JP2003008212A - Resin material with wiring circuit, method of manufacturing the same, and multilayer printed wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin material which hardly decomposes, when it is subjected to chemicals such as an etching solution even if it is semi-cured, serves an insulation layer, is equipped with the wiring that is embedded in a resin sheet at molding and smooth after molding, and provided with a top surface that can be smoothed, and is suitable for fine wiring. SOLUTION: A wiring circuit-attached resin material is equipped with a wiring circuit layer formed on an insulating resin layer in a B-Stage state, and the wiring circuit-attached resin material and an inner plate are laminated, thermocompressed and molded into a printed wiring board in a manufacturing method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin material with a wiring circuit, a method for manufacturing the same, and a multilayer printed wiring board.

[0002]

2. Description of the Related Art A printed wiring board widely used in electronic equipment is obtained by subjecting a metal-clad laminate to a wiring circuit process. As the metal foil-clad laminate, a prepreg obtained by impregnating a woven fabric substrate with a resin varnish of a thermosetting resin composition and drying the laminate has been widely used. That is, the insulating base material layer was composed of a cured product of the thermosetting resin composition and a woven fabric base material, to which a metal foil was adhered. The term "printed wiring board" includes a double-sided printed wiring board and a multilayer printed wiring board. In addition, the conventional multi-layer printed wiring board is a conventional multi-layer printed wiring board and a metal foil that has been bonded and integrated by heating and pressing through a prepreg or resin sheet via a prepreg or resin sheet. It was obtained by applying circuit processing. A four-layer metal-clad laminate is a single-sided printed wiring board with metal foil bonded and integrated on both sides. A six-layer metal-clad laminate is a two-sided printed wiring board between two sheets. A metal foil was bonded and integrated on both sides of the prepreg or resin sheet.

In recent years, along with the miniaturization of electronic devices, it has become necessary to make printed wiring boards thinner and to densify wirings. When a woven fabric substrate is used as a material, there is a limit to reduction in thickness, and therefore it has been proposed to use a resin sheet in the production of a metal-clad multilayer laminate.

[0004]

As electronic devices are becoming smaller, lighter weight, higher performance, and lower cost, printed wiring boards are required to have higher density, thinner thickness, higher reliability, and lower cost. ing. For high density, fine wiring is required, and for that purpose the surface flatness must be good. Polishing is effective for improving the flatness of the surface, but there are problems that the number of steps is large and the cost is high, and it is difficult to obtain a uniform thickness.
Further, even in the case of forming a multi-layer structure, fine wiring is required for high density, and for that purpose, the flatness of the surface must be good. In order to improve the flatness of the surface, it is effective to polish and flatten the inner layer wiring, but the number of steps increases and the cost increases, and processing to a uniform thickness is preferable. There were problems such as difficult things. Therefore, it is conceivable to use a flexible resin sheet and have the wiring embedded in the resin sheet during molding. The resin sheet must be flexible in order to allow wiring to be embedded in a general resin sheet for wiring boards. Therefore, it is conceivable to use the resin in a semi-cured state. However, in the semi-cured state, the resin cannot withstand the etching process for forming the wiring, the resin is decomposed, and the resin does not serve as an insulating layer. In addition, in order to make the wiring flexible until the wiring is submerged in the state where the resin is cured, it may be possible to mix an elastomer as a soft component, but if an elastomer is used for the resin sheet, the water absorption will be high and the heat resistance will be high. There is a problem such as getting worse.

[0005]

[Means for Solving the Problems] As means for solving the above problems, decomposition of chemicals such as an etching solution does not occur even in a semi-cured state, it functions as an insulating layer, and wiring is formed at the time of molding. The present invention proposes a resin material that can be dipped into a resin sheet, has no unevenness of wiring after molding, and can flatten the surface, and is suitable for fine wiring.

The present invention relates to the items described below. (1) A resin material with a wiring circuit having a wiring circuit layer on an insulating resin layer in a B-Stage state. (2) The resin material with a wiring circuit according to (1), which comprises an insulating resin sheet in a B-Stage state and a wiring circuit layer provided on the insulating resin sheet. (3) The resin material with a wiring circuit according to (1), which comprises an insulating resin layer in a B-Stage state provided on the inner layer circuit board and a wiring circuit further provided on the insulating resin layer. (4) The resin material with a wiring circuit according to any one of (1) to (3), wherein the insulating resin layer comprises a resin composition containing a resin-curable silicone polymer, a curing agent, and an inorganic filler. (5) The resin material with a wiring circuit according to (4), wherein the blending amount of the inorganic filler is 100 parts by weight or more based on 100 parts by weight of the resin-curable silicone polymer in the resin composition forming the insulating resin layer. (6) The insulating resin layer is a resin-curable silicone polymer 10
0 parts by weight, curing agent 0.8 to 1 equivalent and inorganic filler 100
The resin material with a wiring circuit according to (4), which comprises a resin composition containing about 2000 parts by weight. (7) The insulating resin layer has a cured product having a thermal expansion coefficient of 50 × 1.
The resin material with a wiring circuit according to any one of (1) to (6), which is an insulating resin layer formed by using a resin composition having a temperature of 0 ^-6 / ° C or less. (8) The insulating resin layer is an insulating resin layer formed by using a resin composition having an elongation of 1.0% or more in a tensile test of a cured product, (1) to (7) The resin material with a wiring circuit according to any one of 1).

(9) A method for manufacturing a printed wiring board, comprising: stacking a resin material with a wiring circuit and an inner layer board on top of each other and heating and pressurizing them. (10) With a wiring circuit characterized in that a circuit is formed by etching away unnecessary metal from a laminate including an insulating resin layer in a B-Stage state and a metal foil arranged on the insulating resin layer. Method for manufacturing resin material. (11) The insulating resin layer is a resin-curable silicone polymer,
The method for producing a resin material with a wiring circuit according to (10), which comprises a resin composition containing a curing agent and an inorganic filler. (12) The method for producing a resin material with a wiring circuit according to (11), wherein the compounding amount of the inorganic filler is 100 parts by weight or more based on 100 parts by weight of the resin-curable silicone polymer. (13) The insulating resin layer is a resin-curable silicone polymer 1
00 parts by weight, 100 to 2000 parts by weight of the inorganic filler, and 0.8 to 1 part by weight of the curing agent with respect to the resin-curable silicone polymer.
The method for producing a resin material with a wiring circuit according to (11), which comprises a resin composition containing an equivalent amount.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The resin material with a wiring circuit in the present invention is a resin material in which a wiring circuit is formed on an insulating layer in a state of having sufficient circuit embedding properties, and for example, B
-Wiring is further provided on a resin sheet with a wiring circuit in which a wiring circuit is formed on a thermosetting resin sheet in a Stage state, or on an insulating layer made of a thermosetting resin in a B-Stage state provided on an inner layer circuit board. Examples include wiring board materials on which circuits are formed. In addition, B-Stage in the present invention
The state means that when the resin is immersed in the same solvent as that used for forming the resin varnish and stirred at 25 ° C. for 1 hour, the resin content is 5 to 5 parts.
It is a cured state in which 95% by weight remains without being dissolved. When the cured state in which the amount of the resin component that remains without being dissolved exceeds 95% by weight is C-
Stage state, 5% by weight less than the cured state A-Sta
ge state.

