JP2009084356A - Sheet-like glass substrate prepreg, layered plate, and printed wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a sheet-like glass substrate prepreg capable of lowering water absorption without spoiling insulation reliability and heat resistance required for a printed wiring board, to provide a layered plate and to provide the printed wiring board. <P>SOLUTION: In the sheet-like glass substrate prepreg formed by impregnating or coating a thermosetting resin (B) in or on a sheet-like glass substrate (A) and drying the resin, an area ratio [R<SB>s</SB>=Sg/2S] is in a range of 0.5 to 1.3, when the sum total area of a glass surface of the sheet-like glass substrate (A) and a sheet area are defined as Sg and S, respectively. The layered plate and the printed wiring board using the same are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a sheet-like glass substrate prepreg, a laminate, and a printed wiring board that provide a wiring board having a low water absorption rate, good electrical characteristics, and excellent fine wiring formability.

    In recent years, demands for smaller, lighter, and faster electronic devices have increased, and the density of printed wiring boards has been increasing. High copper foil adhesion for fine wiring formation, drilling or punching, etc. Processability when processing 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. Various resins are currently being developed to meet these requirements. In general, such a resin is impregnated into a glass cloth to form a B-stage prepreg, and a printed wiring board is produced using the prepreg.

As the prepreg impregnated into the glass cloth and made into a B stage, there is a prepreg called glass paper in which a resin is impregnated with a paper-like non-woven fabric made of glass fiber using an epoxy resin or the like as a binder (for example, Patent Document 1).
However, when a sheet-like glass substrate prepreg as described above is used as a printed wiring board material, the water absorption rate is increased depending on the resin, which adversely affects insulation reliability and heat resistance. If the resin skeleton or compounding composition is changed as a countermeasure, other characteristics inherent to the resin may not be fully exhibited.
JP-A-9-241404

  An object of the present invention is to provide a sheet-like glass substrate prepreg capable of lowering the water absorption without impairing the insulation reliability and heat resistance required for a printed wiring board, a laminate using the same, and a printed wiring board. .

As a result of intensive research to achieve the above object, the present inventors pay attention to moisture accumulated at the interface between the resin and glass, and reduce the ratio of the glass surface area to the sheet area (area ratio). It has been found that the water absorption rate can be lowered as compared with the conventional product.
In addition, when a guanamine compound is contained in a thermosetting resin, particularly an epoxy resin, printed wiring balanced in copper foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with copper and dielectric properties. Although it is possible to produce a plate, the hygroscopicity is slightly higher than other resins, so when impregnated in a normal glass substrate, the water absorption rate will increase, which will adversely affect insulation reliability and heat resistance. On the other hand, the inventors have found that the water absorption rate can be effectively reduced by using a glass substrate having a specific area ratio, and have reached the present invention. The present invention has been completed based on such findings.

That is, the present invention provides the following sheet-like glass substrate prepreg, laminate and printed wiring board.
1. A prepreg obtained by impregnating or applying a thermosetting resin (B) to a sheet-like glass substrate (A) and drying, wherein the total area of the glass surface of the sheet-like glass substrate (A) is Sg, the sheet area An area ratio [R _S = Sg / 2S] where S is S is in the range of 0.5 to 1.3.
2. The sheet-like glass substrate prepreg according to 1 above, wherein the sheet-like glass substrate (A) is a mesh-like and / or thin-film glass.

3. 3. The sheet-like glass substrate prepreg according to 1 or 2 above, wherein the thermosetting resin (B) contains a guanamine compound.
4). The thermosetting resin (B) is an epoxy resin (a) having at least two epoxy groups in one molecule, a maleimide compound (b1) having at least two N-substituted maleimide groups in one molecule, and the following general Compound (b) having an acidic substituent and an unsaturated maleimide group produced by reacting an amine compound (b2) having an acidic substituent represented by formula (1) in an organic solvent (b3), the following general formula A copolymer resin (d) having a 6-substituted guanamine compound (c) shown in (2) and a monomer unit (d1) shown in the following general formula (3) and a monomer unit (d2) shown in the following general formula (4) 3. The sheet-like glass substrate prepreg according to 3 above, which is a resin composition containing

（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; Is an integer from 1 to 5, y is an integer from 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。）

(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.)

5). A laminate obtained by laminating the sheet-like glass substrate prepreg according to any one of 1 to 4 above.
6). A metal-clad laminate obtained by heating and press-molding a metal foil on at least one surface of one or two or more of the prepregs of any one of 1 to 4 above.
7). The printed wiring board obtained by carrying out wiring processing using said 5 laminated board or said 6 metal-clad laminated board.

According to the present invention, it is possible to provide a printed wiring board having a low water absorption rate, good electrical characteristics, and excellent fine wiring formability.
In particular, even when a resin composition in which a guanamine compound is blended in an epoxy resin as described above is used as the resin, the hygroscopicity can be reduced, and the sheet-like glass substrate prepreg produces a laminate. As a prepreg for this purpose, it can be suitably used for electronic parts and the like.

Hereinafter, the present invention will be described in detail.
The sheet-like glass substrate prepreg of the present invention is impregnated or coated with a thermosetting resin (B) on a sheet-like glass substrate (A) having an area ratio R _S of 0.5 to 1.3 and dried. It will be.
In the present invention, the area ratio R _S is obtained by dividing the total area of the glass surface by twice the sheet area of the glass substrate, where Sg is the total area of the glass surface and _S is the sheet area of the glass substrate: It is defined as Sg / 2S. Here, the reason why the denominator is 2S is that the front side and the back side of the sheet-like glass substrate are taken into consideration.
The sheet area (S) is usually an area in a planar state. On the other hand, as a method for obtaining the total area (Sg) of the glass surface, the total area of the glass surface based on the amount of nitrogen gas or krypton gas adsorbed, such as a method obtained by geometric calculation or the BET method. There is a method for obtaining the area ratio R _S , etc., but it is preferable to obtain it based on the adsorption amount of nitrogen gas from the practical point of view.

