JP2000301534A - Prepreg, metal-clad laminated board, and printed wiring board using prepreg and laminated board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a prepreg which can be used in a high speed wire bonding and has a high surface hardness at high temperatures and a small surface roughness, and provide a metal-clad laminated board, and a printed wiring board using the prepreg and laminated board. SOLUTION: A base material is impregnated with a resin composition containing a resin and inorganic filler of 25 vol.% or more and a silicone polymer to provide a prepreg, and a metal foil is superposed on both sides or on one side of the prepreg or a laminated body thereof, which is heated and pressed to provide a metal-clad laminated board, so that the printed wiring board is obtained by printing wiring on the laminated board. The resin composition contains a coupling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a prepreg, a metal-clad laminate, and a printed wiring board using the same.

[0002]

2. Description of the Related Art With the spread of information terminal electronic devices such as personal computers and mobile phones, printed wiring boards mounted thereon have been reduced in size and density. The mounting form has been changed from the conventional pin insertion type to the surface mounting type, and in recent years, to the area array type represented by a BGA (ball grid array) using a plastic substrate. Above all, in the case of a substrate on which a bare chip such as a BGA is directly mounted, the connection between the chip and the substrate is generally performed by wire bonding using thermosonic pressure bonding. For this reason, the substrate on which the bare chip is mounted is exposed to a high temperature of 150 ° C. or higher, and it is necessary to maintain a certain degree of hardness during pressure bonding. Furthermore, with the increase in processing speed, I / O of MPU
The number of terminals is increasing, and the number of terminals connected by wire bonding is increasing and the terminal width is being narrowed. In other words, it is necessary to perform wire bonding connection to a very small terminal in a shorter time than ever before, and a laminate used for this purpose is required to have excellent characteristics capable of coping with high-speed wire bonding. Laminate characteristics corresponding to high-speed wire bonding include excellent surface hardness at high temperatures and excellent surface smoothness of a substrate including connection terminals that are narrowed.

As a technique for improving the surface hardness at a high temperature, improvement in the physical properties of a cured resin by increasing the Tg (glass transition temperature) of the resin has been widely performed (Japanese Patent Application Laid-Open No. Sho.
3-321316). However, simply increasing the Tg by increasing the cross-linking density causes a large decrease in hardness in a temperature region higher than the Tg, which makes it difficult to cope with increasingly severe high-speed wire bonding in the future. In general, a high Tg-based resin cured product has a large amount of shrinkage due to curing and cooling in combination with the bulkiness of the resin skeleton, and when it is used as a laminated board, it tends to spread irregularities of the base material and tends to increase the surface roughness. Is shown.

As a technique for improving the surface hardness and the surface smoothness, there is a method of changing the type of a woven fabric used as a base material of a metal-clad laminate. In order to improve the surface hardness, a woven fabric having a high elastic modulus is effective.In order to improve the surface smoothness, there are methods such as flattening the woven form of the woven fabric as much as possible. It is difficult to improve beyond a certain level only by changing the base material. On the other hand, there is a method of blending an inorganic filler in the resin composition (Japanese Patent Publication No. 2-453).
No. 48). In order to improve the surface hardness and surface smoothness, it is necessary to add a certain amount of inorganic filler. However, if the inorganic filler is highly filled in the resin composition, the aggregation of the inorganic filler itself and the resin composition solution When the metal-clad laminate is heated and pressurized to form a metal-clad laminate after being impregnated into the base material, microvoids and unimpregnated parts occur frequently, resulting in a decrease in the heat resistance of the resulting metal-clad laminate and marked insulation. It causes deterioration.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and provides a prepreg, a metal-clad laminate having a high surface hardness at a high temperature and a small surface roughness capable of coping with high-speed wire bonding. A printed wiring board using the same is provided.

[0006]

The present invention relates to the following. 1. A prepreg obtained by impregnating a base material with a resin composition containing at least 25% by volume of a resin, an inorganic filler and a silicone polymer. 2. Item 2. The prepreg according to Item 1, wherein the inorganic filler has been previously surface-treated with a silicone polymer. 3. Item 3. The prepreg according to item 1 or 2, wherein the resin composition further contains a coupling agent. 4. Item 4. The prepreg according to items 1 to 3, wherein the inorganic filler has been previously treated with a silicone polymer and a coupling agent. 5. Item 3. The prepreg according to item 1 or 2, wherein the resin composition is a resin composition obtained by blending a resin with a solution containing an inorganic filler dispersed in a solution of a silicone polymer. 6. Item 3. The prepreg according to item 1 or 2, wherein the resin composition is a resin composition obtained by blending a resin with a solution containing an inorganic filler dispersed in a solution of a silicone polymer and a coupling agent. 7. Item 7. The prepreg according to any one of Items 1 to 6, wherein the silicone polymer is three-dimensionally crosslinked. 8. Item 8. The prepreg according to item 7, wherein the silicone polymer contains a trifunctional siloxane unit (RSiO _3/2 ) or a tetrafunctional siloxane unit (SiO _4/2 ) in the molecule. (In the above formula, the R groups are the same or different organic groups.) The silicone polymer contains 15 to 100% by mole of a tetrafunctional silane compound or a trifunctional silane compound and 0 to 8 of a bifunctional silane compound based on all siloxane units in the molecule.
Item 9. The prepreg according to item 8, which contains 5 mol%. 10. The silicone polymer contains 15 to 100 mol% of a tetrafunctional siloxane unit and 0 to 85 mol% of a trifunctional siloxane unit and 0 to 85 mol% of a difunctional siloxane unit, based on all siloxane units in the molecule. Item 10. The prepreg according to item 9, wherein 11. Item 10. A metal-clad laminate obtained by laminating a metal foil on both surfaces or one surface of the prepreg or the laminate thereof according to any one of Items 1 to 10, and heating and pressing. 12. Item 12. The metal-clad laminate according to item 11, wherein the metal-clad laminate has a surface hardness (hardness of a nonmetallic surface or a surface excluding a metal) of not less than 30 in Barcol hardness at 200 ° C. 13. Item 13. A printed wiring board obtained by performing circuit processing using the metal-clad laminate according to item 11 or 12.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The resin used in the present invention is not particularly limited, but the resin is preferably a thermosetting resin, and a thermoplastic resin having high heat resistance is also preferable. As the resin, for example, epoxy resin, polyimide resin, triazine resin,
Melamine resin, phenol resin and the like are used. Also,
Two or more of these resins may be used in combination, and various curing agents, curing accelerators, and the like may be added to the resin as necessary. These can be used as a solvent solution. As the solvent, alcohol solvents, ether solvents, ketone solvents, amide solvents, aromatic hydrocarbon solvents, ester solvents, nitrile solvents and the like can be used,
Further, a mixed solvent obtained by mixing two or more solvents can also be used.