As the insulating resin in the present invention, a resin satisfying the chemical resistance required for chemical treatment such as etching removal of metal during wiring circuit processing is used even in the state of having sufficient circuit embedding property. B-Sta
It is preferable to use a thermosetting resin that satisfies the required chemical resistance in the ge state. Further, in consideration of connection reliability of an interlayer conduction path in the case of a multilayer wiring board, it is preferable to use a resin having a thermal expansion coefficient of 50 × 10 ⁻⁶ / ° C. or less as a cured product of an insulating resin. It is more preferable to use a resin having a temperature of 30 × 10 ⁻⁶ / ° C. or less, and it is particularly preferable to use a resin having a thermal expansion coefficient of 15 × 10 ⁻⁶ / ° C. or less. From the viewpoint of handleability when producing a multilayer wiring board and reliability when a multilayer wiring board is used, it is preferable to use a resin having an elongation of 1.0% or more in a tensile test of a cured product, and an elongation of 2.0. It is particularly preferable to use a resin whose content is at least%. Examples of such a resin include a resin composition containing a resin-curable silicone polymer, a curing agent therefor, and an inorganic filler.

The resin-curable silicone polymer has the general formula (I)

Embedded image R ′ _m (H) _k SiX _{4- (m + k)} (I) (wherein X is a group capable of being hydrolyzed and polycondensed, and examples thereof include halogen such as chlorine and bromine, or —OR. Wherein R represents an alkyl group having 1 to 4 carbon atoms and an alkylcarbonyl group having 1 to 4 carbon atoms, and R'is a non-reactive group, for example, an alkyl group having 1 to 4 carbon atoms. Group, an aryl group such as a phenyl group, k is 1 or 2, m is 0 or 1, m
+ K means 1 or 2) and can be obtained by reacting a silane compound represented by the formula (1) and a hydrosilylation reaction agent. The silane compound of the general formula (I) is hydrolyzed and polycondensed to form a Si—H group-containing silicone polymer, and the hydrosilylation reagent is used as a Si—H group-containing silicone polymer S.
A hydrosilylation reaction is carried out with the i-H group to obtain a resin-curable functional group-introduced silicone polymer.

The Si-H group-containing silane compound of the general formula (I) has the general formula (II)

Embedded image R ′ _n SiX _4-n (II) (wherein R ′ and X are the same as in the general formula (I), and n is 0
Means an integer of ~ 2. ) The silane compound represented by the formula (1) can be used in combination.

The Si-H group-containing silane compound represented by the general formula (I) is specifically

Embedded image HCH ₃ Si (OCH ₃ ) ₂ , HC ₂ H ₅ Si (O
CH ₃ ) ₂ , H ₃ CH ₇ Si (OCH ₃ ) ₂ , HC ₄ H ₉ Si
(OCH ₃ ) ₂ , HCH ₃ Si (OC ₂ H ₅ ) ₂ , HC ₂ H ₅ S
i (OC ₂ H ₅ ) ₂ , HC ₃ H ₇ Si (OC ₂ H ₅ ) ₂ , HC ₄
H ₉ Si (OC ₂ H ₅ ) ₂ , HCH ₃ Si (OC ₃ H ₇ ) ₂ , H
C ₂ H ₅ Si (OC ₃ H ₇ ) ₂ , HC ₃ H ₇ Si (OC
₃ H ₇ ) ₂ , HC ₄ H ₉ Si (OC ₃ H ₇ ) ₂ , HCH ₃ Si
(OC ₄ H ₉ ) ₂ , HC ₂ H ₅ Si (OC ₄ H ₉ ) ₂ , HC ₃ H ₇
Si (OC ₄ H ₉ ) ₂ , HC ₄ H ₉ Si (OC ₄ H ₉ ) ₂ , etc. alkyldialkoxysilane

[0013]

[Image Omitted] H ₂ Si (OCH ₃ ) ₂ , H ₂ Si (OC
₂ H ₅ ) ₂ , H ₂ Si (OC ₃ H ₇ ) ₂ , H ₂ Si (OC ₄ H ₉ )
₂ , etc. dialkoxysilane

[0014]

Embedded image HPhSi (OCH ₃ ) ₂ , HPhSi (OC ₂
H ₅ ) ₂ , HPhSi (OC ₃ H ₇ ) ₂ , HPhSi (OC ₄
H ₉ ) ₂ , (wherein Ph represents a phenyl group, and so on) and the like.

[0015]

Embedded image H ₂ Si (OCH ₃ ) ₂ , H ₂ Si (OC
₂ H ₅ ) ₂ , H ₂ Si (OC ₃ H ₇ ) ₂ , H ₂ Si (OC ₄ H ₉ )
₂ , a bifunctional silane compound such as dialkoxysilane (hereinafter, the functionality in the silane compound means having a condensation-reactive functional group).

[0016]

Embedded image HSi (OCH ₃ ) ₃ , HSi (OC ₂ H ₅ ) ₃ ,
There are trifunctional silane compounds such as trialkoxysilane such as HSi (OC ₃ H ₇ ) ₃ and HSi (OC ₄ H ₉ ) ₃ .

The silane compound represented by the general formula (II) is specifically

Embedded image Si (OCH ₃ ) ₄ , Si (OC ₂ H ₅ ) ₄ , Si
A tetrafunctional silane compound such as tetraalkoxysilane such as (OC ₃ H ₇ ) ₄ or Si (OC ₄ H ₉ ) ₄ ;

[0018]

Embedded image H ₃ CSi (OCH ₃ ) ₃ , H ₅ C ₂ Si (OC
_{H 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 , monoalkyltrialkoxysilanes,

[0019]

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), etc.,

[0020]

Embedded image (H ₃ CCOO) ₃ SiCH ₃ , (H ₃ CCO
O) ₃ SiC ₂ H ₅ , (H ₃ CCOO) ₃ SiC ₃ H ₇ , (H ₃
CCOO) ₃ SiC ₄ H _{9 and} other monoalkyltriacyloxysilanes

[0021]

Embedded image Cl ₃ SiCH ₃ , Cl ₃ SiC ₂ H ₅ , Cl ₃ S
_{iC 3 H 7, Cl 3 SiC} 4 H 9 Br 3 SiCH 3, Br 3 Si
Trifunctional silane compounds such as monoalkyltrihalogenosilanes such as C ₂ H ₅ , Br ₃ SiC ₃ H ₇ and Br ₃ SiC ₄ H ₉ .