A sheet-like glass substrate usually used for a printed wiring board is composed of a woven fabric or a non-woven fabric made of yarns of several tens to several thousands of glass fibers having a thickness of several microns. The area ratio R _S is 20 to 400, and the water absorption is very high as described above.
On the other hand, the area ratio R _S of the sheet-like glass substrate (A) used in the present invention is in the range of 0.5 to 1.3, and in order to reliably reduce the water absorption rate, 1.0% It is particularly preferred that
By setting the area ratio R _S to 1.3 or less, the water absorption rate decreases, and the effect of the resin characteristics becomes dominant, and this tendency is further promoted as the area ratio R _S is further lowered. However, if it is less than 0.5, the volume of the glass is considerably reduced, and therefore the effects of using the glass substrate such as strength, handleability, and the effect of reducing the coefficient of thermal expansion are not preferable. In addition, in a highly hygroscopic resin, the water absorption rate may increase due to an increase in the resin content accompanying a decrease in the glass volume. Therefore, it is not effective to make the area ratio R _S less than 0.5. .

The sheet-like glass substrate (A) used in the prepreg of the present invention has a small area ratio R _S of 0.5 to 1.3, and in order to obtain this area ratio, a thin-film or network-like glass is used. Is preferred.
The sheet-like glass substrate (A) is preferably a thin glass with no voids from the viewpoint of electrical characteristics, but in terms of processability and adhesion to the resin, it is a mesh or randomly formed holes. It is preferable that the glass is a thin film glass or a mesh glass.
These mesh-like glass and thin-film glass are both planar, but the thin-film glass has a geometric reason for making the glass substrate having an area ratio R _S of less than 1. It is theoretically essential to have voids. This void may be formed at the time of producing the thin film glass, or may be formed later by a drill or a laser. The mesh glass is preferably produced by knitting flat glass fibers into a mesh shape.

The method for producing these thin glass and flat glass fibers includes a method of forming a thin film by vapor deposition on a substrate such as silicon, a float method for taking out molten glass horizontally, a fusion method for taking down vertically in a vertical direction, etc. Any method may be used as long as the desired product is obtained.
Moreover, what was manufactured by heat-melting the glass cloth normally used for printed wiring boards may be used. Further, the glass thin film can be polished to make it thinner.
In the present invention, it is important that the area ratio R _S is smaller than that of a glass cloth using a conventional yarn in which glass fibers are bundled regardless of the presence or absence and shape of voids.
Examples of the glass include E glass, D glass, S glass, and Q glass.
The thickness of the sheet-like glass substrate is not particularly limited as long as there is no problem in handleability and workability, but 0.01 to 0.5 mm obtained by laminating one or more of the above-mentioned mesh-like glass or thin-film glass. A thing (about 10-500 micrometers) is used.

The sheet-like glass substrate (A) is preferably surface-treated with a silane coupling agent or the like from the viewpoints of heat resistance, moisture resistance, and workability.
Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, epoxy-functional silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N- Amino-functional silanes such as 2- (aminoethyl) 3-aminopropyltrimethoxysilane and N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, vinyltrimethoxysilane, vinylphenyltrimethoxysilane, vinyltris (2 Olefin functional silanes such as -methoxyethoxy) silane, acrylic functional silanes such as 3-acryloxypropyltrimethoxysilane, methacryl functional silanes such as 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysila And mercapto-functional silanes and the like are used. Considering compatibility with the resin to be impregnated later, it is desirable to have an epoxy group or an amino group in the molecule. These may be used alone or in combination.
In the surface treatment with a silane coupling agent, these coupling agents were dissolved in a solvent such as water at a concentration of 0.1 to 15 g / L and adsorbed on glass at a temperature of room temperature (25 ° C.) to 50 ° C. Thereafter, it is carried out by forming a stable bond by heating, ultraviolet irradiation or the like. In general, heating is performed at a temperature of 100 to 200 ° C. for 2 to 60 seconds, and ultraviolet irradiation is performed at a wavelength of 200 to 400 nm and in an irradiation amount range of 200 to 2500 mJ / cm ² .

  As the thermosetting resin (B) used for the sheet-like glass substrate prepreg of the present invention, a resin or a resin composition generally used as an insulating material for a printed wiring board can be used. This thermosetting resin (B) is usually based on a thermosetting resin having good heat resistance and chemical resistance, such as phenol resin, epoxy resin, cyanate ester resin, maleimide resin, isocyanate resin, benzocyclobutene. Examples thereof include, but are not limited to, resins and vinyl resins. These thermosetting resins may be used alone or in combination of two or more.

Epoxy resins are particularly important because they are widely used as insulating resins because they are excellent in heat resistance, chemical resistance and electrical characteristics among the thermosetting resins described above, and are relatively inexpensive.
Epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins and other bisphenol type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and bisphenol A novolak type epoxy resins. Type epoxy resin, cycloaliphatic epoxy resin, aliphatic chain epoxy resin, diglycidyl etherified product of biphenol, diglycidyl etherified product of naphthalenediol, diglycidyl etherified product of phenols and diglycidyl etherified product of alcohols, and these Examples include alkyl-substituted products, halides, hydrogenated products, and the like. One type of epoxy resin may be used alone, or two or more types may be mixed and used.
In addition, an epoxy resin curing agent can be used together with the epoxy resin. This curing agent can be used without limitation as long as it cures an epoxy resin, such as polyfunctional phenols, polyfunctional alcohols, amines, imidazole compounds, acid anhydrides and organophosphorus compounds, and halogens thereof. And the like. These epoxy resin curing agents may be used alone or in combination of two or more.

  In the present invention, as the thermosetting resin (B), a resin containing a guanamine compound in an epoxy resin is preferably used. As such a resin, an epoxy having at least two epoxy groups in one molecule is used. Resin (a) A maleimide compound (b1) having at least two N-substituted maleimide groups in one molecule and an amine compound (b2) having an acidic substituent represented by the following general formula (1) are combined with an organic solvent ( b3) a compound (b) having an acidic substituent and an unsaturated maleimide group produced by reacting in 6-substituted guanamine compound (c) shown in the following general formula (2) and the following general formula (3) There is a resin composition containing a copolymer resin (d) having a monomer unit (d1) shown and a monomer unit (d2) shown in the following general formula (4).

