JP2001081429A - Adhesive composition and circuit laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition which has low specific permittivity and film-forming capability and is excellent in adhesion to a metal and in interlayer insulation properties by incorporating (A1) an epoxidized copolymer formed from at least two monomers selected from among styrene, butadiene and isoprene, (B) a compound having allyl or methylallyl groups and (C) a curable resin component into the same. SOLUTION: Preferably, this composition further contains (A2) a homopolymer of styrene, butadiene or isoprene or a copolymer formed from at least two monomers selected from among styrene, butadiene and isoprene. Preferably, ingredient A is a styrene copolymer having a styrene unit content of 5-90 mol%. It is suitable that ingredient B is a compound represented by formula I or II (wherein R is H or methyl). It is also preferable that ingredient C is an epoxy resin, a phenol resin or a compound containing maleimide groups.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a circuit laminate and an adhesive composition used for electronic parts such as printed wiring boards. In particular, the present invention relates to a circuit laminate suitable for a circuit having a high-density multilayer wiring structure.

[0002]

2. Description of the Related Art A multilayer printed wiring board used in electronic equipment and the like is obtained by hot-pressing an inner circuit board on which a circuit is formed in advance and a copper foil for an outer circuit with a prepreg interposed therebetween. It is obtained by forming a circuit on the outer layer of a multilayer copper-clad laminate containing an inner circuit. Conventionally, a glass cloth base epoxy resin prepreg has been used for this prepreg. In recent years, the signal speed and operating frequency of electronic devices have been dramatically increased, so that electronic devices used in a high-frequency region, particularly electronic devices that are required to be small and lightweight, are required to have heat resistance for forming fine wiring. There is a demand for a thin circuit laminate having excellent characteristics, a low dielectric constant and a low dielectric loss tangent. A thin circuit laminate made of a low dielectric material can increase the propagation speed of an electric signal, so that signal processing can be performed at a higher speed.

At present, a thin multilayer printed wiring board has three
Although a thin glass cloth base epoxy resin prepreg with a thickness of 0 to 100 μm is used, the cross stitches are easily raised, and the unevenness of the inner circuit board cannot be absorbed inside the prepreg, and the unevenness easily appears on the outer layer surface. Has been impaired, which is an obstacle to the formation of fine wiring. Therefore, instead of using a conventional glass cloth base epoxy resin prepreg, a method of using an adhesive film containing no glass cloth as a prepreg, or a resin-coated copper in which an adhesive layer is preliminarily laminated on one side of an outer layer copper foil. A method of using a foil as a prepreg with a copper foil for an outer layer circuit has been proposed. A resin having film forming ability is used for the adhesive film and the resin-coated copper foil, and usable resins are limited to resins having film forming ability. If it does not have the ability to form a film, problems such as cracking or chipping of the resin are likely to occur in the steps of transporting, cutting and laminating the adhesive film, and when forming as an insulating material for interlayer connection of a multilayer board, The interlayer insulating layer may become abnormally thin in the portion where the inner circuit exists. Also,
Troubles such as a decrease in interlayer insulation resistance and a short circuit are likely to occur. As a resin having a film forming ability, a thermoplastic polyimide adhesive film (US Pat. No. 4,545,29)
5), a high molecular weight epoxy resin (JP-A-4-120135)
JP, JP-A-4-29393), phenol resin / butyral resin (JP-A-4-36366), acrylonitrile-butadiene copolymer / epoxy resin (JP-A-4-29366). No. 41581).

[0004]

However, these resins have a high dielectric constant and cannot process signals at a higher speed. Examples of the low dielectric resin include a fluororesin, a polyphenylene ether resin, a thermosetting polybutadiene resin containing 1,2-polybutadiene as a main component, 5 to 20 parts by weight of a polybutadiene resin, 100 parts by weight of a polyphenylene ether resin, and a crosslinkable monomer 5 To 10 parts by weight and a radical crosslinking agent (JP-A-61-8)
No. 3224) has been proposed. However, these resins are inferior in heat resistance, workability and film forming ability, and have problems in practical use.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has a low dielectric constant, a film forming ability, a low dielectric constant adhesiveness which is excellent in adhesiveness to metal and at the same time excellent in interlayer insulation. It is an object to provide an adhesive composition and a circuit laminate having the adhesive composition as an adhesive layer.