[0022]

Embedded image (H ₃ C) ₂ Si (OCH ₃ ) ₂ , (H ₅ C ₂ ) _{2
Si (OCH3) 2, (H} 7 C 3) 2 Si (OCH 3) 2,
_{(H 9 C 4) 2 Si} (OCH 3) 2, (H3C) 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 (OC 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 (OC 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 (O
Dialkyldialkoxysilanes such as C ₄ H ₉ ) ₂ and (H ₉ C ₄ ) ₂ Si (OC ₄ H ₉ ) ₂ ;

[0023]

Embedded image Ph ₂ Si (OCH ₃ ) ₂ , Ph ₂ Si (OC ₂
Diphenyl dialkoxy silane such as H ₅ ) ₂ ,

[0024]

Embedded image (H ₃ CCOO) ₂ Si (CH ₃ ) ₂ , (H ₃ C
COO) ₂ Si (C ₂ H ₅ ) ₂ , (H ₃ CCOO) ₂ Si (C
_{3 H 7) 2, (H} 3 CCOO) 2 Si (C 4 H 9) dialkyl acyloxysilanes of ₂ or the like,

[0025]

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 , B
r ₂ Si (CH ₃ ) ₂ , Br ₂ Si (C ₂ H ₅ ) ₂ , Br ₂ Si
There are bifunctional silane compounds such as alkyldihalogenosilanes such as (C ₃ H ₇ ) ₂ and Br ₂ Si (C ₄ H ₉ ) ₂ .

The Si-H group-containing silane compound represented by the general formula (I) used in the present invention is used as an essential component, and the silane compound represented by the general formula (II) is an optional component. . As the hydrolyzable / polycondensable group contained in the silane compound of the general formula (I) or the general formula (II), an alkoxy group is preferable in view of reactivity and the like. Si-H represented
The group-containing silane compound is particularly preferably trialkoxysilane or monoalkyldialkoxysilane, and the silane compound represented by the general formula (II) is particularly preferably tetraalkoxysilane, monoalkyltrialkoxysilane or dialkyldialkoxysilane. . Further, in the case of producing a silicone polymer having a high degree of polymerization, it is preferable that the silane compound represented by the general formula (I) contains a trifunctional silane compound, and the general formula (II)
When a silane compound represented by
It is preferable to include a functional silane compound represented by the general formula (II).

In the method for producing a silicone polymer of the present invention, 35 mol% or more of Si-H group-containing silane compound is added to the total amount of silane compounds. ) 35 to 100 mol% of the Si-H group-containing silane compound represented by the formula (more preferably 35
~ 85 mol%) and the silane compound represented by the general formula (II) are preferably used in a proportion of 0 to 65 mol% (15 to 65 mol%).

The silicone polymer of the present invention is preferably three-dimensionally crosslinked. Therefore, 3 to 100 mol% of all silane compounds are preferably trifunctional or higher functional silane compounds, and 3 to 10 mol% of all silane compounds are preferable.
It is particularly preferable that 75 mol% is a trifunctional or higher functional silane compound. Further, 15 to 100 mol% of the silane compound is preferably a tetrafunctional silane compound or a trifunctional silane compound, and 20 to 85 mol% is preferably a tetrafunctional silane compound or a trifunctional silane compound. More preferable. That is, in the silane compound represented by the general formula (II), the content of the bifunctional silane compound is 0 to 85 mol%.
Is preferable, and more preferably 0 to 80 mol%.
Used in proportion. Particularly preferably, the compound of the general formula (II)
In the silane compound represented by, the tetrafunctional silane compound is 15 to 100 mol%, more preferably 20 to 100 mol%, and the trifunctional silane compound is 0 to 85 mol%, more preferably 0 to 80 mol%. The bifunctional silane compound is 0
It is used in a proportion of 85 mol%, more preferably 0 to 80 mol%.

When the content of the bifunctional silane compound exceeds 85 mol%, the chain of the silicone polymer becomes long and there is a high possibility that it will be laterally oriented to the surface of the inorganic material due to the orientation of the hydrophobic group such as methyl group and the like. Since it is easy to form a layer, it is difficult to reduce the stress.

The silicone polymer according to the present invention is obtained by hydrolyzing and polycondensing the Si-H group-containing silane compound represented by the general formula (I) and the silane compound represented by the general formula (II). It is produced by a hydrosilylation reaction. At this time, as the hydrolysis / polycondensation catalyst, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, hydrofluoric acid, oxalic acid, maleic acid, sulfonic acid, formic acid, etc. It is preferable to use an organic acid, and a basic catalyst such as ammonia or trimethylammonium can also be used. These hydrolysis / polycondensation catalysts are Si-H represented by the general formula (I).
It is used in an appropriate amount depending on the amounts of the group-containing silane compound and the silane compound represented by the general formula (II), and preferably the Si—H group-containing silane compound represented by the general formula (I) and the general formula ( It is used in the range of 0.001 to 10 mol per 1 mol in total of the silane compound represented by II). As the hydrosilylation catalyst, platinum, palladium, rhodium-based transition metal compounds can be used, and it is particularly preferable to use a platinum compound such as chloroplatinic acid. Zinc peroxide, calcium peroxide, hydrogen peroxide, peroxide Peroxides such as di-tert-butyl oxide, strontium peroxide, sodium peroxide, lead peroxide and barium peroxide, as well as tertiary amines and phosphines can also be used. These hydrosilylation catalysts are preferably used in the range of 0.0000001 to 0.0001 mol with respect to 1 mol of the Si-H group of the Si-H group-containing silane compound represented by the general formula (I).

The hydrosilylation reaction agent of the present invention has a double bond such as a vinyl group for the hydrosilylation reaction and a resin-curable functional group such as an epoxy group or an amino group. The resin-curable functional group is a functional group that reacts or interacts with an organic compound or an inorganic compound. Here, as the functional group, a reactive organic group that reacts with a curing agent or a cross-linking agent, a reactive organic group that undergoes a self-curing reaction, an organic group that reacts or interacts with a functional group present on the surface of an inorganic filler. , And groups that react with hydroxyl groups. As a specific example,
As the hydrosilylation reagent having an epoxy group, allyl glycidyl ether and the like can be used, and as the hydrosilylation reagent having an amino group, allylamine, allylamine hydrochloride, aminoalkyl acrylate such as aminoethyl acrylate, and amino such as aminoethyl methacrylate. Alkyl methacrylate or the like can be used. These hydrosilylation reaction agents are Si- of the Si-H group-containing silane compound represented by the general formula (I).
It is preferably in the range of 0.1 to 2 equivalents, more preferably 0.5 to 1.5 equivalents, and particularly preferably 0.9 to H group.
It is preferable to set it to 1.1 equivalents.

The above-mentioned hydrolysis / polycondensation and hydrosilylation reaction can be carried out by using 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, It is preferably carried out in an amide solvent such as N, N-dimethylformamide, an aromatic hydrocarbon solvent such as toluene or xylene, an ester solvent such as ethyl acetate, or a nitrile solvent such as butyronitrile. These solvents may be used alone, or a mixed solvent of several kinds may be used together. Further, the hydrolysis / polycondensation proceeds in the atmosphere without particularly adding water, but water may be added. The amount of water is appropriately determined, but if it is too large, there is a problem that the storage stability of the coating solution decreases, so the amount of water is 0 to 5 relative to 1 mol of the total amount of the silane compound.
It is preferably in the range of moles, particularly preferably 0.5 to 4 moles.