（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、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。）

(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.)

  In the above resin composition, the epoxy resin (a) having at least two epoxy groups in one molecule [hereinafter also referred to as epoxy resin (a)] is not particularly limited, and examples thereof include bisphenol A and bisphenol F. Glycidyl ethers, glycidyl amines, glycidyl esters, etc., such as bismuth, biphenyl, novolac, polyfunctional phenol, naphthalene, alicyclic, alcohol, etc. 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 copper 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.

An epoxy resin curing agent or curing accelerator may be used for the epoxy resin (a). Examples of the curing agent for the epoxy resin (a) include acid anhydrides such as maleic anhydride and maleic anhydride copolymers. Products, amine compounds such as dicyanodiamide, 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 the curing accelerator for the epoxy resin (a) include imidazoles and derivatives thereof, tertiary amines and quaternary ammonium salts.

  The compound (b) having an acidic substituent and an unsaturated maleimide group includes a maleimide compound (b1) having at least two N-substituted maleimide groups in one molecule and an amine having an acidic substituent represented by the general formula (1) It is produced by reacting compound (b2) with organic solvent (b3).

  Examples of maleimide compound (b1) having at least two N-substituted maleimide groups in one molecule [hereinafter also referred to as maleimide compound (b1)] include bis (4-maleimidophenyl) methane, poly (maleimidophenyl) 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) Sulfone are 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 (b2) having an acidic substituent represented by the general formula (1) [hereinafter also referred to as amine compound (b2)] 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-dicarboxyl Among these, m-aminophenol, p-aminophenol, p-aminobenzoic acid, m-aminobenzoic acid and 3,5-dihydroxyaniline are preferred in view of solubility and synthesis yield. Preferably, m-aminophenol and p-aminophenol are more preferable from the viewpoint of heat resistance, and m-aminophenol is preferable from the viewpoint of low toxicity. Phenol is particularly preferred.

The amount of the maleimide compound (b1) and amine compound (b2) used in the production of the compound (b) having an acidic substituent and an unsaturated maleimide group is the equivalent of the maleimide group of the maleimide compound (b1) and the amine compound. The equivalent ratio of (b2) to the equivalent of —NH ₂ group is represented by the following formula:
1.0 ≦ (maleimide group equivalent) / (- equivalent of NH ₂ groups in terms) ≦ 10.0
It is preferable that it is the quantity used as the range shown in this, and it is still more preferable that this equivalent ratio is the quantity used as the range of 2.0-10.0.
By setting the equivalent 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 (b3) used in this reaction is not particularly limited, but alcohol solvents such as ethanol, propanol, butanol, methyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, ether solvents such as tetrahydrofuran, aromatic solvents such as toluene, xylene, mesitylene, nitrogen atom containing solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, sulfur atom containing solvents such as dimethyl sulfoxide, etc. 1 type or 2 types or more 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 (b3) 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 amine compound (b1) and the maleimide compound (b2). 200 to 500 parts by mass is particularly preferable.

The reaction temperature for producing the compound (b) having an acidic substituent and an unsaturated maleimide group is 50 to 200 ° C., preferably 100 to 160 ° C., and the reaction time is 0.1 to 10 hours, preferably 1 ~ 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. A mixture of seeds or more can be used.
By this reaction, for example, by using a bis (4-maleimidophenyl) compound as the maleimide compound (b1) and reacting with the amine compound (b2), an acidic substituent and an unsaturated maleimide group represented by the following general formula (5) Is synthesized.

（式中、Ｒ₁は、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の和が５である。Ａはアルキレン基、アルキリデン基、エーテル基又はスルフォニル基を示す。）

(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 and y is an integer of 0 to 4 and the sum of x and y is 5. A represents an alkylene group, an alkylidene group, an ether group or a sulfonyl group.

  The 6-substituted guanamine compound (c) is a compound represented by the general formula (2). For example, 2,4-diamino-6-phenyl-s-triazine called benzoguanamine, 2 called acetoguanamine. , 4-diamino-6-methyl-s-triazine, 2,4-diamino-6-vinyl-s-triazine, and the like. Among these, benzoguanamine having a high reaction rate and higher heat resistance And 2,4-diamino-6-vinyl-s-triazine are more preferable, and benzoguanamine is particularly preferable from the viewpoint of low toxicity and low cost.

The copolymer resin (d) is a copolymer resin having a monomer unit (d1) represented by the general formula (3) and a monomer unit (d2) represented by the general formula (4).
Examples of the monomer unit (d1) represented by the general formula (3) include styrene compounds such as styrene, 1-methylstyrene, vinyltoluene, dimethylstyrene, chlorostyrene, and bromostyrene, and vinyl compounds such as ethylene, propylene, and isobutylene. If necessary, two or more monomers may be mixed and used. Further, the monomer unit (d2) represented by the general formula (4) is obtained from maleic anhydride.
The copolymer resin (d) may further contain various polymerizable monomer units (d3) in addition to the above monomer units. Examples of the monomer unit (d3) include N-phenylmaleimide. , N-hydroxyphenylmaleimide, N-carboxyphenylmaleimide, N-cyclohexylmaleimide and other maleimide compounds, methyl methacrylate, methyl acrylate and other methacryloyl group or acryloyl group-containing compounds, etc. From the viewpoint of moisture and heat resistance and adhesiveness, N-phenylmaleimide and N-hydroxyphenylmaleimide are more preferable.

When the number of monomer units of the monomer unit (d1) in the copolymer resin (d) is m, the number of monomer units of the monomer unit (d2) is n, and the number of monomer units of the monomer unit (d3) is r, the monomer ratio ( m / n) is preferably 0.8 to 19.0, and more preferably 1.0 to 6.0, considering the balance between dielectric properties, glass transition temperature, moisture and heat resistance, and adhesiveness.
Further, the monomer ratio [m / (n + r)] in the case of containing the monomer unit (d3) is 0.1 to 9.0 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.
The weight average molecular weight of the copolymer resin (d) 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.