[0006]

The adhesive composition of the present invention comprises an epoxidized copolymer comprising at least two components selected from the group consisting of component (A-1): styrene, butadiene and isoprene. Component (B): a compound having an allyl group or methylallyl group, and component (C): a curable resin component. here,
(A-2) As the component, a homopolymer of styrene, butadiene or isoprene, or 2 selected from these.
Those containing a copolymer composed of a monomer having at least one component are desirable. The component (A-1) is preferably a copolymer having at least a styrene monomer, and preferably has a styrene copolymerization ratio of 5 to 90 mol%.

The component (B) is preferably a compound represented by the following formula (b-1) or (b-2).

Embedded image (In the formula, R is a hydrogen atom or a methyl group.) The curable resin component of the component (C) is preferably any one of an epoxy resin, a phenol resin, and a compound having a maleimide group. Further, a reaction accelerator is used as the component (D),
It is desirable to contain a coupling agent as the component (E) and a filler having an average particle diameter of 1 μm or less as the component (F). The relative dielectric constant after curing is desirably 3.4 or less. The circuit laminate of the present invention is obtained by laminating an adhesive layer containing the above adhesive composition and a peelable film or a metal layer. At this time, it is desirable that the relative permittivity after curing of the adhesive layer is 3.4 or less.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive composition of the present invention comprises an epoxidized copolymer comprising at least a component (A-1): two or more components selected from the group consisting of styrene, butadiene and isoprene. It is a thermosetting resin composition containing a component (B): a compound having an allyl group or a methylallyl group, and a component (C): a curable resin component.

[Component (A-1)] The component (A-1) used in the present invention is an epoxidized copolymer of two or more components selected from styrene, butadiene and isoprene.
Specifically, styrene-butadiene copolymer (SBS),
An epoxidized copolymer of styrene-isoprene copolymer (SIS) or styrene-butadiene-isoprene copolymer (SBIR) may be used. The epoxidized copolymer is obtained by copolymerizing the epoxy-modified monomer or oligomer of the above component, or a styrene-butadiene copolymer (SBS) or a styrene-isoprene copolymer obtained by a known polymerization method. Either (SIS) or styrene-butadiene-isoprene copolymer (SBIR) obtained by epoxidation using an oxidizing agent can be used. The epoxidized copolymer has a structure in which some or all of the double bonds contained in the copolymer are epoxidized, and the latter epoxidized copolymer has control of the degree of polymerization and control of epoxidation. It is easy and suitable for use in the present invention.

[0010] The copolymer preferably contains styrene as a copolymer component. At that time, the copolymer ratio of styrene is preferably 5 to 90 mol%, more preferably 1 to 90 mol%.
It is 0 to 50 mol%, optimally 15 to 40 mol%. If the copolymer ratio is less than 5 mol%, tackiness is likely to occur in the adhesive layer, and if it exceeds 90 mol%, the adhesive layer becomes brittle during drying. As a method for producing the latter epoxidized copolymer, that is, as an oxidizing agent used for oxidizing the copolymer obtained by a known method, any oxidizing agent capable of epoxidizing a double bond contained in the copolymer is used. Well, for example, peracetic acid, formic acid, perpropionic acid, organic peracids such as perbenzoic acid, t-butyl hydroperoxide, cumyl hydroperoxide, tetralyl hydroperoxide,
Hydroperoxides such as diisopropylbenzene hydroperoxide, hydrogen peroxide and the like can be mentioned. At the time of epoxidation, a catalyst can be used if necessary. For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid is used as a catalyst. In the case of hydroperoxides, a catalytic effect is obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, or an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with t-butyl hydroperoxide. be able to.