The production of the silicone polymer is carried out under the above conditions,
The formulation is adjusted so that gelation does not occur. From the viewpoint of workability, the silicone polymer is preferably used by dissolving it in the same solvent as the above reaction solvent. For this purpose, the above reaction product solution may be used as it is, or the silicone polymer may be separated from the reaction product solution and dissolved again in the above solvent.

The silicone polymer in the present invention is three-dimensionally crosslinked but is not completely cured or gelled, and the polymerization of the silicone polymer in the present invention is controlled, for example, to such an extent that it is dissolved in a reaction solvent. It For this reason, in the production, storage and use of the resin-curable silicone polymer, the temperature is preferably room temperature or higher and 200 ° C. or lower, and more preferably 150 ° C. or lower.

In producing the silicone polymer of the present invention, a Si-H group-containing silicone polymer can be produced as an intermediate product. Si-H groups of the Si-H group-containing silicone polymer is Si-H group-containing difunctional siloxane units (HR'SiO _2/2) or (H ₂ SiO
_2/2 ) (in the formula, _{R'is as} described above, and the R'groups in the silicone polymer may be the same or different from each other. The same applies hereinafter) or Si-H group-containing 3 It is introduced by a functional siloxane unit (HSiO _3/2 ).

The silicone polymer of the present invention has a degree of polymerization of 3
The above is sufficient, and the degree of polymerization is preferably 7,000 or less. The polymerization degree is preferably 2000 or less, and particularly preferably in the range of 3 to 500, in consideration of the efficiency when used as a solution. A resin-curable functional group introduced by a hydrosilylation reaction with respect to the Si-H group is present on the side chain and terminal of this silicone polymer. Here, the degree of polymerization of the silicone polymer was 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. It is a thing.

When the silicone polymer is produced, the hydrosilylation reaction may be carried out by adding the hydrosilylation reaction agent after producing the silicone polymer as described above. May be added at the same time as the silane compound, and the hydrosilylation reaction may be carried out simultaneously with or during the hydrolysis / polycondensation of the silane compound.

The thermosetting resin composition containing the above-mentioned silicone polymer having a resin-curable functional group (referred to as a resin-curable silicone polymer in the present invention) contains a large amount of an inorganic filler. Can be blended with. The type of the inorganic filler is not particularly limited, and examples thereof include calcium carbonate, alumina, titanium oxide, mica, aluminum carbonate, aluminum hydroxide, magnesium silicate, aluminum silicate, silica, short glass fibers, aluminum borate. Various whiskers such as whiskers and silicon carbide whiskers are used. Moreover, you may use these together in several types. The shape and particle size of the inorganic filler are not particularly limited, and the commonly used particle size is 0.001 to 50 μm.
Those having a thickness of 0.01 to 10 μm can be preferably used in the present invention. The blending amount of these inorganic fillers is preferably 100 to 2000 parts by weight, and particularly preferably 300 to 1500 parts by weight, based on 100 parts by weight of the resin-curable silicone polymer. If the content of the inorganic filler is too small, the coefficient of thermal expansion tends to increase, and if the content of the inorganic filler is too large, it tends to be difficult to form a film.

The curing agent for the thermosetting resin composition containing the silicone polymer in the present invention is not particularly limited as long as it is a compound that reacts (cures) with the resin-curable functional group of the silicone polymer. For example, when the resin-curable functional group is an epoxy group, those generally used as epoxy resin curing agents such as amine-based curing agents and phenol-based curing agents can be used. A polyfunctional phenol compound is preferable as the curing agent for the epoxy resin. As the polyfunctional phenol compound, there are polyphenols such as bisphenol A, bisphenol F, bisphenol S, resorcin, and catechol. Further, monovalent phenol compounds such as these polyphenols, phenol and cresol are reacted with formaldehyde. There are novolac resins and the like. The polyfunctional phenol compound may be substituted with halogen such as bromine. The amount of the curing agent used is 1 equivalent of the resin-curable functional group of the silicone polymer.
It is preferable to use 0.2 to 1.5 equivalents, and 0.5 to
It is particularly preferred to use 1.2 equivalents. In order to improve the adhesion between the cured product and the metal, the curing agent for epoxy resin preferably contains an amine compound, and it is preferable that the curing agent is contained in excess. This amine compound acts as an adhesive reinforcing agent, and specific examples will be described later. Considering the balance between other properties such as heat resistance and adhesiveness, it is preferable to use a curing agent containing an amine compound in an amount of 1.0 to 1.5 equivalents per equivalent of the resin-curable functional group of the silicone polymer. It is particularly preferable to use 1.0 to 1.2 equivalents relative to 1 equivalent of the resin-curable functional group.

A curing accelerator may be added together with the curing agent. For example, when the resin-curable functional group is an epoxy group, an imidazole compound or the like is generally used,
This can also be used in the present invention. Specific examples of the imidazole compound used as a curing accelerator include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole 2-phenylimidazole,
2-undecyl imidazole, 1-benzyl-2-methyl imidazole, 2-heptadecyl imidazole, 4,
5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2
-Phenyl-4-methylimidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline and the like can be mentioned. In order to obtain the sufficient effect of the curing accelerator, it is necessary that the amount of the curing accelerator be 0.1% with respect to 100 parts by weight of the silicone polymer.
It is preferably used in an amount of 01 parts by weight or more, and is preferably 10 parts by weight or less from the viewpoint of thermal expansion coefficient and elongation.

The silicone resin-containing thermosetting resin composition of the present invention may optionally contain a silyl group-modified elastomer at both ends. By adding the elastomer modified with silyl groups at both ends to the thermosetting resin composition, the breaking stress of the cured resin becomes large and the handleability is improved. The both-end silyl group-modified elastomer in the present invention is a long-chain elastomer having a weight average molecular weight of about 3,000 to 100,000 and has an alkoxysilyl group at both ends of its main chain. There are no particular restrictions on the main chain of the elastomer,
Polyolefin such as polyisobutylene or polypropylene, polyether such as polypropylene oxide, elastomer having a main chain skeleton such as butadiene rubber or acrylic rubber can be used. The alkoxysilyl group may be a Si element to which 1 to 3 alkoxy groups are bonded, and the alkoxy group bonded to the Si element preferably has 1 to 4 carbon atoms. Elastomer modified with silyl groups at both ends
For example, SAT200 (polyether modified with silyl groups at both ends, trade name manufactured by Kanegafuchi Chemical Co., Ltd.), EP103S,
EP303S (polyisobutylene modified with silyl groups at both ends,
Kanebuchi Chemical Industry Co., Ltd.) can be used. The compounding amount of the silyl group-modified elastomer at both ends is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the silicone polymer. If the amount is less than 0.1 part by weight, the effect due to the compounding is difficult to appear, and if it exceeds 30 parts by weight, the coefficient of thermal expansion tends to increase.