Resin composition in which thermosetting resin (B) contains epoxy resin (a), compound (b) having acidic substituent and unsaturated maleimide group, 6-substituted guanamine compound (c) and copolymer resin (d) The content of each component in the case of a product is preferably as follows as the mass in 100 parts by mass of the total mass of the components (a) to (d).
The epoxy resin (a) is preferably 1 to 96 parts by mass, more preferably 20 to 96 parts by mass, and particularly preferably 20 to 90 parts by mass. By setting the content of the epoxy resin (a) to 1 part by mass or more, flame retardancy, adhesiveness, and heat resistance are not insufficient, and by setting the content to 96 parts by mass or less, the low dielectric loss property is lowered. There is nothing.
The compound (b) having an acidic substituent and an unsaturated maleimide group is preferably 1 to 96 parts by mass, more preferably 20 to 96 parts by mass, and particularly preferably 20 to 90 parts by mass. By setting the content of the compound (b) having an acidic substituent and an unsaturated maleimide group to 1 part by mass or more, flame retardancy, adhesiveness, and flexibility are not deficient, and 96 parts by mass or less. Therefore, the heat resistance is not lowered.
The 6-substituted guanamine compound (c) is preferably 1 to 96 parts by mass, more preferably 20 to 96 parts by mass, and particularly preferably 20 to 90 parts by mass. By setting the content of the 6-substituted guanamine compound (c) to 1 part by mass or more, flame retardancy, adhesiveness, and dielectric properties are not insufficient, and by setting the content to 96 parts by mass or less, heat resistance decreases. There is nothing.
The copolymer resin (d) 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 the copolymer resin (d) to 1 part by mass or more, the solubility and dielectric properties are not insufficient, and by setting the content to 50 parts by mass or less, flame retardancy does not decrease.

  The resin containing the above guanamine compound is excellent in various properties as described above, but has a slightly higher hygroscopicity than other resins, so by applying the present invention, the hygroscopic property of other resins. Can be equivalent to sex. In other words, the above guanamine resin is thermosetting because it can produce a printed wiring board balanced in all of copper foil adhesion, heat resistance, moisture resistance, flame resistance, heat resistance with copper, dielectric properties and moisture absorption. Suitable as the resin (B).

As the thermosetting resin (B), a cyanate ester resin is also preferably used. The cyanate ester resin is a resin that generates a cured product having a triazine ring as a repeating unit by heating, and the cured product is excellent in dielectric characteristics, and is often used particularly when high-frequency characteristics are required. Examples of cyanate ester resins include 2,2-bis (4-cyanatophenyl) propane, bis (4-cyanatophenyl) ethane, 2,2-bis (3,5-dimethyl-4-cyanatophenyl) methane, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, α, α′-bis (4-cyanatophenyl) -m-diisopropylbenzene, phenol novolac And cyanate esterified products of alkylphenol novolac and the like.
Among the above-mentioned cyanate ester resins, 2,2-bis (4-cyanatophenyl) propane is preferable because it has a particularly good balance between the dielectric properties and curability of the cured product and is inexpensive in terms of cost. One kind of cyanate ester resin may be used alone, or two or more kinds may be mixed and used. Moreover, the cyanate ester resin used here may be partially oligomerized in advance to a trimer or a pentamer.
Moreover, a curing catalyst or a curing accelerator can be used for the cyanate ester resin. As the curing catalyst, metals such as manganese, iron, cobalt, nickel, copper, and zinc are used. Specifically, organic metal salts such as 2-ethylhexanoate, naphthenate, octylate, and acetylacetone are used. Used as organometallic complexes such as complexes. These may be used alone or in combination of two or more. Phenols are preferably used as the curing accelerator, and monofunctional phenols such as nonylphenol and paracumylphenol, bifunctional phenols such as bisphenol A, bisphenol F, and bisphenol S, or polyfunctional phenols such as phenol novolac and cresol novolac. Etc. can be used. These may be used alone or in combination of two or more.

  In consideration of dielectric properties, impact resistance, film processability, etc., the thermosetting resin (B) can contain a thermoplastic resin to such an extent that the properties as a thermosetting resin are not impaired. Examples of the thermoplastic resin include, but are not limited to, fluororesin, polyphenylene ether, modified polyphenylene ether, polyphenylene sulfide, polycarbonate, polyether imide, polyether ether ketone, polyarylate, polyamide, polyamide imide, and polybutadiene. I don't mean. One type of thermoplastic resin may be used alone, or two or more types may be mixed and used.

  Among thermoplastic resins, blending polyphenylene ether and modified polyphenylene ether is useful because it improves the dielectric properties of the cured product. Examples of polyphenylene ether and modified polyphenylene ether include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene alloyed polymer, poly Alloyed polymer of (2,6-dimethyl-1,4-phenylene) ether and styrene-butadiene copolymer, Alloyed polymer of poly (2,6-dimethyl-1,4-phenylene) ether and styrene-maleic anhydride copolymer Alloying polymer of poly (2,6-dimethyl-1,4-phenylene) ether and polyamide, alloying polymer of poly (2,6-dimethyl-1,4-phenylene) ether and styrene-butadiene-acrylonitrile copolymer, etc. Is mentioned. In addition, in order to impart reactivity and polymerizability to polyphenylene ether, functional groups such as amino groups, epoxy groups, carboxyl groups, styryl groups, and methacryl groups are introduced at the ends of polymer chains, or amino groups are introduced into the side chains of polymer chains. In addition, a functional group such as an epoxy group, a carboxyl group, a styryl group, or a methacryl group may be introduced.

  Among thermoplastic resins, polyamideimide resin is useful because it has excellent heat resistance and moisture resistance, and also has good adhesion to metal. Among the raw materials of polyamideimide, trimellitic anhydride, trimellitic anhydride monochloride, as the acid component, and metaphenylene diamine, paraphenylene diamine, 4,4′-diaminodiphenyl ether, 4,4′- as the amine component. Examples include, but are not limited to, diaminodiphenylmethane, bis [4- (aminophenoxy) phenyl] sulfone, 2,2′-bis [4- (4-aminophenoxy) phenyl] propane, and the like. In order to improve drying property, it may be modified with siloxane. In this case, siloxane diamine is used as the amino component. In consideration of film processability, it is preferable to use a molecular weight of 50,000 or more.