The epoxidation ratio and the number of epoxy groups can be controlled by controlling the amount of the oxidizing agent and the reaction time. The reaction temperature of the epoxidation depends on the decomposition reaction temperature of the oxidizing agent. For example, the upper limit is preferably 70 ° C. for peracetic acid and 150 ° C. for t-butyl hydroperoxide. It is not always necessary to use a solvent for the reaction, but for stabilization by dilution of the oxidizing agent, etc., benzene, aromatics such as toluene, halides, esters, ketones, and ether-based solvents are used, The reaction is preferably performed in a nitrogen atmosphere. Some of the epoxidized copolymers are generally commercially available. For example, an epoxidized styrene butadiene copolymer is commercially available from Daicel Chemical Industries, Ltd. under the trade name “Epofriend”. By using the epoxidized copolymer of the component (A-1), the film forming ability of the resin composition is improved, so that the handleability during the operation of forming the prepreg into a multilayer is good, and a high-density multilayer wiring board is manufactured. The yield when performing is improved.

The epoxidized copolymer of the component (A-1) is
Those having a weight average molecular weight of 5,000 to 1,000,000, a glass transition temperature of 150 ° C. or less, and a relative dielectric constant of 4.0 or less are preferred. Weight average molecular weight of 10,000 to 50
More preferably, it has a glass transition temperature of 140 ° C. or less and a relative dielectric constant of 3.8 or less, a weight average molecular weight of 20,000 to 300,000, and a glass transition temperature of 1
Those having a temperature of 30 ° C. or less and a dielectric constant of 3.5 or less are more preferred. When the weight average molecular weight is smaller than the lower limit of the above range, thermal stability becomes poor and heat resistance is reduced. If it exceeds the upper limit, the melt viscosity increases, and when used as a resin composition, workability, adhesiveness, and the like become poor. If the glass transition temperature is higher than 150 ° C., the melt viscosity will increase, resulting in an increase in the working temperature and poor adhesion. If the relative dielectric constant is higher than 4.0, it is difficult to achieve a low dielectric constant of the resin base material layer, and it is not suitable for high-speed signal processing. In the present invention, the glass transition temperature (T
g) is the shoulder value of the change in the shear modulus when measured under the following conditions. Measurement conditions of glass transition temperature (Tg): Apparatus: Shear modulus measurement apparatus (Rheo Stress R manufactured by HAAKE)
S75) Measurement temperature range: -10 ° C to 300 ° C Heating rate: 3 ° C / min Measurement frequency: 1 Hz Strain rate: 0.01% ± 0.0025%

[Component (A-2)] The component (A-2) which can be used in the present invention is a homopolymer of styrene, butadiene or isoprene or a copolymer of two or more selected from the above components. The use in addition to the adhesive composition of the present invention makes it easy to control the handleability. Component (A-2) is specifically a styrene polymer, a butadiene polymer, an isoprene polymer, a styrene-butadiene copolymer (SBS), a styrene-isoprene copolymer (SIS), a styrene-butadiene-isoprene copolymer ( SBIR). These homopolymers are synthesized from the monomers by known radical polymerization,
In the case of a rubber-like material, it is preferable to synthesize by an aqueous radical polymerization. The homopolymer or copolymer preferably has a weight average molecular weight of 5,000 to 1,000,000, more preferably 1 to 500,000, and still more preferably 20 to 300,000. The homopolymer is preferably a styrene polymer, and the copolymer preferably contains styrene as a copolymer component. In the copolymer, the preferred styrene content is 20 to 99 mol%, more preferably 50 to 95 mol%.
It is.

The component (A-1) and / or (A-2) may be used, if necessary, in combination of two or more components, for example, (A-1)
It is also one of preferred embodiments to use a mixture of two species of the component (A-2). By using two or more types, the relative permittivity and handleability can be appropriately controlled and used.

