) A compound having an acidic substituent and an unsaturated maleimide group produced by reacting (b-2) is preferably used.

Wherein R ₂ is independently an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and R ₃ 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.)

  Examples of the amine compound (b-2) represented by the general formula (3) 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 preferable from the viewpoint of the yield of synthesis, and o-aminophenol, m- Aminophenol and p-aminophenol are more preferred, and p-aminophenol is particularly preferred from the viewpoint of dielectric properties.

  In this reaction, an organic solvent is preferably used, and the organic solvent to be used is not particularly limited. For example, alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone and cyclohexanone, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene and mesitylene, nitrogen atom-containing solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, dimethyl sulfoxide, etc. These sulfur atom-containing solvents can be used, and one or more of these can be mixed and used.

  Among these organic solvents, cyclohexanone, propylene glycol monomethyl ether and methyl cellosolve are preferable from the viewpoint of solubility, cyclohexanone and propylene glycol monomethyl ether are more preferable from the viewpoint of low toxicity, and high volatility as a residual solvent at the time of production of the prepreg. Propylene glycol monomethyl ether which is difficult to remain is particularly preferable.

The amount of the organic solvent used is preferably 10 to 1000 parts by mass, more preferably 100 to 500 parts by mass, per 100 parts by mass of the total of the maleimide compound (b-1) and the amine compound (b-2). Preferably, it is particularly preferably 200 to 500 parts by mass.
When the amount of the organic solvent used is 10 parts by mass or more, the solubility becomes sufficient, and when it is 1000 parts by mass or less, the reaction time is not too long.

The amount of the maleimide compound (b-1) and the amine compound (b-2) used is such that the equivalent ratio of the maleimide group equivalent of the maleimide compound and the equivalent of the amine compound in terms of —NH ₂ group is represented by the following formula:
1.0 <(maleimide group equivalent) / (-NH ₂ group equivalent) ≦ 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 reaction temperature is preferably 50 to 200 ° C. and the reaction time is preferably in the range of 0.1 to 10 hours, more preferably in the range of 100 to 160 ° C. and 1 to 8 hours.

  In this reaction, a reaction catalyst can be used as necessary. Examples of the reaction catalyst include, for example, amines such as triethylamine, pyridine, and tributylamine, imidazoles such as methylimidazole and phenylimidazole, and organophosphorus compounds such as triphenylphosphine. Can be mixed and used.

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

（式中、Ｒ₂、Ｒ₃、ｘ及びｙは一般式（３）と同じものを示し、Ｒ₄は各々独立に、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。）

(In the formula, R ₂ , R ₃ , x and y are the same as those in the general formula (3), and each R ₄ independently represents an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom.)

（式中、Ｒ₂、Ｒ₃、ｘ及びｙは一般式（３）と同じものを示し、Ｒ₅及び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（６）に示す基である。）

(Wherein R ₂ , R ₃ , x and y are the same as those in the general formula (3), and R ₅ and R ₆ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom) A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group, or a group represented by the following formula (6).

  The component (C) is a 6-substituted guanamine compound or dicyandiamide 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 these, benzoguanamine and 2,4-, which have a high reaction rate and can achieve higher heat resistance and lower dielectric constant. Diamino-6-vinyl-s-triazine is more preferable, and benzoguanamine is particularly preferable from the viewpoint of low cost and solubility in a solvent. Further, dicyandiamide is particularly preferable because it is excellent in storage stability of varnish, can have high heat resistance and low dielectric constant, and is inexpensive. A 6-substituted guanamine compound represented by the general formula (2) and dicyandiamide may be used in combination.

（式中、Ｒ₁はフェニル基、メチル基、ブチル基、アリル基、メトキシ基又はベンジルオキシ基を示す。）

(In the formula, R ₁ represents a phenyl group, a methyl group, a butyl group, an allyl group, a methoxy group, or a benzyloxy group.)

The component (D) 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, bisphenol F, biphenyl, novolac, polyfunctional phenol, naphthalene Examples thereof include glycidyl ethers, glycidyl ethers, glycidyl amines, and glycidyl esters such as alicyclic, alicyclic, and alcohols, and one kind or a mixture of two or more kinds can be used.
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 content of the components (A) to (D) in the thermosetting resin composition is as follows as the mass in 100 parts by mass of the total mass of the components (B) to (D) in terms of solid content. It is preferable.
The component (A) is preferably 1 to 98 parts by mass, more preferably 5 to 70 parts by mass, and particularly preferably 5 to 30 parts by mass. When the content of the component (A) is 1 part by mass or more, flame retardancy is improved, and when it is 98 parts by mass or less, heat resistance and adhesiveness are not reduced.
Component (B) is preferably 1 to 98.9 parts by mass, more preferably 20 to 98.9 parts by mass, and particularly preferably 50 to 90 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 by setting the content to 98.9 mass or less, heat resistance is not lowered.
The component (C) is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 50 parts by mass, and particularly preferably 0.5 to 30 parts by mass. By setting the content of component (C) to 0.1 parts 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.
The component (D) is preferably 1 to 80 parts by mass, more preferably 10 to 70 parts by mass, and particularly preferably 20 to 60 parts by mass. When the content of the component (D) is 1 part by mass or more, heat resistance and flame retardancy are improved, and when used as a prepreg, moldability is improved. There is no decline.