As the curing agent, various conventionally known curing agents can be used. For example, when an epoxy resin is used as the resin, an amine compound such as dicyandiamide, diaminodiphenylmethane, diaminodiphenylsulfone, phthalic anhydride, Examples thereof include acid anhydride compounds such as pyromellitic acid, and polyfunctional phenol compounds such as phenol novolak resins and cresol novolak resins. Some of these curing agents can be used in combination. The polyimide resin, triazine resin, and the like are generally cured with a commonly used epoxy resin, amine compound, or the like, but are not limited thereto. The amount of the curing agent is not particularly limited, but is preferably 0.5 to 1.5 equivalents to the functional group of the main material such as an epoxy resin. Accelerators may be used to promote curing with any of the resin systems. The type of the accelerator is not particularly limited, and examples thereof include an imidazole compound, an organic phosphorus compound, a secondary amine, a tertiary amine, and a quaternary ammonium salt. Good. The amount of the accelerator is not particularly limited, either, but is not limited to 100 parts by weight of the resin as the main material.
It is preferably from 0.01 to 10.0 parts by weight.

The imidazole compounds include imidazole compounds such as imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole,
-Phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2- Heptadecylimidazoline, 2-isopropylimidazole, 2,4-
Examples thereof include dimethylimidazole, 2-phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, and 2-phenyl-4-methylimidazoline. These may be masked by a masking agent. As a masking agent, acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate,
Melamine acrylate and the like.

The organic phosphorus compounds include triphenylphosphine and the like; the secondary amines include piperidine; and the tertiary amines include dimethylbenzylamine and tris (dimethylaminomethyl) phenol; Examples of the ammonium salt include tetrabutylammonium bromide and tetrabutylammonium chloride.

In the present invention, an inorganic filler is used in an amount of 25% by volume or more based on the total solid content of the resin composition for the purpose of improving the surface hardness and surface roughness at a high temperature. The type of the inorganic filler is not particularly limited, for example, calcium carbonate, alumina,
Titanium oxide, mica, aluminum carbonate, aluminum hydroxide, magnesium silicate, aluminum silicate, silica, short glass fibers, various whiskers such as aluminum borate whiskers and silicon carbide whiskers are used. These may be used in combination of several types. The blending amount of these inorganic fillers is 25% by volume based on the total amount of the resin composition solids.
Although not particularly limited as long as it is above, the surface hardness of the laminated plate (however, the hardness of the non-metal surface or the surface excluding the metal) becomes 30 or more in Barcol hardness at 200 ° C., In order to improve the surface roughness as much as possible, 25 to 65% by volume is preferable. The measurement of the blending amount of the inorganic filler is not particularly limited,
Weight of cured product of resin composition containing inorganic filler and 400
It is calculated by converting the volume from the value of the specific gravity of the cured product of the resin composition containing no inorganic filler and the specific gravity of the inorganic filler from the ratio with the weight of the inorganic component remaining after heating at about 700 ° C. for several hours. General.

In the present invention, a silicone polymer is used for the purpose of improving the dispersibility of the inorganic filler in the cured product of the resin composition. The inorganic filler is preferably surface-treated with this silicone polymer. The silicone polymer can be directly added to the resin composition containing an inorganic filler, which also has the effect of surface treatment of the inorganic filler with the silicone polymer.

The inorganic filler is preferably surface-treated in advance with a silicone polymer.
Preferably, an inorganic filler is incorporated into the silicone polymer solution. Next, it is particularly preferable to prepare a resin composition for producing a prepreg by blending the obtained solution with other resin materials. In the above, the temperature at the time of mixing is not particularly limited, but is equal to or higher than normal temperature
Or less, more preferably 150 ° C. or less.

Further, an inorganic filler is mixed with the silicone polymer solution, and the inorganic filler having the silicone polymer adhered to the surface is separated and dried to prepare an inorganic filler surface-treated with the silicone polymer. May be mixed with other components of the resin composition. At this time, the drying temperature is 50 to
200 ° C is preferable, and 80 to 150 ° C is more preferable.
The drying time is preferably 5 to 60 minutes, and 10 to 3 minutes.
0 minutes is more preferable.

The silicone polymer is preferably used in an amount of 0.01 to 10% by weight based on the weight of the inorganic filler.
It is preferable to use 0.05 to 5% by weight.