[Component (B)] As the component (B), any compound having an allyl group or a methylallyl group can be used. Among them, those having a structure represented by the following formula (b-1) or (b-2) are preferable. The component (B) improves the heat resistance after curing and can lower the dielectric constant of the resin composition. The compound having the structure represented by the formula (b-1) or (b-2) is generally commercially available and can be easily obtained.

[0016]

Embedded image

[(C) component] The curable resin component of the component (c) can be used as long as it is a resin having curability such as thermosetting property and ultraviolet curing property. Among them, an epoxy resin, a phenol resin or a compound having a maleimide group is preferable. More preferably, a compound containing two or more maleimide groups is preferable because of its excellent heat resistance. Above all, the following formula (c-1)
And bismaleimide compounds represented by (c-5) are particularly preferred because of their excellent electrical reliability and solvent solubility. These compounds are generally commercially available and can be easily obtained. Further, it can be synthesized by a conventionally known method.

[0018]

Embedded image (In the formula (c-4), p is an integer of 1 to 8.)

The mixing ratio of the adhesive composition depends on the component (A-
1) Component (B) and component (C) based on 100 parts by weight
Is 10 to 3000 parts by weight, preferably 50 to 30 parts by weight.
00 parts by weight, more preferably 100 to 3000 parts by weight. When the total of the components (B) and (C) is less than 10 parts by weight, the heat resistance of the resin composition after heat curing, particularly the Tg and Young's modulus are remarkably reduced, which is not suitable for the intended use. Also, if it exceeds 3000 parts by weight,
When the resin composition is cured to the B stage, the resin composition itself becomes brittle and causes scattering of the resin. When the component (A-2) is used, the component (A-1) + (A-
2) It is preferable to set the mixing ratio to 100 parts by weight. The mixing ratio of the component (B) and the component (C) is such that the component (C) is equivalent to 1 mole equivalent of the functional group of the component (C).
Is required to be 0.1 to 2.0 molar equivalents, preferably 0.3 to 1.8.
It is set to a molar equivalent, more preferably 0.5 to 1.5 molar equivalent. If the equivalent of the allyl group or methylallyl group is less than the lower limit of the above range, the electrical reliability of the resin composition after curing becomes poor, and if the equivalent is more than the upper limit, a uniform resin composition is prepared for gelling at the time of mixing. You will not be able to do it.

The mixing of the components (A-1), (B) and (C) in a solvent in which they are dissolved results in a mixture having better dispersibility. Examples of the solvent include methanol, ethanol, propanol, isopropanol, methyl acetate, ethyl acetate, benzene, toluene, xylene, acetone, methyl ethyl ketone (ME
K), diethyl ether, dioxane, 1,2-dimethoxyethane, diethylene glycol dimethyl ether,
Methyl cellosolve, cellosolve acetate, tetrahydrofuran, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide,
1,3-dimethyl-2-imidazolidone, hexamethylphosphoric triamide, dimethyl sulfoxide, sulfolane, acetonitrile, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, chlorobenzene, and the like. Several types and amounts are appropriately selected and used so as to be dissolved or dispersed.