In the thermosetting resin composition of the present invention, the resin-curable silicone polymer of the present invention may be used in combination with a silicone oil having an epoxy group (referred to as an epoxy-modified silicone oil in the present invention). . The mixing ratio of the resin-curable silicone polymer and the epoxy-modified silicone oil is preferably such that the resin-curable silicone polymer is contained in an amount of 0.1 part by weight or more based on 100 parts by weight of the total of these, and the coefficient of thermal expansion is From the viewpoint of elongation and breaking stress, the resin-curable silicone polymer is more preferably contained in an amount of 5 parts by weight or more, and particularly preferably 20 parts by weight or more. From the viewpoint of elongation and breaking stress, it is preferable that the epoxy-modified silicone oil is contained in an amount of 5 parts by weight or more based on 100 parts by weight of the total of the resin-curable silicone polymer and the epoxy-modified silicone oil, and 40 parts by weight. Part or more is particularly preferable. When the amount of the resin-curable silicone polymer is less than 0.1 part by weight, the dispersibility of the inorganic filler tends to decrease. The compounding ratio of the resin-curable silicone polymer and the epoxy-modified silicone oil can be determined according to the purpose from the values of thermal expansion coefficient and elongation. That is, the larger the compounding ratio of the resin-curable silicone polymer, the smaller the coefficient of thermal expansion,
The elongation value can be increased by increasing the compounding ratio of the epoxy-modified silicone oil. Here, the epoxy-modified silicone oil is a chain polysiloxane compound having a functional group containing an epoxy group in its side chain, and has a viscosity at 25 ° C. in the range of 10 ⁻² to 10 ³ Pa · s. The viscosity in the present invention is the value of Tokyo Keiki Co., Ltd.
It measured at 25 degreeC using the EMD viscometer made from. Epoxy equivalent of epoxy-modified silicone oil is 150-50
00 is preferable, and 300 to 1000 is particularly preferable.

In the thermosetting resin composition containing the above epoxy-modified silicone oil, a silicone polymer containing no resin-curable functional group in place of a part or all of the resin-curable silicone polymer of the present invention (the present invention In the above, it is also referred to as a non-resin curable silicone polymer). When the non-resin curable silicone polymer is used, the amount of the non-resin curable silicone polymer compounded is preferably 30 parts by weight or less based on 100 parts by weight of the total of the epoxy-modified silicone oil and the silicone polymer. . When the amount of the non-resin curable silicone polymer exceeds 30 parts by weight, the elongation value of the resin cured product tends to decrease.

Here, the non-resin curable silicone polymer means a bifunctional siloxane unit (R ₂ SiO _2/2 ), a trifunctional siloxane unit (RSiO _3/2 ), where R is an organic group. R groups in the silicone polymer may be the same as or different from each other) and at least one siloxane unit selected from tetrafunctional siloxane units (SiO _4/2 ). , Having at least one functional group that reacts with a hydroxyl group at the terminal. Degree of polymerization is 2-70
00 is preferable, and the more preferable degree of polymerization is 2 to 100,
A particularly preferred degree of polymerization is 2 to 70. Examples of R include an alkyl group having 1 to 4 carbon atoms and an aromatic group such as a phenyl group. Examples of the functional group that reacts with a hydroxyl group include a silanol group, an alkoxyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms.
4 includes an acyloxy group of 4, a halogen other than bromine such as chlorine, and the like.

Such a non-resin curable silicone polymer can be obtained by hydrolyzing and polycondensing the silane compound represented by the general formula (II). The above-mentioned general formula (II) used for the synthesis of a non-resin curable silicone polymer
As the silane compound represented by, a tetrafunctional silane compound or a trifunctional silane compound is used as an essential component, and a difunctional silane compound is appropriately used as necessary. Particularly, the tetrafunctional silane compound is preferably tetraalkoxysilane, the trifunctional silane compound is preferably monoalkyltrialkoxysilane, and the bifunctional silane compound is preferably dialkyldialkoxysilane. The use ratio of the silane compound is preferably
Tetrafunctional silane compound or trifunctional silane compound 15 to
100 mol% and 0 to 85 mol% of the bifunctional silane compound are preferable, 20 to 100 mol% of one or more kinds of the tetrafunctional silane compound or the trifunctional silane compound, and 0 to 80 mol of the bifunctional silane compound. % Is more preferable. Further, it is particularly preferable to use the tetrafunctional silane compound in an amount of 15 to 100 mol%, the trifunctional silane compound 0 to 85 mol%, and the bifunctional silane compound 0 to 85 mol%. 20 to 100 mol% of the compound,
It is more preferable to use the trifunctional silane compound in an amount of 0 to 80 mol% and the bifunctional silane compound in an amount of 0 to 80 mol%. As the catalyst and solvent for the hydrolysis / polycondensation reaction, the same ones as those used in the hydrolysis / polycondensation reaction for producing the resin-curable silicone polymer can be applied. The non-resin curable silicone polymer is produced by adjusting the conditions and blending so as not to gel. The non-resin curable silicone polymer is three-dimensionally crosslinked but not completely cured or gelled, and the three-dimensional crosslinking is controlled, for example, to such an extent that it is dissolved in the reaction solvent. Therefore, the temperature is preferably room temperature or higher and 200 ° C. or lower during the production, storage and use of the non-resin curable silicone polymer.
It is more preferably 0 ° C. or lower.

When a resin-curable silicone polymer or a non-resin-curable silicone polymer is used in combination with an epoxy-modified silicone oil, a comparison is made with the case where only the non-resin-curable silicone polymer is used as the silicone polymer component. When the resin-curable silicone polymer is contained, it is preferable from the viewpoint of thermal expansion coefficient, elongation and breaking stress, and it is particularly preferable to use only the resin-curable silicone polymer as the silicone polymer component.

An adhesive reinforcing agent is added to the thermosetting resin composition of the present invention, if necessary, in order to enhance the adhesiveness to the metal foil and the peeling strength between the cured resin and the metal foil. be able to. A compound having a plurality of reactive functional groups such as amino groups and hydroxyl groups can be used as the adhesion reinforcing agent, and these also act as an epoxy resin curing agent.
As the amine compound having a plurality of reactive functional groups, for example, m-phenylenediamine, 4,4′-diaminobenzanilide, 4,4′-diamino-2,2′-dimethylbiphenyl and the like can be used. A compound having a plurality of active NH groups in a molecule such as a compound having a group or dicyandiamide, a compound having both an amino group and a hydroxyl group in a molecule such as 3-amino-1-propanol and 4-aminophenol is used. be able to. The compounding amount of the adhesive reinforcing agent is 0.1 with respect to 100 parts by weight of the silicone polymer.
It is preferably from 01 to 9 parts by weight, particularly preferably from 0.1 to 6 parts by weight. If the amount is less than 0.01 part by weight, the effect of the composition tends to be difficult to appear, and 9
When it exceeds the weight part, the heat resistance of the cured product tends to decrease.