In the present invention, the silicone polymer may be a trifunctional siloxane unit (RSiO _3/2 ) wherein R is an organic group, and the R groups in the silicone polymer may be the same as each other; And at least one selected from tetrafunctional siloxane units (SiO _4/2 )
Contains siloxane units of various types and has a degree of polymerization of 2 to 7000
Is preferred. A more preferred lower limit is 3. A more preferred degree of polymerization is 5 to 5000, and a particularly preferred degree of polymerization is 10
-100, and has at least one functional group that reacts with a hydroxyl group at the terminal. Here, the degree of polymerization is calculated from the molecular weight of the polymer (in the case of a low degree of polymerization) or the number average molecular weight measured by gel permeation chromatography using a calibration curve of standard polystyrene or polyethylene glycol. As the siloxane unit, besides, a bifunctional siloxane unit (R ₂ SiO _2/2 )
May be contained in an amount of 0 to 85% with respect to the total number of units. Examples of the R include an alkyl group having 1 to 4 carbon atoms and a phenyl group. Examples of the functional group that reacts with a hydroxyl group include:
Examples include a silanol group, an alkoxyl group having 1 to 4 carbon atoms, an acyloxy group having 2 to 5 carbon atoms, and halogens such as chlorine and bromine.

The silicone polymer used in the present invention is three-dimensionally crosslinked. For example, a product consisting of only trifunctional siloxane units, a product consisting of only tetrafunctional siloxane units, a product consisting of difunctional siloxane units and trifunctional siloxane units, a product consisting of difunctional siloxane units and 4
Consisting of a functional siloxane unit, consisting of a trifunctional siloxane unit and a tetrafunctional siloxane unit, and 2
What consists of a functional siloxane unit, a trifunctional siloxane unit, and a tetrafunctional siloxane unit is preferable. As a specific content, a tetrafunctional siloxane unit or a trifunctional siloxane unit is 15 to 1 based on all siloxane units.
The content of 00 mol% and the amount of the bifunctional siloxane unit is preferably 0 to 85 mol%, and the content of at least one of the tetrafunctional siloxane unit and the trifunctional siloxane unit is 20 to 100 mol% and the content of the bifunctional siloxane unit is 0 to 80 mol. % Is more preferred. In particular, based on the total siloxane units, 15 to 100 mol% of the 4-functional siloxane units, 0 to 85 mol% of the trifunctional siloxane units, and 0 to 85 mol% of the bifunctional siloxane units.
85 mol% is preferred, and a tetrafunctional siloxane unit of 20 to
60 mol%, 0 to 80 mol% of trifunctional siloxane unit
And more preferably contains 0 to 80 mol% of a bifunctional siloxane unit.

The silicone polymer of the present invention has the general formula (I)

Embedded image R ′ _n SiX _4-n (I) (wherein X represents halogen such as chlorine or bromine or —OR, wherein R is an alkyl group having 1 to 4 carbon atoms, 1 carbon atom)
Represents an alkylcarbonyl group having an alkyl of 4 to 4,
R 'is an alkyl group having 1 to 4 carbon atoms, an aryl group such as a phenyl group, and n is an integer of 0 to 2).

The silane compound represented by the general formula (I) is specifically described below.

Embedded image Tetraalkoxysilane such as Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si (OC ₃ H ₇ ) ₄ , Si (OC ₄ H ₉ ) _4, etc. Hereinafter, the functionality in the silane compound means that the silane compound has a condensation-reactive functional group.)

Embedded image H ₃ CSi (OCH ₃ ) ₃ , H ₅ C ₂ Si (OCH ₃ ) ₃ , H ₇ C ₃ Si (OCH ₃ ) ₃ , H ₉ C ₄ Si (OCH ₃ ) ₃ , H ₃ CSi ( _{OC 2 H 5) 3, H} 5 C 2 Si (OC 2 H 5) 3, H 7 C 3 Si (OC 2 H 5) 3, H 9 C 4 Si (OC 2 H 5) 3, H 3 CSi ( _{OC 3 H 7) 3, H} 5 C 2 Si (OC 3 H 7) 3, H 7 C 3 Si (OC 3 H 7) 3, H 9 C 4 Si (OC 3 H 7) 3, H 3 CSi ( _{OC 4 H 9) 3, H} 5 C 2 Si (OC 4 H 9) 3, H 7 C 3 Si (OC 4 H 9) 3, H 9 C 4 Si (OC 4 H 9) 3, monoalkyl etc. Trialkoxysilane,

Embedded image PhSi (OCH ₃ ) ₃ , PhSi (OC ₂ H ₅ ) ₃ , PhSi (OC ₃ H ₇ ) ₃ , PhSi (OC ₄ H ₉ ) ₃ (wherein Ph represents a phenyl group; the same applies hereinafter) Phenyl trialkoxysilane such as,

Embedded image (H ₃ CCOO) ₃ SiCH ₃ , (H ₃ CCOO)
₃ SiC ₂ H ₅ , (H ₃ CCOO) ₃ SiC ₃ H ₇ , (H ₃ CCOO) ₃ SiC
Monoalkyl triacyloxy silanes such as ₄ H ₉

Embedded image Cl ₃ SiCH ₃ , Cl ₃ SiC ₂ H ₅ , Cl ₃ SiC ₃ H ₇ , Cl ₃ SiC ₄ H ₉ Br ₃ SiCH ₃ , Br ₃ SiC ₂ H ₅ , Br ₃ SiC ₃ H ₇ , Br ₃ trifunctional silane compounds such as monoalkyl trihalogenosilane such SiC ₄ H _9,