  The thermosetting resin (B) can contain an inorganic filler. Examples of the inorganic filler include alumina, aluminum hydroxide, magnesium hydroxide, clay, talc, antimony trioxide, antimony pentoxide, zinc oxide, fused silica, glass powder, quartz powder, and shirasu balloon. These inorganic fillers may be used alone or in combination of two or more.

An organic solvent can be mix | blended with a thermosetting resin (B). Examples of the organic solvent include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and trimethylbenzene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether solvents such as tetrahydrofuran; Alcohol solvents; ether alcohol solvents such as 2-methoxyethanol and 2-butoxyethanol; amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide are used. The
When preparing the prepreg, the amount of the organic solvent in the varnish is preferably in the range of 40 to 80% by mass, and the viscosity of the varnish is preferably in the range of 20 to 1000 cP.

You may make a thermosetting resin (B) contain a flame retardant. Examples of flame retardants include bromine compounds such as decabromodiphenyl ether, tetrabromobisphenol A, tetrabromophthalic anhydride, tribromophenol, triphenyl phosphate, tricresyl phosphate, trixyl phosphate, cresyl diphenyl phosphate, etc. Known metal compounds such as phosphorus compounds, magnesium hydroxide and aluminum hydroxide, red phosphorus and its modified products, antimony compounds such as antimony trioxide and antimony pentoxide, and triazine compounds such as melamine, cyanuric acid and melamine cyanurate Conventional flame retardants can be used.
If necessary, the thermosetting resin (B) may contain various additives and fillers such as a curing agent, a curing accelerator, thermoplastic particles, a colorant, an ultraviolet opaque agent, an antioxidant, and a reducing agent. It can be included.

The sheet-like glass substrate prepreg of the present invention is a prepreg obtained by impregnating or applying a thermosetting resin (B) to a sheet-like glass substrate (A) and drying, and is usually a sheet-like glass substrate ( A) The thermosetting resin (B) is impregnated or coated on the substrate so that the resin content of the prepreg after drying is 20 to 90% by mass, and then 1 to 30 at a temperature of 100 to 200 ° C. It is manufactured by heating and drying for half a minute to bring it into a semi-cured state (B stage state).
Further, the laminate of the present invention is obtained by usually laminating and molding 1 to 20 sheet-like glass substrate prepregs, and the metal-clad laminate usually accumulates 1 to 20 prepregs, at least of which It is obtained by heating and pressing in a configuration in which a metal foil is disposed on one surface.
As a forming method, a method of a normal laminated plate can be applied, for example, using a multistage press, a multistage vacuum press, continuous forming, an autoclave molding machine, etc. It shape | molds in the range for 0.1 to 5 hours, or it carries out on the conditions of pressure reduction and atmospheric pressure on the conditions of lamination conditions 50-150 degreeC and 0.1-5 MPa using a vacuum laminating apparatus. Although the thickness of the prepreg layer used as an insulating layer changes with uses, it is 0.01-5.0 mm normally.

The surface roughness of the metal foil used for forming the metal-clad laminate of the present invention is not particularly limited, but the electrical characteristics are that the 10-point average roughness (Rz) shown in JIS B0601 is 2.0 μm or less on both sides. Above preferred. Although copper foil, nickel foil, aluminum foil, etc. can be used for metal foil, copper foil is usually used. In the case of a copper sulfate bath, the manufacturing conditions of the copper foil are 50 to 100 g / L of sulfuric acid, 30 to 100 g / L of copper, a liquid temperature of 20 to 80 ° C., a current density of 0.5 to 100 A / dm ² , pyrophosphoric acid In the case of a copper bath, the conditions of potassium pyrophosphate 100-700 g / L, copper 10-50 g / L, liquid temperature 30-60 ° C., pH 8-12, current density 1-10 A / dm ² are commonly used, Various additives can also be used in consideration of the physical properties and smoothness of copper.

The thickness of the metal foil is not particularly limited, and may be a metal foil having a thickness of 105 μm or less that is generally used for a printed wiring board. However, in order to form fine wiring, the thickness is preferably 3.0 μm or less. Peelable type metal foil may be used. Here, the peelable type metal foil is a metal foil having a carrier, which is a metal foil that can be peeled off by the carrier. For example, in the case of a peelable type ultra-thin copper foil, a metal oxide or organic layer to be a release layer is formed on a carrier foil having a thickness of 10 to 50 μm, and a sulfuric acid 50 to 100 g / h is used on the copper sulfate bath. L, copper 30 to 100 g / L, liquid temperature 20 ° C. to 80 ° C., current density 0.5 to 100 A / dm ² , potassium pyrophosphate bath 100 to 700 g / L potassium pyrophosphate, copper 10 to 50 g / L, a liquid temperature of 30 ° C. to 60 ° C., a pH of 8 to 12, and a current density of 1 to 10 A / dm ² are produced by forming a metal foil having a thickness of 0.3 to 3.0 μm. When such a foil is used for the power feeding layer, the wiring formability is good as described later. Note that an etchable type copper foil having an aluminum carrier or a nickel carrier can be used instead of the peelable type.