The resin composition can be dissolved or dispersed in a solvent to form a resin varnish. The concentration of the resin varnish is appropriately determined in consideration of workability and the like. Further, when the resin composition is prepared after the synthesis of the silicone polymer, it is preferable to use the same solvent as that used for the synthesis of the silicone polymer. Examples of the solvent include 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, amide solvents such as N, N-dimethylformamide, and toluene. Aromatic hydrocarbon solvents such as xylene, ester solvents such as ethyl acetate, nitrile solvents such as butyronitrile are preferably used. It is also possible to use a mixed solvent in which several kinds of these solvents are used in combination.

(Metal Foil with Resin) The resin varnish is applied to the metal foil and dried in a drying oven at 80 to 200 ° C. to produce the metal foil with resin. The drying time may be such that the resin loses fluidity at room temperature, and may be such that the resin does not completely cure when dried at high temperature. The metal foil is not particularly limited, and a metal foil generally used as a wiring circuit conductor in the field of wiring boards can be used, and it is preferable to use a copper foil in consideration of electrical characteristics and cost. Particularly preferably, an electrolytic copper foil having at least one roughened surface, a rolled copper foil, or an ultrathin copper foil with a carrier film can be used. The metal foil having a thickness of 5 to 200 μm which is usually used can be used. In addition, nickel, nickel-phosphorus, nickel-tin alloy, nickel-iron alloy, lead, lead-
It is also possible to use a composite foil having a three-layer structure in which a tin alloy or the like is used as an intermediate layer and copper layers are provided on both surfaces thereof, or a composite foil such as a composite foil in which aluminum and copper foil are composited.

The thickness of the insulating resin layer of the metal foil with resin is preferably equal to or more than the thickness of the copper foil, and when laminated on the inner wiring circuit board after processing the wiring circuit, the thickness of the conductor of the inner wiring circuit is It is preferably larger than the sum of the copper foil thicknesses of the metal foil with resin. Further, if it is too thick, the weight increases more than necessary, and in addition, the cost tends to increase. The thickness is preferably 6 to 200 μm, but may be thicker than this. In order to produce a thick insulating resin layer, coating and drying can be repeated several times. The inner layer wiring circuit board is a wiring board in which a circuit is formed in the outermost layer, and for example, a wiring board in which a circuit is formed on one side or both sides of a substrate obtained by impregnating and curing a base material such as paper or fiber into a resin or Examples thereof include a multilayer wiring board in which a plurality of wiring boards are laminated via a prepreg, a multilayer wiring board multilayered by a build-up method, and the like.

(Resin Sheet with Wiring Circuit) A resin sheet with a wiring circuit is produced by processing a wiring circuit in a state where the insulating resin layer of the metal foil with resin has a sufficient circuit embedding property. As a state in which the insulating resin layer has a sufficient circuit embedding property, B-Stage in the thermosetting resin is used.
State. As a method of adjusting the insulating resin layer to a B-Stage state, a method of adjusting a drying temperature and a drying time when applying / drying a resin varnish on the metal foil, a method of processing a wiring circuit on the metal foil with resin, The method of adjusting to a B-Stage state by heating is mentioned.
It is preferable that the conditions for forming B-Stage for adjusting to the B-Stage state are a temperature of 80 to 200 ° C. and a time of 1 to 120 minutes.

The resin material with a wiring circuit of the present invention can be produced by subjecting the metal foil with a resin to a wiring circuit process. A generally known method such as a subtractive method can be applied to the wiring circuit processing. For example, a wiring pattern is formed by forming a resist pattern on the surface of a resin-coated metal foil, removing unnecessary portions of the copper foil by etching, and peeling the resist pattern. The holes may be formed in advance on the resin-coated metal foil with a laser, a drill, or the like, or the holes may be formed after the wiring circuit processing. Furthermore, the holes may be filled with a conductive paste, or the holes may be filled with a metal by plating or the like.

A multilayer wiring board can be produced by laminating and molding a resin sheet with a wiring circuit and an inner layer wiring circuit board, and establishing interlayer conduction. Laminate molding and interlayer conduction are
It can be performed according to a conventional method. The conditions for lamination molding are 13
In the temperature range of 0 to 200 ° C., preferably 150 to 180
It is carried out by heating and pressurizing in the range of 0 ° C. and at a pressure of 0.5 to 20 MPa, preferably at a pressure of 2 to 8 MPa, and is appropriately selected depending on the capacity of the press machine, the target thickness and the like. The treatment time of heating and pressurizing is appropriately determined according to other conditions such as temperature and pressure, but is generally about 30 minutes to 2 hours. Interlayer conduction can be achieved by a general method using a conductive paste or plating. For example, after laminating a resin material with a wiring circuit and an inner wiring circuit board, forming a hole with a laser or a drill to provide an interlayer conduction path, forming a resist pattern on the wiring circuit, and plating the inner layer wiring circuit. Is obtained and the resist pattern is peeled off to obtain a multilayer wiring board having interlayer conduction.

The metal foil with resin or the resin sheet with circuit can be further laminated on the multilayer wiring board manufactured as described above, and integration and interlayer conduction formation can be repeated to build up. The build-up layer produced using the resin material with a wiring circuit of the present invention can be thinned by burying the wiring circuit layer in the resin when laminated and molded. Alternatively, a plurality of resin materials with wiring circuits may be used for a single layering.

(Resin Material with Wiring Circuit with Inner Layer Circuit) A B-Stage state resin layer made of the above resin varnish is laminated on the inner layer circuit board, and a wiring board is further processed by wiring circuit processing. As a result, a resin material with a wiring circuit can be manufactured. As a method for producing a laminated board used for producing the resin material with a wiring circuit, a method of laminating / integrating the metal foil with a resin on an inner layer circuit board or a method of applying the resin varnish to the inner layer circuit board and drying it Examples thereof include a method of laminating / integrating a metal foil, a method of laminating / integrating a resin sheet and a metal foil obtained by applying the resin varnish to a carrier film on an inner circuit board and drying. As a method of adjusting to the B-Stage state, it is preferable to simultaneously adjust to the B-Stage state at the time of stacking and integration. It can also be adjusted by further heating after being integrated. B-Stage for adjusting to an appropriate B-Stage state by stacking and unifying
It is preferable that the conditions for the reaction are set such that the temperature is 80 to 200 ° C., the time is 1 to 120 minutes, and the pressure is 0.1 to 8 MPa.

A multilayer wiring board is manufactured by laminating a build-up material such as the resin-coated metal foil and the wiring-circuit-equipped resin sheet on the resin material with the wiring circuit and integrating them to form interlayer conduction. You can Further, by repeating this and building up, it is possible to further increase the number of layers. The build-up layer produced using the resin material with a wiring circuit of the present invention can be thinned by burying the wiring circuit layer in the resin when laminated and molded.