Embedded image (H ₃ C) ₂ Si (OCH ₃ ) ₂ , (H ₅ C ₂ ) ₂ S
i (OCH ₃ ) ₂ , (H ₇ C ₃ ) ₂ Si (OCH ₃ ) ₂ , (H ₉ C ₄ ) ₂ Si (OC
_{H 3) 2, (H 3} C) 2 Si (OC 2 H 5) 2, (H 5 C 2) 2 Si (OC
_{2 H 5) 2, (H} 7 C 3) 2 Si (OC 2 H 5) 2, (H 9 C 4) 2 Si (O
C ₂ H ₅ ) ₂ , (H ₃ C) ₂ Si (OC ₃ H ₇ ) ₂ , (H ₅ C ₂ ) ₂ Si (OC
_{3 H 7) 2, (H} 7 C 3) 2 Si (OC 3 H 7) 2, (H 9 C 4) 2 Si (O
_{C 3 H 7) 2, (} H 3 C) 2 Si (OC 4 H 9) 2, (H 5 C 2) 2 Si (OC
_{4 H 9) 2, (H} 7 C 3) 2 Si (OC 4 H 9) 2, (H 9 C 4) 2 Si (O
Dialkyl dialkoxysilane of C ₄ H _{9) 2} and the like,

Embedded image Diphenyldialkoxysilanes such as Ph ₂ Si (OCH ₃ ) ₂ and Ph ₂ Si (OC ₂ H ₅ ) ₂

Embedded image (H ₃ CCOO) ₂ Si (CH ₃ ) ₂ , (H ₃ CC
OO) ₂ Si (C ₂ H ₅ ) ₂ , (H ₃ CCOO) ₂ Si (C ₃ H ₇ ) ₂ , (H ₃ CCOO) ₂
Si dialkyl acyloxysilane such as (C ₄ H _{9) 2,}

Embedded image Cl ₂ Si (CH ₃ ) ₂ , Cl ₂ Si (C ₂ H ₅ ) ₂ , Cl ₂ Si (C ₃ H ₇ ) ₃ , Cl ₂ Si (C ₄ H ₉ ) ₂ , Br ₂ Si ( Bifunctional silane compounds such as alkyl dihalogenosilanes such as CH ₃ ) ₂ , Br ₂ Si (C ₂ H ₅ ) ₂ , Br ₂ Si (C ₃ H ₇ ) ₂ and Br ₂ Si (C ₄ H ₉ ) ₂ There is.

As the silane compound represented by the general formula (I) used in the present invention, a tetrafunctional silane compound or a trifunctional silane compound is used as an essential component.
The functional silane compound is appropriately used as needed. In particular, the tetrafunctional silane compound is preferably a tetraalkoxysilane, the trifunctional silane compound is preferably a monoalkyl trialkoxysilane, and the bifunctional silane compound is preferably a dialkyldialkoxysilane. The proportion of the silane compound used is preferably a tetrafunctional silane compound or a trifunctional silane compound 15 to 100.
The mol% and the bifunctional silane compound are preferably 0 to 85 mol%, and at least one of the tetrafunctional silane compound and the trifunctional silane compound is 20 to 100 mol% and the bifunctional silane compound is 0 to 80 mol%. Is more preferred. In addition, it is particularly preferable to use a tetrafunctional silane compound in a proportion of 15 to 100 mol%, a trifunctional silane compound of 0 to 85 mol%, and a bifunctional silane compound of 0 to 85 mol%.
More preferably, the tetrafunctional silane compound is used at a ratio of 20 to 100 mol%, the trifunctional silane compound is used at a ratio of 0 to 80 mol%, and the bifunctional silane compound is used at a ratio of 0 to 80 mol%.

The silicone polymer of the present invention hydrolyzes the silane compound represented by the above general formula (I),
It is produced by polycondensation.At this time, as a catalyst, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, or hydrofluoric acid, or an organic acid such as oxalic acid, maleic acid, sulfonic acid, formic acid, or acetic acid is used. It is preferable to use a basic catalyst such as ammonia or trimethylammonium. These catalysts are used in an appropriate amount depending on the amount of the silane compound represented by the general formula (I). It is used in a range of 5 mol.

The above-mentioned hydrolysis and polycondensation are preferably carried out in a solvent used for varnish formation described below, and more preferably carried out in an alcohol solvent or a ketone solvent. In this reaction, water is present. The amount of water is also appropriately determined. However, if the amount is too large, there is a problem that storage stability of the coating solution is reduced. Therefore, the amount of water is determined based on 1 mol of the silane compound represented by the general formula (I). Therefore, the content is preferably 0 to 5 mol%, more preferably 0.5 to 4 mol.

[0023] These silicone polymers may be used in combination with various coupling agents. Examples of the coupling agent include a silane-based coupling agent and a titanate-based coupling agent. Examples of the silane-based coupling agent include an epoxysilane-based coupling agent, an aminosilane-based coupling agent, and a cationic silane-based coupling agent. , A vinylsilane-based coupling agent, an acrylsilane-based coupling agent, a mercaptosilane-based coupling agent, and a composite thereof. When the coupling agent is used, it is most preferable to use it simultaneously with the silicone polymer in various preparation operations and the like. When a coupling agent is used, it is added to the inorganic filler in an amount of 0.1%.
It is preferably used in an amount of from 0.01 to 10% by weight,
It is preferable to use 5% by weight.

The resin composition containing these resin materials, inorganic fillers and the like is preferably diluted with a solvent to form a varnish before use. The type of the solvent used at this time is not particularly limited. For example, alcohol solvents such as methanol and ethanol, ether solvents such as ethylene glycol monomethyl ether, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; There are amide solvents such as N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene, ester solvents such as ethyl acetate, nitrile solvents such as butyronitrile, and the like. Good. The solid content concentration of the varnish is not particularly limited, and can be appropriately changed depending on the resin composition, the type and the amount of the inorganic filler, and the like.
The range of from 80% by weight to 80% by weight is preferred. If it is less than 50% by weight, the varnish viscosity tends to be low, and the resin content of the prepreg tends to be low. If it exceeds 80% by weight, the appearance and the like of the prepreg tend to be remarkably deteriorated due to thickening of the varnish. Preferably it is 55 to 75% by weight.