In the thermosetting resin composition of the present invention, an epoxy resin curing agent or curing accelerator may be used in combination as the component (E). Examples of epoxy resin curing agents include acid anhydrides such as maleic anhydride and maleic anhydride copolymers, amine compounds such as diaminodiphenylmethane, and phenolic compounds such as phenol novolac and cresol novolac. Examples of epoxy resin curing accelerators include imidazoles and derivatives thereof, tertiary amines, and quaternary ammonium salts. Among these, a maleic anhydride copolymer with good heat resistance is preferable, and a polymer monomer composed of carbon atoms and hydrogen atoms such as styrene, ethylene, propylene, isobutylene and the like and maleic anhydride can be reduced in dielectric constant. An acid copolymer resin is more preferable, and a copolymer resin of styrene and maleic anhydride or isobutylene and maleic anhydride is particularly preferable from the viewpoint of solubility in a solvent and compatibility with a blended resin.
The content of the component (E) is preferably 0 to 50 parts by mass, and preferably 5 to 40 parts by mass with respect to 100 parts by mass of the total mass of the components (B) to (D) in terms of solid content. Is more preferable, and 5 to 30 parts by mass is particularly preferable. (E) By making content of a component into 50 mass parts or less, a moldability, adhesiveness, and a flame retardance do not fall.

The thermosetting resin of the present invention can optionally contain an inorganic filler as the component (F). 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 (F) is preferably 0 to 300 parts by mass and preferably 20 to 200 parts by mass with respect to 100 parts by mass of the total mass of the components (B) to (D) in terms of solid content. Is more preferable and it is especially preferable to set it as 20-150 mass parts. (F) 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 optionally contain a known thermoplastic resin, elastomer, flame retardant, organic filler, etc. to such an extent that the thermosetting properties of the resin composition are not impaired. Can do.
Examples of thermoplastic resins include polytetrafluoroethylene, polyethylene, polypropylene, polystyrene, polyphenylene ether resin, phenoxy resin, polycarbonate resin, polyester resin, polyamide resin, polyimide resin, xylene resin, petroleum resin, silicon 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 environmental viewpoint. In addition, it is 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.

  Further, 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, but is not particularly limited. UV absorbers such as benzotriazoles, antioxidants such as hindered phenols and styrenated phenols, photopolymerization initiators such as benzophenones, benzyl ketals, thioxanthones, and fluorescent whitening agents such as stilbene derivatives And 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 sheet-like reinforcing base material, and then forming a B-stage. That is, after impregnating or coating the thermosetting resin composition of the present invention on a sheet-like reinforcing base material, 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 sheet-like reinforcing 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 sheet-like reinforcing substrate is not particularly limited, but for example, a sheet having a thickness of about 0.03 to 0.5 mm can be used, and the surface treated with a silane coupling agent or the like or mechanically opened. What gave the process is suitable from the surface of heat resistance, moisture resistance, or workability.
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.

In the laminate of the present invention, the insulating resin layer is formed using the resin composition or prepreg of the present invention. When using a prepreg, a laminated board is obtained by carrying out the lamination | stacking shaping | molding of the prepreg of this invention, for example by the structure which piled 1-20 sheets, and has arrange | positioned metal foil, such as copper and aluminum, on the single side | surface or both surfaces. As the molding conditions, for example, a laminate for electric insulating material and a multilayer board method can be applied. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine, etc. are used, and a temperature is 100 to 250 ° C., a pressure is 0.2 to It can be molded in the range of 10 MPa and heating time of 0.1 to 5 hours. In addition, the prepreg of the present invention and the inner layer wiring board can be combined and laminated to produce a multilayer board.
The wiring board of the present invention is obtained by subjecting a metal foil disposed on one or both sides of an insulating resin layer in a laminate to circuit processing, and is obtained by subjecting the above-mentioned laminate to general circuit processing. Can do.

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) Measurement of relative dielectric constant and dielectric loss tangent Using a Hewlett Packard network analyzer (8722C), measurement of relative dielectric constant and dielectric loss tangent of copper-clad laminate at 1-10 GHz is performed by the triplate structure linear line resonator method. did. The test piece size is 200mm x 50mm x thickness 0.8mm. A straight line (line length 200mm) with a width of 1.0mm is formed by etching at the center of one MCL single side, and copper is left on the entire surface, leaving copper on the entire surface. Layered. The other was etched on one side and the back side was a ground layer. Next, two MCL ground layers were placed outside to form a strip line. The measurement was performed at 25 ° C.
(2) Measurement data analysis by JMP The dielectric constant and dielectric loss tangent measurement data were analyzed using JMP (statistical analysis software).

Production Example 1: Production of Aluminum Diethylphosphinate Fine Salt Product (A-1) Diethylphosphinic acid aluminum salt (DEPAL) manufactured by Clariant Co., Ltd. was pulverized to produce a salt fine product having an average particle size of 1.5 μm.