[0057]

(Reference example) In a glass flask equipped with a stirrer, a condenser and a thermometer, 20 g of tetramethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 g of dimethoxydimethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.), 67 g of dimethoxymethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.),
Methanol as a synthetic solvent (made by Tokyo Chemical Industry Co., Ltd.)
In a solution containing 37 g of the above compound, 1.5 g of maleic acid as a synthetic catalyst and 50 g of distilled water were mixed and stirred at 80 ° C. for 2 hours, then 72 g of allyl glycidyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.) and chloroplatinic acid. 0.2 g of a salt (2 wt% isopropyl alcohol solution) was added, and the mixture was stirred for 4 hours to synthesize an epoxy-modified silicone polymer. The degree of polymerization of siloxane units of the obtained silicone polymer is 6
5 (converted from the number average molecular weight measured by GPC using a calibration curve of standard polystyrene, the same applies hereinafter).

(Example 1) In a glass flask equipped with a stirrer, a condenser and a thermometer, 100 parts by weight of a solid content of a silicone polymer synthesized in the same manner as in the above-mentioned Reference Example was mixed with silica powder (product name: SO-25R, average particle size:
(0.5 μm, manufactured by Admatechs Co., Ltd.) 450 parts by weight and 202 parts by weight of methanol as a diluent solvent are mixed,
After stirring at 0 ° C. for 1 hour, the mixture was cooled to room temperature, and 78 parts by weight of tetrabromobisphenol A and 3 parts by weight of 2-ethyl-4-methylimidazole were added to 100 parts by weight of the solid content of the silicone polymer. A resin varnish was prepared by stirring at room temperature for 1 hour. The cured product of this resin varnish had a thermal expansion coefficient of 22 × 10 ⁻⁶ / ° C. and an elongation of 3.1%.

In the present invention, a resin varnish having a thickness of 50 μm is used for measuring the thermal expansion coefficient and elongation of the cured resin.
m polyethylene terephthalate film was used as a carrier film, coated with a knife coater so that the thickness after heating and drying would be 50 μm, heated and cured at 170 ° C. for 2 hours, and the carrier film was removed to prepare. The resin sheet was used as a sample. The coefficient of thermal expansion is measured by thermomechanical analysis (TMA: MAC SCIENCE).
It was measured in tensile mode by TMA manufactured by the company. Elongation is measured by a tensile tester (Shimadzu Autograph AG-100C) using a film having a width of 10 mm × a length of 80 mm and a thickness of 50 to 100 μm as a sample, and a chuck distance: 60 mm, a pulling speed: 5 mm / As min
It was measured by a tensile test.

Using a polyethylene terephthalate film having a thickness of 50 μm as a carrier film, this resin varnish was applied by a knife coater so that the thickness after heating and drying would be 50 μm, followed by heating and drying at a temperature of 130 ° C. for 10 minutes and heating. After drying, the carrier film was peeled off to prepare a resin sheet.

This resin varnish was applied to the roughened surface side by a knife coater so that the thickness of the resin sheet after heating and drying was 50 μm, using a single-sided roughened copper foil having a thickness of 18 μm. It heat-dried at 130 degreeC for 10 minute (s), and produced the resin sheet with a copper foil.

The resin varnish was formed into a single-sided roughened copper foil having a thickness of 18 μm, and the thickness of the resin sheet after heating and drying was 50.
It is coated on the roughened surface side with a knife coater so as to have a thickness of μm, heated and dried at a temperature of 130 ° C. for 60 minutes, and an etching solution (200 g of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Inc. is dissolved in 1 kg of water)) is used. Wiring circuit processing is applied, and wiring material with wiring circuit (resin sheet with wiring circuit)
(Fig. 1).

0.8 mm thick glass cloth substrate epoxy resin double-sided copper clad laminate (MCL-manufactured by Hitachi Chemical Co., Ltd.)
E-67 (trade name) is used for wiring circuit processing, and the copper foil-attached resin sheet prepared above is placed on the upper and lower sides of the wiring circuit processing.
The outermost insulating layer is B when heated and pressed at 0 ° C. and 3 MPa for 60 minutes.
A copper clad 4-layer laminate A1 in the −Stage state was produced. A wiring circuit process was performed on the copper-clad 4-layer laminate A1 by etching to obtain an insulating resin material with a circuit (FIG. 2). The above-prepared resin sheet with a copper foil was laminated on both surfaces of this insulating resin material with a circuit, and heated and pressed at a temperature of 175 ° C. and a pressure of 3 MPa for 60 minutes to produce a copper-clad 6-layer laminate B1 (FIG. 3).

0.8 mm thick glass cloth substrate epoxy resin double-sided copper clad laminate (MCL-manufactured by Hitachi Chemical Co., Ltd.)
E-67 (trade name) is used for wiring circuit processing, and the copper foil-attached resin sheet prepared above is stacked on the top and bottom of the wiring circuit processing.
By heating and pressing at 5 ° C. and 3 MPa for 60 minutes, a copper clad 4-layer laminate C1 in which the outermost insulating layer was in the C-Stage state was produced. A wiring circuit process is performed on the copper-clad laminate C1 by etching, and the copper foil-coated resin sheets prepared above are stacked on both surfaces of the copper-clad laminate C1 and heated and pressed at a temperature of 175 ° C. and a pressure of 3 MPa for 60 minutes to form a copper-clad 6-layer laminate D1. It was made.

0.8 mm thick glass cloth substrate epoxy resin double-sided copper clad laminate (MCL-manufactured by Hitachi Chemical Co., Ltd.)
E-67 (trade name) is used for wiring circuit processing, the resin sheet with a wiring circuit prepared in the above is overlaid on the upper and lower sides thereof, and the resin sheet with the copper foil produced in the above is overlaid on the upper and lower sides thereof to obtain a temperature of 175. A copper clad 6-layer laminate E1 was produced by heating and pressurizing at 60 ° C. and a pressure of 3 MPa for 60 minutes.

(Example 2) Solid content of silicone polymer 1
Silica powder (trade name: SO-25
R, average particle size: 0.5 μm, Admatechs Co., Ltd.
Made) is 900 parts by weight, and the amount of methanol is 2
Resin resin was prepared in the same manner as in Example 1 except that the amount was changed to 50 parts by weight.
A varnish was prepared. Thermal expansion coefficient of the cured product of this resin varnish
Is 15 × 10 ^-6/ ° C and the elongation is 2.2%
It was Using this resin varnish, in the same manner as in Example 1.
Resin sheet, resin sheet with copper foil, resin sheet with wiring circuit
G, copper-clad 4-layer laminate A2, copper-clad 6-layer laminate B2, copper-clad 4
Layer laminated plate C2, copper clad 6 layer laminated plate D2 and copper clad 6 layer laminated
A plate E2 was produced.

(Example 3) Solid content of silicone polymer 1
Silica powder (trade name: SO-25
R, average particle size: 0.5 μm, manufactured by Admatechs Co., Ltd.) A resin varnish was prepared in the same manner as in Example 1 except that the compounding amount was changed to 1300 parts by weight and the compounding amount of methanol was changed to 490 parts by weight. The cured product of this resin varnish had a thermal expansion coefficient of 10 × 10 ⁻⁶ / ° C. and an elongation of 1.2%. Using this resin varnish, a resin sheet, a resin sheet with a copper foil, a resin sheet with a wiring circuit, a copper-clad 4-layer laminate A3, a copper-clad 6-layer laminate B3, and a copper-clad 4 were prepared in the same manner as in Example 1.
A layer laminate C3, a copper clad 6 layer laminate D3 and a copper clad 6 layer laminate E3 were produced.