Rust prevention treatment is preferably performed on the surface of the metal foil that comes into contact with the prepreg or resin. This rust prevention treatment can be performed using any of nickel, tin, zinc, chromium, molybdenum, cobalt, or an alloy thereof, but is preferably performed using zinc and chromium. In these methods, a thin film is formed on a metal foil by sputtering, electroplating or electroless plating, but electroplating is preferable from the viewpoint of cost. Specifically, the rust prevention treatment is performed by performing plating using a plating layer containing one or more metal salts of nickel, tin, zinc, chromium, molybdenum, and cobalt. From the viewpoint of reliability and the like later, it is preferable to perform plating containing zinc. In order to facilitate the precipitation of metal ions, a complexing agent such as citrate, tartrate or sulfamic acid can be added in the required amount.
The plating solution is usually used in an acidic region and is performed at a temperature of room temperature (25 ° C.) to 80 ° C. In general, the plating is appropriately selected from the range of current density of 0.1 to 10 A / dm ² , energization time of 1 to 60 seconds, preferably 1 to 30 seconds. The amount of the rust-proofing metal varies depending on the type of metal, but is preferably 10 to 2000 μg / dm ^{2 in} total. If the rust preventive treatment is too thick, it may cause etching inhibition and deterioration of electrical characteristics, and if it is too thin, it may cause a reduction in peel strength with the resin.

Furthermore, if a chromate treatment layer is formed on the rust prevention treatment, it is useful because a reduction in peel strength with the resin can be suppressed. Specifically, it is performed using an aqueous solution containing hexavalent chromium ions. The chromate treatment can be performed by a simple immersion treatment, but is preferably performed by a cathode treatment. It is good to carry out under conditions of sodium dichromate 0.1-50 g / L, pH 1-13, bath temperature 0-60 ° C., current density 0.1-5 A / dm ² , electrolysis time 0.1-100 seconds. It can also carry out using chromic acid or potassium dichromate instead of sodium dichromate.

  In the present invention, it is preferable that a silane coupling agent is further adsorbed on the surface of the metal foil. Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, epoxy-functional silanes such as 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and N-2. Amino-functional silanes such as-(aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, vinyltrimethoxysilane, vinylphenyltrimethoxysilane, vinyltris (2- Olefin functional silane such as methoxyethoxy) silane, acrylic functional silane such as 3-acryloxypropyltrimethoxysilane, methacryl functional silane such as 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane Such as mercapto functional silane is used. Considering compatibility with the prepreg, it is desirable to have an epoxy group or an amino group in the molecule. These may be used alone or in combination.

These coupling agents are dissolved in a solvent such as water at a concentration of 0.1 to 15 g / L and applied to a metal foil at a temperature of room temperature (25 ° C.) to 50 ° C. or electrodeposited for adsorption. Let These silane coupling agents form a film by condensation bonding with a hydroxyl group of a rust-preventing metal on the surface of the metal foil. After the silane coupling treatment, a stable bond is formed by heating, ultraviolet irradiation or the like. If it is heating, it is dried at a temperature of 100 to 200 ° C. for 2 to 60 seconds. In the case of ultraviolet irradiation, it is performed in the range of 200 to 400 nm and 200 to 2500 mJ / cm ² . The copper foil as described above can be integrated with the prepreg by a known method to obtain a laminated sheet.

Next, an example of a printed wiring board manufacturing method using an ultrathin copper foil having a thickness of 3 μm as the metal foil among the metal-clad laminates will be described. First, through-holes for interlayer connection are formed in the metal-clad laminate. If the through hole diameter is 100 μm or more, processing by a drill is suitable, and if the through hole diameter is 100 μm or less, a gas laser such as CO ₂ , CO, or excimer, or a solid laser such as YAG is suitable.

  Next, catalyst nuclei are provided on the metal foil and inside the through hole. For providing the catalyst nucleus, an activator neogant (trade name, manufactured by Atotech Japan Co., Ltd.), which is a palladium ion catalyst, and HS201B (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a palladium colloid catalyst, are used. When the palladium catalyst is applied, a conditioning treatment such as CLC-201 (trade name, manufactured by Hitachi Chemical Co., Ltd.) is performed in advance.

  Next, a thin electroless plating layer is formed on the metal foil provided with the catalyst nucleus and inside the through hole. For this electroless plating, commercially available electroless copper plating such as CUST2000 (manufactured by Hitachi Chemical Co., Ltd., trade name) or CUST201 (product name of Hitachi Chemical Co., Ltd.) can be used. These electroless copper platings are mainly composed of copper sulfate, formalin, complexing agent and sodium hydroxide. The thickness of the plating is not limited as long as the next electroplating can be performed, and about 0.1 to 1 μm is sufficient. If interlayer connection is not required, electroless copper plating can be omitted.

  Next, after performing electroless plating, a plating resist is formed. The thickness of the plating resist is preferably set to a thickness that is about the same as or thicker than the conductor to be subsequently plated. Resins that can be used for the plating resist include liquid resists such as PMER P-LA900PM (trade name, manufactured by Tokyo Ohka Co., Ltd.), HW-425 (trade name, Hitachi Chemical Co., Ltd.), RY-3325 (Hitachi Chemical). There are dry films such as Kogyo Co., Ltd. (trade name). A plating resist is not formed on the via hole and the portion to be a conductor circuit.

  Next, a circuit pattern is formed by electroplating. For the electroplating, copper sulfate electroplating usually used for printed wiring boards can be used. The plating thickness may be used as a circuit conductor, and is preferably in the range of 1 to 100 μm, and more preferably in the range of 5 to 50 μm.

  Next, the resist is stripped using an alkaline stripping solution, sulfuric acid, or a commercially available resist stripping solution, and copper other than the pattern portion is removed by etching. In this case, etching is generally performed by high-pressure spraying or the like, but the exchange of the liquid is inevitably worsened for fine portions of the wiring. Therefore, it is desirable that the reaction between the copper and the etching solution is not diffusion-limited but reaction-limited. If the reaction between copper and the etchant is reaction-controlled, the etching rate does not change even if diffusion is further increased. That is, a difference in etching rate between a place where the liquid exchange is good and a place where the liquid exchange is bad does not occur much. Specifically, an etching solution mainly containing hydrogen peroxide and an acid not containing a halogen element is preferably used. When hydrogen peroxide is used as the oxidizing agent, strict etching rate control is possible by controlling the hydrogen peroxide concentration. If a halogen element is mixed in the etching solution, the dissolution reaction tends to be diffusion-limited. As the acid not containing halogen, nitric acid, sulfuric acid, organic acid, and the like can be used, but sulfuric acid is preferable because it is inexpensive. Furthermore, when sulfuric acid and hydrogen peroxide are the main components, the respective concentrations are preferably 5 to 300 g / L and 5 to 200 g / L from the viewpoints of etching rate and liquid stability.