Production Example 2: Production of maleimide compound (B-1) 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. : 1000 g, p-aminophenol: 80 g and N, N-dimethylacetamide: 850 g [(maleimide group equivalent) / (-NH ₂ group equivalent) = 4.0] and reacted at 100 ° C. for 2 hours. A solution of the maleimide compound (B-1) was obtained.

Examples 1-2 and Comparative Examples 1-2
Methyl ethyl ketone was used as a diluent solvent, and the following components were mixed at a blending ratio (parts by mass) shown in Table 1 to produce a uniform varnish having a resin content of 45% by mass.
(A) Component: Aluminum salt of diethylphosphinic acid A-1: Atomized product according to Production Example 1 DEPAL [manufactured by Clariant Co., Ltd., average particle size 4 μm]
(B) Component: Maleimide compound (B-1) obtained in Production Example 2
Component (C): Dicyandiamide [manufactured by Kanto Chemical Co., Inc.]
Component (D) (epoxy resin)
D-1: Phenol novolac type epoxy resin [Dainippon Ink Chemical Co., Ltd., trade name N-695]
D-2: Dicyclopentadiene type epoxy resin [Dainippon Ink Chemical Co., Ltd., trade name: HP-7200H],
Component (E) (epoxy resin curing agent): copolymer resin of styrene and maleic anhydride [manufactured by Sartomer Co., Ltd., trade name: SMA-EF-40]
Component (F) (inorganic filler): Oligomer-treated fused silica [manufactured by Admatech Co., Ltd., trade name: SC2050-KC]
A phosphate ester flame retardant [manufactured by Daihachi Chemical Co., Ltd., trade name: PX-200] was used in combination.

The prepared varnish was impregnated into a 0.1 mm thick glass cloth (trade name: # 2116, manufactured by Asahi Shweer Co., Ltd.), heated and dried at 160 ° C. for 5 minutes to obtain a prepreg having a resin content of 45 mass%. Eight prepregs were stacked, 18 μm electrolytic copper foils were placed one above the other, and pressed at a pressure of 4.0 MPa and a temperature of 185 ° C. for 60 minutes to obtain a copper clad laminate.
Using the obtained copper-clad laminate, the relative dielectric constant and dielectric loss tangent were measured and evaluated. JMP statistical software was used to evaluate variations in dielectric properties (relative dielectric constant and dielectric loss tangent). The evaluation results are shown in Table 1, FIG. 1 (Example), and FIG. 2 (Comparative Example). It is determined that the closer the value of R square is to 1, the smaller the variation.

  As is apparent from Table 1 and FIGS. 1 and 2, in the examples of the present invention, the use of an aluminum salt of diethylphosphinic acid having a small particle diameter reduces variations in relative permittivity and dielectric loss tangent. I understand that.

  The thermosetting resin composition of the present invention is halogen-free and has a characteristic with small variations in relative permittivity and dielectric loss tangent, and is used in computers and information equipment terminals that process a large amount of data at high speed. It is suitably used for a wiring board of an electronic device.

Claims (7)

An aluminum salt of diethylphosphinic acid (A) having a structure represented by the following general formula (1) and having an average particle diameter of 0.5 to 3 μm, and a maleimide compound (B) having an N-substituted maleimide group in the molecule A curing agent (C) composed of a 6-substituted guanamine compound or dicyandiamide represented by the following general formula (2), and an epoxy resin (D) having at least two epoxy groups in one molecule. Thermosetting resin composition.

(In the formula, R ₁ represents a phenyl group, a methyl group, a butyl group, an allyl group, a methoxy group, or a benzyloxy group.) The maleimide compound (B) having an N-substituted maleimide group in the molecule and the maleimide compound (b-1) having at least two N-substituted maleimide groups in one molecule and the acidity represented by the following general formula (3) The thermosetting resin composition according to claim 1, which is a compound having an unsaturated maleimide group obtained by reacting an amine compound (b-2) having a substituent.

Wherein R ₂ is independently an acidic substituent selected from a hydroxyl group, a carboxy group, and a sulfonic acid group, and R ₃ 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.) The thermosetting resin composition according to claim 1 or 2, wherein the maleimide compound (B) having an N-substituted maleimide group in the molecule contains a compound represented by the following general formula (4) or general formula (5).

(Wherein R ₂ , R ₃ , x and y are the same as those in the general formula (3), and each R ₄ independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom. Show.)

(Wherein R ₂ , R ₃ , x and y are the same as those in the general formula (3), and R ₅ and R ₆ are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 5 carbon atoms or a halogen atom) A represents an alkylene group, an alkylidene group, an ether group, a sulfonyl group, or a group represented by the following formula (6).

  The thermosetting resin composition according to any one of claims 1 to 3, wherein the curing agent (C) is dicyandiamide.   A prepreg characterized in that the resin composition according to any one of claims 1 to 4 is B-staged after being impregnated or coated in a sheet-like reinforcing base material.   The insulating resin layer is formed using the resin composition according to any one of claims 1 to 4 or the prepreg according to claim 5.   The wiring board obtained by carrying out circuit processing of the metal foil arrange | positioned at the single side | surface or both surfaces of the insulating resin layer in the laminated board of Claim 6.

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