[Component (D)] The adhesive composition of the present invention preferably contains a reaction accelerator of the component (D) in order to accelerate the reaction during drying or heat curing. Specific examples of the reaction accelerator include diazabicyclooctane, methyl ethyl ketone peroxide, cyclohexane peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1-bis (t
-Butylperoxy) -3,3,5-trimethylhexane, 1,1-bis (t-butylperoxy) -cyclohexane, 2,2-bis (t-butylperoxy) octane, n-
Butyl-4,4-bis (t-butylperoxy) valate,
2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, di-isopropylbenzene hydroperoxide, p-menthane hydroperoxide, 2,5-dimethylhexane-2, 5-dihydroperoxide, 1,
1,3,3-tetramethylbutyl hydroperoxide, di-cumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, α, α′-
Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) Oxy) hexyne, acetyl peroxide, isobutyl peroxide, octanoyl peroxide,
Decanoyl peroxide, benzoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, succinic acid peroxide, 2,4-dichlorobenzoyl peroxide, m-toluoyl peroxide, di-isopropyl Peroxydicarbonate, di-2-ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-myristyl peroxydicarbonate, di- 2-ethoxyethyl peroxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di-allylperoxydicarbonate, t-butyl -Oxyacetate, t
-Butylperoxyisobutyrate, t-butylperoxypivalate, t-butylperoxyneodecanate, cumylperoxyneodecanate, t-butylperoxy-2-ethylhexanate, t-butylperoxy- 3,5,5-trimethylhexanate, t-butylperoxylaurate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate, 2,5-
Dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate, cumylperoxyoctate, t-hexylperoxyneodecanate, t-hexylperoxy Organic peroxides such as pivalate, t-butylperoxyneohexanate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyallylcarbonate, 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, Methylimidazole, 2-ethyl-4-methylimidazole,
2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 1-benzyl-2
-Methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitate, 1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, -Ethylimidazole, 2-isopropylimidazole, 2-phenyl-4-benzylimidazole, 1-cyanoethyl-2-methylimidazole, 1-
Cyanoethyl-2-ethyl-4-methylimidazole,
1-cyanoethyl-2-undecylimidazole, 1-
Cyanoethyl-2-isopropylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazolium trimellitate, 1-
Cyanoethyl-2-phenylimidazolium trimellitate, 1-cyanoethyl-2-phenyl-4,5-di (cyanoethoxymethyl) imidazole, 2,4-diamino-
6- [2'-methylimidazolyl- (1 ')]-ethyl-s-
Triazine, 2,4-diamino-6- [2'-ethyl-4
-Methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2-methylimidazolium isocyanate Nouric acid adduct, 2-phenylimidazolium isocyanuric acid adduct, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-
s-triazine-isocyanuric acid adduct, 2-phenyl-4,5-dihydroxylmethylimidazole, 2-
Phenyl-4-benzyl-5-hydroxylmethylimidazole, 4,4'-methylene-bis (2-ethyl-5-
1-aminoethyl-2-methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole / benzotriazole adduct, 1-aminoethyl-2-
Ethyl imidazole, 1- (cyanoethylaminoethyl)
-2-methylimidazole, N, N '-[2-methylimidazolyl- (1) -ethyl] -adipoyldamide, N, N'-
Bis- [2-methylimidazolyl- (1) -ethyl] urea;
N- [2-methylimidazolyl-1-ethyl] urea, N, N '
-[2-methylimidazolyl- (1) -ethyl] dodecandioyldiamide, N, N '-[2-methylimidazolyl-
(1) -Ethyl] eicosandioildiamide, imidazoles such as 1-benzyl-2-phenylimidazole / hydrochloride, and reaction accelerators such as triphenylphosphine, but organic peroxides are reactive. Is more preferable because it is excellent.

[Component (E)] In the adhesive composition of the present invention, it is preferable to add a coupling agent of the component (E) in order to increase the adhesive strength to a metal. As the coupling agent, silane-based, titanium-based, and aluminum-based coupling agents can be preferably used. As the silane coupling agent, vinyltrimethoxysilane, vinyltriethoxysilane, N-
(2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) 3-
Aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltriethoxysilane, 3-
Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3
-Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1
-Propanamine, N- [2- (vinylbenzylamino)
Ethyl] -3-aminopropyltrimethoxysilane.hydrochloride, N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, and the like are preferably used. As a titanium-based coupling agent, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl tri (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis
(Di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearyl titanate,
Isopropyl isostearyl diacryl titanate,
Isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, isopropyl tri (N-amidoethylaminoethyl) titanate, dicumyl phenyloxy acetate titanate,
Diisostearoyl ethylene titanate is preferably used. As the aluminum-based coupling agent, acetoalkoxyaluminum diisopropylate or the like is used, but a silane-based coupling agent is more preferable because it effectively acts on the adhesiveness.