As mentioned above, although the method of producing a board | substrate by the semi-additive method using ultra-thin copper foil was shown, other methods, such as a general semi-additive method and a subtractive method, may be used.
A core substrate composed of two layers is completed by the method described above. A prepreg may be further laminated thereon to produce a multilayer wiring board. The prepreg used in this case is produced by the same method as that for the core substrate. After lamination, an interlayer connection hole (IVH) is formed in the interlayer resin insulation layer from above the metal foil. As a method for forming IVH, it is preferable to use a laser. Lasers that can be used here include gas lasers such as CO ₂ , CO, and excimer, and solid lasers such as YAG. Since a CO ₂ laser can easily obtain a large output, it is suitable for processing IVH having a diameter of 50 μm or more. When processing a fine IVH having a diameter of 50 μm or less, a YAG laser having a shorter wavelength and good condensing property is suitable.

  Conformal drilling can also be used for IVH formation. In this case, a window hole is formed in the copper foil by a photolithography method, and IVH is formed with a laser diameter larger than that of the window hole. In addition, IVH formation by a large window method is also possible, and in this case, plating peeling does not occur in a portion where the resin around IVH is exposed.

  Next, the resin residue inside the IVH is removed using an oxidizing agent such as permanganate, chromate or chromic acid, and then catalyst nuclei are imparted on the metal foil and inside the IVH. In the present invention, since the resin residue inside the IVH is removed and at the same time the portion where the resin is exposed can be roughened, the plateability in the subsequent plating process is improved.

  Next, a thin electroless plating layer is formed on the metal foil provided with catalyst nuclei and inside IVH. For this electroless plating, commercially available electroless copper plating such as CUST2000 (manufactured by Hitachi Chemical Co., Ltd., trade name) or CUST201 (product name of Hitachi Chemical Co., Ltd.) can be used. These electroless copper platings are mainly composed of copper sulfate, formalin, complexing agent and sodium hydroxide. The thickness of the plating is not limited as long as the next electroplating can be performed, and about 0.1 to 1 μm is sufficient.

  Next, after performing electroless plating, a plating resist is formed. The thickness of the plating resist is preferably about the same as or thicker than the conductor to be subsequently plated. Resins that can be used for the plating resist include liquid resists such as PMER P-LA900PM (trade name, manufactured by Tokyo Ohka Co., Ltd.), HW-425 (trade name, manufactured by Hitachi Chemical Co., Ltd.), RY-3325 (Hitachi). There are dry films such as those manufactured by Kasei Kogyo Co., Ltd. A plating resist is not formed on the via hole and the portion to be a conductor circuit.

  Next, a circuit pattern is formed by electroplating. For the electroplating, copper sulfate electroplating usually used for printed wiring boards can be used. The plating thickness may be used as a circuit conductor, and is preferably in the range of 1 to 100 μm, and more preferably in the range of 5 to 50 μm. Next, the resist is stripped using an alkaline stripping solution, sulfuric acid, or a commercially available resist stripping solution. Next, the formation of the circuit is completed by removing the copper other than the pattern portion by using an etchant preferably containing 10 to 300 g / L sulfuric acid and 10 to 200 g / L hydrogen peroxide as main components.

  Further, electroless gold plating is performed on the circuit to form a gold plating layer. As a gold plating method, the conductor interface is activated with an activation treatment solution such as SA-100 (manufactured by Hitachi Chemical Co., Ltd., trade name), and NIPS-100 (manufactured by Hitachi Chemical Co., Ltd., product). Electroless nickel plating such as HGS-100 (made by Hitachi Chemical Co., Ltd., trade name) and HGS- Electroless gold plating such as 2000 (manufactured by Hitachi Chemical Co., Ltd., trade name) is performed for about 0.1 to 1 μm. Further, when electroless palladium plating is performed between electroless nickel plating and electroless gold plating as disclosed in JP-A-11-140659, connection reliability is further improved. For electroless palladium plating, a pallet (trade name, manufactured by Kojima Chemical Co., Ltd.) is used in an amount of 0.01 to 1 μm. In consideration of electrical characteristics, electroless nickel plating can be omitted. These combinations vary depending on the product application, and are determined in consideration of cost, electrical characteristics, and connection reliability. The present invention is effective regardless of which method is used.

Next, the present invention will be described in more detail with reference to the following examples, but these examples do not limit the present invention.
In the following examples and comparative examples, the area ratio of the sheet-like glass substrate and the water absorption rate of the copper clad laminate are numerical values obtained by the following method.
(1) Area ratio (R _S )
The sheet area (S) of the sheet-like glass substrate was calculated from the length and width of the sheet-like glass substrate, and the total area (Sg) of the glass surface was measured by the BET method to determine the area ratio according to the following formula. .
Area ratio R _S = Sg / 2S
(2) Water absorption rate (S _W )
After etching the copper-clad laminate, the resin plate from which the copper foil was completely removed was dried at 80 ° C. for 30 minutes, and the mass (W _d ) at the time of drying was measured, and then at 121 ° C. and 2 atm (0.2 MPa) After 5 hours of PCT (Pressure Cooker Test) treatment, the mass (W _w ) after water absorption was measured, and the water absorption rate (%) was determined according to the following formula.
Water absorption S _W = [(W _w −W _d ) / W _d ] × 100

Example 1
(Manufacture of varnish A)
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, bis (4-maleimidophenyl) methane: 358.00 g and m-aminophenol: 54.50 g And propylene glycol monomethyl ether: 412.50 g was added and reacted for 5 hours while refluxing to obtain a solution (1) of the compound (b) having an acidic substituent and an unsaturated maleimide group.