A base material is impregnated with a varnish of a resin composition containing a resin, an inorganic filler and a silicone polymer.
The prepreg is dried by drying at a temperature of 00 ° C. The substrate is not particularly limited as long as it is used when manufacturing a metal foil-clad laminate or a multilayer printed wiring board,
Usually, a fibrous base material such as a woven or nonwoven fabric is used. Examples of the material of the fiber base include glass, alumina, asbestos, boron, silica-alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, inorganic fibers such as zirconia, aramid, polyetheretherketone, polyetherimide, and polyether. There are organic fibers such as sulfone, carbon, cellulose and the like, and a mixed system thereof, and a woven fabric of glass fiber is particularly preferably used. As a substrate used for the prepreg, a glass cloth of 30 μm to 200 μm is particularly preferably used.

Although the production conditions of the prepreg are not particularly limited, it is preferable that the solvent used for the varnish is volatilized by 80% by weight or more. For this reason, the production method and drying conditions are not limited, and the drying temperature is 80 ° C to 200 ° C.
The temperature and the temperature are not particularly limited in consideration of the gel time of the varnish.

The impregnated amount of the varnish is 35 to 70% by weight based on the total amount of the varnish solid and the substrate.
It is preferable that

The method for producing an insulating plate, a laminate or a metal-clad laminate is as follows. The prepreg of the present invention or a laminate obtained by laminating a plurality of the prepregs, if necessary, has a metal foil layered on one or both sides thereof, usually at 130 to 250 ° C, preferably at a temperature in the range of 150 ° C to 200 ° C, usually 0 ° C. .5-
At a pressure in the range of 20 MPa, preferably 1 to 8 MPa,
An insulating plate, a laminate, or a metal-clad laminate can be manufactured by heating and pressing. By using a metal foil to form a metal-clad laminate, circuit processing can be performed on the laminate to form a printed circuit board. The metal-clad laminate preferably has a surface hardness in the absence of a metal, in other words, a hardness of a non-metal surface or a surface excluding a metal of not less than 30 in terms of Barcol hardness at 200 ° C.

As the metal foil used in the present invention, a copper foil or an aluminum foil is generally used, but a metal foil having a thickness of 5 to 200 μm which is usually used for a laminated board can be used. Also,
Nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-tin alloy, etc. were used as an intermediate layer, and a copper layer of 0.5 to 15 μm and a copper layer of 10 to 300 μm were provided on both surfaces. A composite foil having a layer structure or a composite foil having a two-layer structure in which aluminum and copper foil are combined can be used.

Using the metal-clad laminate of the present invention, a printed wiring board can be manufactured by performing circuit processing on a metal foil surface or a metal foil etched surface by a conventional method. In particular, these two-sided or one-sided wiring boards are used as inner layers, prepregs are arranged on both sides or one side thereof, and after press molding, drilling or plating is performed for interlayer connection, and circuit processing is performed in the same manner as described above. By applying, a multilayer printed wiring board can be manufactured.

The above circuit processing can be performed by a known method. For example, by forming necessary through holes with a drill, applying plating for conduction to the through holes, forming a resist pattern, removing unnecessary plating by etching, and finally peeling off the resist pattern Can be. On the surface of the printed wiring board thus obtained, the above-mentioned metal foil-clad laminate is further laminated under the same conditions as described above, and further, circuit processing is performed in the same manner as above to obtain a multilayer printed wiring board. be able to. In this case, it is not necessary to form a through hole, and a via hole may be formed, or both may be formed. Such multilayering is performed by laminating a predetermined number of sheets.

[0032]

EXAMPLES The present invention will now be described in detail with reference to Examples, but it should not be construed that the present invention is limited thereto.

Example 1 A glass flask equipped with a stirrer, a condenser and a thermometer was charged with 40 g of tetramethoxysilane and 9 g of methanol.
0.47 g of acetic acid and 1 part of distilled water were added to the solution containing 3 g.
8.9 g were blended and then stirred at 50 ° C. for 8 hours to synthesize a silicone polymer. The average of the siloxane repeating units of the obtained silicone polymer was 20. Methyl ethyl ketone was added to this silicone polymer solution to prepare a treatment liquid having a solid content of 10% by weight. 1300 g of calcined clay was added to this treatment liquid as an inorganic filler and stirred at room temperature for 1 hour to prepare a solution containing the treatment filler. The obtained solution containing the treated filler is heated to 50 ° C., and the resin and the compound in the following amounts, and methyl ethyl ketone and ethylene glycol monomethyl in a weight ratio of 50:50 are added to 180 parts by weight of the inorganic filler in the solution. An ether solvent was added to prepare a resin composition varnish having a solid content of 70% by weight. Here, the ratio of the inorganic filler to the total amount of the resin composition solids was about 37% by volume. 50 parts by weight of brominated bisphenol A type epoxy resin (ESB400T, Sumitomo Chemical Co., Ltd., epoxy equivalent: 400) 50 parts by weight of ortho-cresol novolak type epoxy resin (ESCN195, epoxy equivalent: 195 of Sumitomo Chemical Co., Ltd.) Phenol novolak resin 42 parts by weight (HP850N manufactured by Hitachi Chemical Co., Ltd., hydroxyl equivalent: 108) 0.5 parts by weight of 2-ethyl-4-methylimidazole 0.5 g by weight of the prepared varnish was applied to a glass cloth (style 2116, E-glass having a thickness of about 0.1 mm). ), And heated and dried at 150 ° C. for 5 minutes to obtain a prepreg having a resin content of 43% by weight. Four prepregs were laminated, and a copper foil having a thickness of 18 μm was laminated on both sides thereof, and a double-sided copper-clad laminate was produced at 170 ° C. for 90 minutes at 4.0 MPa.