Comparative Example 100 parts of bisphenol A novolac type epoxy resin (epoxy equivalent 210, manufactured by Dainippon Ink and Chemicals, Inc., Epicron N865 (trade name) is used) 100 parts, bisphenol A novolac resin (hydroxyl equivalent 118, Dainippon 60 parts of Priofen VH-4170 (trade name) manufactured by Ink Kagaku Kogyo Co., Ltd. and 2 parts of dicyandiamide are added to methyl ethyl ketone 120.
And then stirred at room temperature for 1 hour to prepare a resin varnish. Using this resin varnish, a resin sheet, a resin sheet with a copper foil, a copper clad four-layer laminate A4, in the same manner as in Example 1.
Copper-clad 6-layer laminate B4, Copper-clad 4-layer laminate C4 and Copper-clad 6
A layer laminate D4 was produced. Note that the resin sheet with a wiring circuit and the copper clad 6-layer laminate E4 could not be manufactured because the shape of the resin sheet with a wiring circuit could not be maintained during etching.

Resin sheets 10 of Examples 1 to 4 and Comparative Example
g with an etching solution (200 g of ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Inc. is dissolved in 1 kg of water) at room temperature.
Table 1 shows the weight reduction and the resin sheet shape after the time treatment. Copper-clad 6-layer laminates B1 to B4, Copper-clad 6-layer laminates D1
The surface roughness of D4 and the copper clad 6-layer laminates E1 to E3 was measured with a stylus type surface roughness meter. The measurement point has a length of 25 from the part where the inner layer wiring circuit exists directly below to the part that does not exist.
The 10-point average roughness of the step between the portion where the inner layer wiring circuit exists and the portion where the inner layer wiring circuit does not exist immediately below was measured. The results are shown in Table 1. Also, copper-clad 6-layer laminates B1 to B
4, copper-clad 6-layer laminate D1 to D4, copper-clad 6-layer laminate E1
E3 was floated in a solder bath at 260 ° C. for 30 seconds, and solder heat resistance was evaluated. The results are shown in Table 1.

[0070]

[Table 1]

As shown in Table 1, the resin sheet of the present invention does not dissolve in the etching solution even when it is cured at a low temperature. Therefore, even in the state of the copper-clad 6-layer laminate B or the copper-clad 6-layer laminate E, the solder heat resistance is high. It can be seen that, in addition, it has excellent circuit embedding properties and excellent solder heat resistance.

[0072]

EFFECTS OF THE INVENTION According to the present invention, by using a resin that does not decompose into a chemical liquid such as an etching liquid even when it is not completely cured, it functions as an insulating layer and the wiring is formed into a resin sheet during molding. The resin material suitable for fine wiring can be provided because it can be made to sneak in, the surface of the resin can be flattened because the influence of the projections of the inner layer wiring circuit is small after molding.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a resin material with a wiring circuit according to the present invention.

FIG. 2 is a cross-sectional view showing an example of a resin material with a wiring circuit according to the present invention.

FIG. 3 is a cross-sectional view showing a copper-clad 6-layer laminate manufactured using the resin material with a wiring circuit of the present invention.

[Explanation of symbols]

1,1 ', 1' '. Resin layer (derived from resin sheet with copper foil) 2, 2 '. Wiring conductor (derived from resin sheet with copper foil) 3. Insulation layer of inner layer circuit board 4. Circuit wiring of inner layer circuit board 5. Copper layer (from resin sheet with copper foil)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05K 3/06 H05K 3/06 A (72) Inventor Tetsuya Saito 1500 Ogawa, Shimodate-shi, Ibaraki Hitachi Chemical Co., Ltd. Research Institute Co., Ltd. F-term (reference) 4J002 CP031 CP041 DE136 DE146 DE236 DE246 DJ006 DJ016 DJ056 DK006 DL006 FA046 FA066 FD016 FD147 5E339 AB02 AC10 AD05 BC02 BE11 5E346 AA05 AA06 AA12 AA15 AA22 AA51 CC02 CC08 CC32 DD14 EEEEEEEEEE EE20 GG22 GG28 HH11 HH13 HH31

Claims (13)

[Claims] 1. A resin material with a wiring circuit having a wiring circuit layer on an insulating resin layer in a B-Stage state. 2. An insulating resin sheet in a B-Stage state,
The resin material with a wiring circuit according to claim 1, comprising a wiring circuit layer provided on the insulating resin sheet. 3. A B-Stage provided on an inner layer circuit board.
2. The resin material with a wiring circuit according to claim 1, comprising an insulating resin layer in a state and a wiring circuit provided on the insulating resin layer. 4. The resin material with a wiring circuit according to claim 1, wherein the insulating resin layer comprises a resin composition containing a resin-curable silicone polymer, a curing agent and an inorganic filler. . 5. The resin material with a wiring circuit according to claim 4, wherein the compounding amount of the inorganic filler is 100 parts by weight or more based on 100 parts by weight of the resin-curable silicone polymer in the resin composition forming the insulating resin layer. . 6. An insulating resin layer comprising 100 parts by weight of a resin-curable silicone polymer, 0.8-1 equivalent of a curing agent and 1 inorganic filler.
The resin material with a wiring circuit according to claim 4, comprising a resin composition containing 100 to 2000 parts by weight. 7. The insulating resin layer, wherein the cured product has a thermal expansion coefficient of 50.
It is an insulating resin layer formed using the resin composition which is ^{x10 -6} / ° C or less, and the resin material with a wiring circuit according to any one of claims 1 to 6. 8. The insulating resin layer is an insulating resin layer formed using a resin composition having an elongation of 1.0% or more in a tensile test of a cured product. 7. The resin material with a wiring circuit according to any one of 7. 9. A method for producing a printed wiring board, comprising stacking the resin material with a wiring circuit according to claim 2 and an inner layer board and heating and pressurizing them. 10. A wiring characterized in that a circuit is formed by etching away unnecessary metal from a laminated body including an insulating resin layer in a B-Stage state and a metal foil provided on the insulating resin layer. Manufacturing method of resin material with circuit. 11. The method for producing a resin material with a wiring circuit according to claim 10, wherein the insulating resin layer comprises a resin composition containing a resin-curable silicone polymer, a curing agent and an inorganic filler. Method. 12. The method for producing a resin material with a wiring circuit according to claim 11, wherein the compounding amount of the inorganic filler is 100 parts by weight or more based on 100 parts by weight of the resin-curable silicone polymer. 13. The insulating resin layer comprises 100 parts by weight of a resin-curable silicone polymer, 100 to 2000 parts by weight of an inorganic filler, and 0.8% of a curing agent with respect to the resin-curable silicone polymer.
The method for producing a resin material with a wiring circuit according to claim 11, wherein the resin composition comprises a resin composition containing 1 to 1 equivalent.