  In a reaction vessel with a volume of 2 liters, which can be heated and cooled, equipped with a thermometer, a stirrer, and a moisture quantifier with a reflux condenser, a copolymer resin of styrene and maleic anhydride (manufactured by Elf Atchem, trade name EF-40) ): 514.00 g, cyclohexanone: 462.60 g and toluene: 51.40 g were added, and the mixture was heated to 70 ° C. and uniformly dissolved, and then aniline: 46.50 g was gradually added dropwise. 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 solution (2) of a copolymer resin (d) composed of styrene, maleic anhydride and N-phenylmaleimide. The weight average molecular weight was 10,000. 40 parts by mass of the resin of the solution (1), 10 parts by mass of the benzoguanamine, 10 parts by mass of the resin of the solution (2), 40 parts by mass of a phenol novolac type epoxy resin, 80 parts by mass of aluminum hydroxide as an inorganic filler, 10 parts by mass of crushed silica In addition, uniform varnish A having a resin content of 70% by mass was obtained using methyl ethyl ketone as a diluent solvent.

(Manufacture of sheet-like glass substrate A)
A flat glass fiber having a thickness of 5 μm and a width of 20 μm is woven in a mesh shape with a pitch (distance between centers of adjacent glass fibers) of 39 μm vertically and horizontally, and 3-glycidoxypropyltrimethoxysilane is added to water. It was immersed in a 0.1 g / L solution for 60 seconds, washed with water, and then dried at 120 ° C. for 60 seconds to obtain a sheet-like glass substrate A having a thickness of 10 μm. The area ratio (R _S ) of this sheet-like glass substrate was 1.27.

(Manufacture of prepreg A)
Varnish A was applied to the sheet-like glass substrate A with a tabletop coating machine and dried by heating at 160 ° C. for 10 minutes to obtain a prepreg A having a resin content of 55% by mass.

(Manufacture of copper-clad laminate A)
Four prepregs A were stacked, and an electrolytic copper foil having a thickness of 18 μm was placed on top and bottom, and pressed at a pressure of 2.5 MPa and a temperature of 185 ° C. for 90 minutes to obtain a copper-clad laminate A. The water absorption (Sw) of the copper clad laminate A was 0.44%. When the copper clad laminate A was floated on a solder bath at 288 ° C. for 10 minutes and subjected to a heat resistance test, no blistering occurred.

(Manufacture of printed wiring boards)
The copper-clad laminate A was etched to a thickness of 5 μm, and wiring was formed by a method according to the semi-additive method using the ultrathin copper foil described above to obtain a printed wiring board A. When an insulation reliability test was performed using a comb pattern of L / S = 30/30, no insulation failure occurred even after 100 hours of HAST (Highly Accelerated Stress Test).

Example 2
A flat glass fiber having a thickness of 5 μm and a width of 50 μm was used and woven with a glass fiber pitch of 155 μm in the same manner as in Example 1 to produce a sheet-like glass substrate B having a thickness of 10 μm. The area ratio (R _S ) of this sheet-like glass substrate was 0.71.
Next, a prepreg and a copper clad laminate B were produced in the same manner as in Example 1. The water absorption (S _W ) of the copper clad laminate B was 0.38%.

Example 3
A flat glass fiber having a thickness of 5 μm and a width of 50 μm was used, and the pitch of the glass fiber was woven as 180 μm in the same manner as in Example 1 to produce a sheet-like glass substrate C having a thickness of 10 μm. The area ratio (R _S ) of the sheet-like glass substrate C was 0.61.
Next, a prepreg and a copper clad laminate C were produced in the same manner as in Example 1. The water absorption (S _W ) of the copper clad laminate C was 0.43%.

Comparative Example 1
In Example 1, instead of the sheet-like glass substrate A, a sheet-like glass substrate D (manufactured by Asahi Schwer, glass cloth 1027, thickness 20 μm) was used. Plate D was produced. The area ratio (R _S ) of the sheet-like glass substrate D was 139, and the water absorption rate (S _W ) of the copper-clad laminate D was 0.68%.
When the copper clad laminate D was floated on a solder bath at 288 ° C. for 10 minutes and subjected to a heat resistance test, no blistering occurred.

(Manufacture of printed wiring boards)
Wiring was formed in the same manner as in Example 1, and a printed wiring board D was obtained. When an insulation reliability test was performed using a comb pattern of L / S = 30/30, no insulation failure occurred even after 100 hours of HAST.

  From the above examples, by using the prepreg of the present invention, it becomes possible to reduce the water absorption rate of the laminate, thereby providing a printed wiring board excellent in heat resistance, insulation reliability, and electrical characteristics. It turns out that it is possible.

Claims (7)

A prepreg obtained by impregnating or applying a thermosetting resin (B) to a sheet-like glass substrate (A) and drying, wherein the total area of the glass surface of the sheet-like glass substrate (A) is Sg, the sheet area An area ratio [R _S = Sg / 2S] where S is S is in the range of 0.5 to 1.3.   The sheet-like glass substrate prepreg according to claim 1, wherein the sheet-like glass substrate (A) is a mesh-like and / or thin-film glass.   The sheet-like glass substrate prepreg according to claim 1 or 2, wherein the thermosetting resin (B) is a resin containing a guanamine compound. The thermosetting resin (B) is an epoxy resin (a) having at least two epoxy groups in one molecule, a maleimide compound (b1) having at least two N-substituted maleimide groups in one molecule, and the following general Compound (b) having an acidic substituent and an unsaturated maleimide group produced by reacting an amine compound (b2) having an acidic substituent represented by formula (1) in an organic solvent (b3), the following general formula A copolymer resin (d) having a 6-substituted guanamine compound (c) shown in (2) and a monomer unit (d1) shown in the following general formula (3) and a monomer unit (d2) shown in the following general formula (4) The sheet-like glass substrate prepreg according to claim 3, which is a resin composition containing

(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 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.)

  The laminated board obtained by carrying out lamination molding of the sheet-like glass base material prepreg in any one of Claims 1-4.   A metal-clad laminate obtained by superposing one or more sheets of the sheet-like glass substrate prepreg according to any one of claims 1 to 4 on at least one surface and then heating and pressing. Board.   The printed wiring board obtained by carrying out wiring processing using the laminated board of Claim 5, or the metal-clad laminated board of Claim 6.