Example 2 As in Example 1, trimethoxymethylsilane was added to 40
g, 93 g of methanol in a solution containing 0.5 g of acetic acid.
3 g and 15.8 g of distilled water were blended and then stirred at 50 ° C. for 8 hours to synthesize a silicone polymer. The average number of siloxane repeating units in the obtained silicone polymer was 15. Methyl ethyl ketone was added to this silicone polymer solution to prepare a treatment liquid having a solid content of 10% by weight. 1300 g of calcined clay was added to this treatment liquid as an inorganic filler and stirred at room temperature for 1 hour to prepare a solution containing the treatment filler. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler.

Example 3 As in Example 1, dimethoxydimethylsilane was added to 34
g, 8 g of tetramethoxysilane and 98 g of methanol
0.60 g of acetic acid and 14.0 g of distilled water were added to the blended solution.
g, and then stirred at 50 ° C. for 8 hours to synthesize a silicone polymer. The average number of siloxane repeating units in the obtained silicone polymer was 28. Methyl ethyl ketone was added to the silicone polymer solution to obtain a solid content of 10%.
By weight, a treatment liquid was prepared. 1300 g of calcined clay was added to this treatment liquid as an inorganic filler and stirred at room temperature for 1 hour to prepare a solution containing the treatment filler. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler.

Example 4 As in Example 1, dimethoxydimethylsilane was added to 20
g, 25 g of tetramethoxysilane and 10 g of methanol.
0.60 g of acetic acid and 1 part of distilled water were added to the solution containing 5 g.
7.8 g were blended and then stirred at 50 ° C. for 8 hours to synthesize a silicone polymer. The average number of siloxane repeating units in the obtained silicone polymer was 30. Methyl ethyl ketone was added to this silicone polymer solution to prepare a treatment liquid having a solid content of 10% by weight. 1300 g of calcined clay was added to this treatment liquid as an inorganic filler and stirred at room temperature for 1 hour to prepare a solution containing the treatment filler. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler.

Example 5 As in Example 1, trimethoxymethylsilane was added to 20
g, 22 g of tetramethoxysilane, 98 g of methanol
acetic acid 0.52 g and distilled water 18.
3 g were blended and then stirred at 50 ° C. for 8 hours to synthesize a silicone polymer. The average of the siloxane repeating units in the obtained silicone polymer was 25. Methyl ethyl ketone was added to the silicone polymer solution to obtain a solid content of 1%.
A treatment solution of 0% by weight was prepared. 1300 g of calcined clay was added to this treatment liquid as an inorganic filler and stirred at room temperature for 1 hour to prepare a solution containing the treatment filler. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler.

Example 6 As in Example 1, dimethoxydimethylsilane was added to 10
g, 10 g of trimethoxymethylsilane, 20 g of tetramethoxysilane, and 93 g of methanol, 0.52 g of acetic acid and 16.5 g of distilled water were added, and then the mixture was stirred at 50 ° C. for 8 hours to obtain a silicone polymer. Was synthesized. The average of the siloxane repeating units in the obtained silicone polymer was 23. Methyl ethyl ketone was added to this silicone polymer solution to prepare a treatment liquid having a solid content of 10% by weight. 1300 g of calcined clay was added to this treatment liquid as an inorganic filler and stirred at room temperature for 1 hour to prepare a solution containing the treatment filler. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler.

Example 7 As the inorganic filler, 2300 was used instead of 1300 g of calcined clay.
A filler-containing solution was prepared in the same manner as in Example 1 except that 000 g was blended. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler. However, the blending amounts of the resin and the compound with respect to 200 parts by weight of the inorganic filler in the solution were as follows, and the ratio of the inorganic filler to the total amount of the solid content of the resin composition was about 40% by volume. 50 parts by weight of brominated bisphenol A type epoxy resin (ESB400T, Sumitomo Chemical Co., Ltd., epoxy equivalent: 400) 50 parts by weight of ortho-cresol novolak type epoxy resin (ESCN195, epoxy equivalent: 195 of Sumitomo Chemical Co., Ltd.) Phenol novolak resin 42 parts by weight (HP850N manufactured by Hitachi Chemical Co., Ltd., hydroxyl equivalent: 108) 0.5 parts by weight of 2-ethyl-4-methylimidazole

Example 8 A treated filler-containing solution was prepared in the same manner as in Example 1, except that talc was used instead of calcined clay as the inorganic filler. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler. At this time, the ratio of the inorganic filler to the total amount of the resin composition solids was about 37% by volume.

Example 9 A treated filler-containing solution was prepared in the same manner as in Example 1 except that silica was used instead of calcined clay as an inorganic filler. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler. At this time, the ratio of the inorganic filler to the total amount of the resin composition solids was about 31% by volume.

Example 10 γ-glycidoxypropyltrimethoxysilane (trade name: A-187, manufactured by Nippon Unicar Co., Ltd.) was added to the silicone polymer solution obtained in Example 1 as a silane coupling agent.
Made) and methyl ethyl ketone, and the solid content is 10% by weight.
Was prepared. Here, the silicone polymer and A-
187 was blended at a weight ratio of 50:50. 1300 g of calcined clay was added to this treatment liquid as an inorganic filler and stirred at room temperature for 1 hour to prepare a solution containing the treatment filler. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler.

Example 11 To the silicone polymer solution obtained in Example 4 was added isopropyl tris (dioctyl pyrophosphate) titanate (trade name: KR46) as a titanate coupling agent.
B, Ajinomoto Co.) and methyl ethyl ketone
A treatment liquid having a solid content of 10% by weight was prepared. Here, the silicone polymer and KR46B were blended in a weight ratio of 50:50. A calcined clay as an inorganic filler is added to this treatment liquid at 130.
0 g was mixed and stirred at room temperature for 1 hour to prepare a solution containing the treated filler. A prepreg and a double-sided copper-clad laminate were thereafter manufactured in the same manner as in Example 1 using the solution containing the treated filler.

Example 12 2 parts by weight of the silicone polymer solution obtained in Example 1, methyl ethyl ketone and ethylene glycol monomethyl ether were added to the following resin, compound and inorganic filler to give a solid content of 70% by weight. A varnish was prepared. The prepared varnish was impregnated into a glass cloth (style 2116, E-glass) having a thickness of about 0.1 mm, heated and dried at 150 ° C. for 5 minutes to obtain a prepreg having a resin content of 43% by weight. Four prepregs were laminated, and a copper foil having a thickness of 18 μm was laminated on both sides thereof, and a double-sided copper-clad laminate was produced at 170 ° C. for 90 minutes at 4.0 MPa. 50 parts by weight of brominated bisphenol A type epoxy resin (ESB400T, Sumitomo Chemical Co., Ltd., epoxy equivalent: 400) 50 parts by weight of ortho-cresol novolak type epoxy resin (ESCN195, epoxy equivalent: 195 of Sumitomo Chemical Co., Ltd.) Phenol novolak resin 42 parts by weight (HP850N manufactured by Hitachi Chemical Co., Ltd., hydroxyl equivalent: 108) 0.5 parts by weight of 2-ethyl-4-methylimidazole 180 parts by weight calcined clay (about 37% by volume)

Example 13 2 parts by weight of the silicone polymer solution obtained in Example 10, methyl ethyl ketone and ethylene glycol monomethyl ether were added to the resin, compound and inorganic filler shown in Example 12 to give a solid content of 70%. A weight percent varnish was made. A prepreg and a double-sided copper-clad laminate were produced in the same manner as in Example 12 using the produced varnish.

Example 14 2 parts by weight of the silicone polymer solution obtained in Example 11, methyl ethyl ketone and ethylene glycol monomethyl ether were added to the resin, compound and inorganic filler shown in Example 12 to give a solid content of 70%. A weight percent varnish was made. A prepreg and a double-sided copper-clad laminate were produced in the same manner as in Example 12 using the produced varnish.

Comparative Example 1 An untreated calcined clay, a resin, a compound, methyl ethyl ketone and ethylene glycol monomethyl ether which were not treated with the treatment solution and were mixed in the following amounts were mixed.
A varnish having a solid content of 70% by weight was prepared. Using this varnish, a prepreg and a double-sided copper-clad laminate were produced in the same manner as in Example 12. 50 parts by weight of brominated bisphenol A type epoxy resin (ESB400T, Sumitomo Chemical Co., Ltd., epoxy equivalent: 400) 50 parts by weight of ortho-cresol novolak type epoxy resin (ESCN195, epoxy equivalent: 195 of Sumitomo Chemical Co., Ltd.) Phenol novolak resin 42 parts by weight (HP850N manufactured by Hitachi Chemical Co., Ltd., hydroxyl equivalent: 108) 0.5 parts by weight of 2-ethyl-4-methylimidazole 180 parts by weight calcined clay (about 37% by volume)

Comparative Example 2 The varnish of Comparative Example 1 was further blended with 2 parts by weight of γ-glycidoxypropyltrimethoxysilane (trade name: A-187, manufactured by Nippon Unicar Co., Ltd.) as a silane coupling agent. A varnish was prepared in the same manner as in Comparative Example 1 except for the above. Using this varnish, in the same manner as in Example 12,
A prepreg and a double-sided copper-clad laminate were produced.

Comparative Example 3 Epoxy-modified silicone oil (trade name: KF101, manufactured by Shin-Etsu Chemical Co., Ltd.) instead of the silicone polymer
A filler-containing solution was prepared in the same manner as in Example 1 except that the solution was used. Using this filler-containing solution, a prepreg and a double-sided copper-clad laminate were produced in the same manner as in Example 1.

Comparative Example 4 A treatment liquid having a solid content of 1% by weight was prepared with silane coupling agent (γ-glycidoxypropyltrimethoxysilane (trade name: A-187, manufactured by Nippon Unicar Co., Ltd.)) and methanol. The untreated calcined clay was immersed and stirred at room temperature for 1 hour, and then dried at 120 ° C. for 1 hour to perform a surface treatment. Using this treated calcined clay, a varnish was produced in the same manner as in Comparative Example 1. Using this varnish, a prepreg and a double-sided copper-clad laminate were produced in the same manner as in Example 12.

Comparative Example 5 The same procedure as in Example 1 was carried out except that the amount of the inorganic filler was changed to 100 parts by weight (about 20% by volume based on the total amount of the resin composition solids) instead of 180 parts by weight. A varnish was prepared. Using this varnish, a prepreg and a double-sided copper-clad laminate were produced in the same manner as in Example 12.

Next, Examples 1 to 14 and Comparative Examples 1 to 5
Using the double-sided copper-clad laminate prepared in the above, circuit processing was performed to produce a printed wiring board. For circuit processing, use a drill to form the required through-holes on the double-sided copper-clad laminate, apply plating for conduction to the through-holes, form a resist pattern, remove unnecessary copper foil and plating by etching, By removing the resist pattern. At this time, the hole diameter before plating was selected from 0.05 mm to 1.0 mm depending on the location. Further, the line (L) / space (S) by pattern formation is represented by L /
S = 100 μm / 100 μm to L / S = 25 μm / 25
Processing was performed by appropriately selecting from μm.

The thus obtained double-sided copper-clad laminates of Examples 1 to 14 and Comparative Examples 1 to 5 were evaluated for surface smoothness, Barcol hardness, wire bonding property, solder heat resistance and corrosion resistance. Table 1 shows the results.

The test method is as follows. The surface smoothness was measured in the lateral direction of the double-sided copper-clad laminate with a contact-type surface roughness meter, and the surface roughness was represented by Rmax (maximum height) at a reference length of 8 mm based on JIS B0601. The Barcol hardness was measured by heating a hot plate using a laminate obtained by etching the entire surface of a copper foil.
Barcol hardness when the temperature reached 00 ° C. was measured. For the wire bonding property, a printed wiring board having a pattern for wire bonding evaluation was prepared using a double-sided copper-clad laminate, and the adhesion rate and adhesion strength during 100 wire bondings were evaluated. Solder heat resistance was measured by holding in a pressure cooker tester for 2 hours and then soldering at 260 ° C.
After immersion for 0 second, the appearance was visually inspected. "O" in the table
"K" means that there is no measling (peeling of the resin due to thermal strain in the overlapping portion of the glass fiber weave) or blistering. The electrolytic corrosion resistance was measured using a drill having a diameter of 0.4 mmφ with a rotation speed of 80,000 rpm and a feed speed of 3,20.
A hole was drilled at 0 mm / min, and after plating about 20 μm, a through-hole with a hole wall interval of 300 μm was used. The time until conduction breakdown was measured at a temperature of 85 ° C., a relative humidity of 85%, and an applied voltage of 100 V. . In addition, it was confirmed that all the conduction breakdown locations occurred in CAF (CONDUCTIVE ANODIC FILAMENT) between the through holes.

[0055]

[Table 1]

The following can be understood from the above results. In Examples 1 to 14, there is no decrease in solder heat resistance or electric corrosion resistance,
The surface roughness was as small as 5 μm or less, and the Barcol hardness at 200 ° C. was 30 or more. In addition, 200 ° C
Is 100% (0% defect rate) at the time of wire bonding, the adhesion strength is sufficiently high, and excellent wire bonding properties are obtained.

[0057]

The metal-clad laminate obtained by using the prepreg according to the present invention and the printed wiring board using the same do not have a decrease in heat resistance and electrolytic corrosion resistance even when filled with a large amount of an inorganic filler, and have a smooth surface. It has excellent wire bonding properties due to its excellent properties and high surface hardness at high temperatures.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08J 5/08 CFH C08J 5/08 CFH 5/24 CFH 5/24 CFH H05K 1/03 610 H05K 1/03 610R // B29K 105: 08 105: 16 B29L 9:00 31:34 (72) Inventor Masato Miyatake 1500 Oji Ogawa, Shimodate-shi, Ibaraki Pref. Hitachi Chemical Co., Ltd. (72) Inventor Masahisa Oze Shimodate, Ibaraki 1500 Ogawa, Oita-shi, Hitachi Chemical Industry Co., Ltd.

Claims (13)

[Claims] 1. A prepreg obtained by impregnating a base material with a resin composition containing a resin, at least 25% by volume of an inorganic filler and a silicone polymer. 2. The prepreg according to claim 1, wherein the inorganic filler has been previously surface-treated with a silicone polymer. 3. The prepreg according to claim 1, wherein the resin composition further comprises a coupling agent. 4. The prepreg according to claim 1, wherein the inorganic filler has been previously treated with a silicone polymer and a coupling agent. 5. The prepreg according to claim 1, wherein the resin composition is a resin composition obtained by mixing a resin with a solution containing an inorganic filler dispersed in a solution of a silicone polymer. 6. The prepreg according to claim 1, which is a resin composition obtained by blending a resin with a solution containing an inorganic filler dispersed in a solution of a silicone polymer and a coupling agent. 7. The prepreg according to claim 1, wherein the silicone polymer is three-dimensionally crosslinked. 8. The prepreg according to claim 7, wherein the silicone polymer contains a trifunctional siloxane unit (RSiO _3/2 ) or a tetrafunctional siloxane single unit (SiO _4/2 ) in the molecule. (In the above formula, the R groups are the same or different organic groups). 9. A silicone polymer containing 15 to 100 mol% of a tetrafunctional siloxane unit or trifunctional siloxane unit and 0 to 85 mol% of a difunctional silane compound, based on all siloxane units in the molecule. The prepreg according to claim 8, wherein 10. The silicone polymer contains 15 to 1 tetrafunctional siloxane units based on all siloxane units in the molecule.
00 mol%, 0 to 85 mol% of trifunctional siloxane unit
The prepreg according to claim 9, wherein the prepreg contains 0 to 85 mol% of a bifunctional siloxane unit. 11. A metal-clad laminate obtained by laminating a metal foil on both surfaces or one surface of the prepreg or the laminate thereof according to any one of claims 1 to 10, and applying heat and pressure. 12. The metal-clad laminate according to claim 11, wherein the metal-clad laminate has a surface hardness (hardness of a nonmetallic surface or a surface excluding metal) of not less than 30 in Barcoal hardness at 200 ° C. 13. A printed wiring board obtained by performing circuit processing using the metal-clad laminate according to claim 11 or 12.