[Component (F)] It is preferable to add a filler having an average particle diameter of 1 μm or less to the adhesive composition of the present invention. The filler can be either an inorganic or organic filler. By using the component (F), the fluidity of the resin composition layer can be suppressed, and the thermal dimensional stability can be increased. Therefore, it is preferable to use a filler in applications requiring dimensional stability. Average particle size is 1μm
When the filler is larger, the dispersibility in the resin composition and the film-forming property deteriorate, so that the particle size is more preferably 1 μm or less.
The filler content is 5 to 70% by weight of the total solids, preferably 10 to 60% by weight, more preferably 15 to 50% by weight. When the content is less than 5% by weight, the effect of fluidity stabilization is reduced, and when the content is more than 70% by weight, the adhesive strength is reduced and the relative dielectric constant is too high. As the filler, for example, silica, quartz powder, alumina,
Calcium carbonate, magnesium oxide, diamond powder,
Inorganic fillers such as mica, fluororesin and zircon are preferably used.

The relative permittivity after curing of the resin composition of the present invention is preferably 3.4 or less, more preferably 3.2 or less. When the relative dielectric constant is 3.4 or less, the adhesive can sufficiently cope with miniaturization of circuit wiring and speeding up of a semiconductor device.

[Circuit Laminated Material (Resin Film, Metal Layer with Resin Layer)] In the first circuit laminated material of the present invention, an adhesive layer composed of the above adhesive composition and a peelable film are laminated. Things. This laminate can be obtained, for example, by applying an adhesive composition solution obtained by dissolving and dispersing the above-described adhesive composition in a solvent onto a peelable film. Examples of the releasable film include olefin films such as polyethylene and polypropylene, fluororesin-based films, and polyethylene terephthalate films (hereinafter referred to as PET).
Abbreviated), triacetyl cellulose, paper, and the like. Those in which a releasability is imparted to these films by a silicone resin or the like are preferably used. The film has a thickness of 1 to 20
0 μm is preferable, and 10 to 100 μm is more preferable.
The peelable film is used as a temporary support, and is peeled off in actual use.

The second circuit laminate of the present invention is obtained by laminating an adhesive layer composed of the above adhesive composition and a metal layer. As the adhesive layer, those described above can be used. The metal layer has a thickness of 5 to 300 μm, preferably 200 μm.
m, more preferably 100 μm, particularly preferably 3 μm.
Metal foils of 6 μm or less such as copper, white copper, silver, iron, 42 alloy, stainless steel, and aluminum can be used. If the metal layer is too thick, it becomes difficult to form fine wiring, so that it is preferably 300 μm or less. The above resin composition can be used by laminating it on one side or both sides of a metal surface.

These circuit laminates are formed by applying the above-mentioned adhesive composition to one side of a peelable film, one side or both sides of a metal layer, and drying. At that time, the coating thickness is 5
It is preferably in the range of 10 to 100 µm. If it is less than 5 μm, the insulation of the circuit in the Z-axis direction (between circuits) may be insufficient, and
This is because if the thickness is larger than μm, it becomes impossible to cope with miniaturization of the internal circuit.

[Protective Film] A protective film can be provided on the adhesive layer of the circuit laminate of the present invention, if necessary, and is peeled off when used. As the protective film, the aforementioned peelable film or the like is used. Those that are easier to peel than the temporary support are preferable.

The first circuit laminate is formed by hot-pressing the protective film between the inner circuit board on which the circuit is formed in advance and the metal layer for the exterior circuit, and forming a multilayer metal-clad laminate containing the inner circuit. Or by applying a general circuit forming process such as etching to the outer layer, or by forming a circuit by plating etc. after forming a resin film with a peelable film peeled off on the inner layer circuit board surface and then plating. It becomes a printed wiring board. Further, the second circuit laminate is bonded to an inner circuit board on which a circuit is formed, and is subjected to circuit formation processing on its metal layer to form a multilayer printed wiring board. These can be further multi-layered as an inner layer circuit. These multilayer printed wiring boards are suitable for forming a fine circuit having a high surface smoothness because the cross-eye, which is a problem of the prior art, does not emerge on the surface and absorbs the unevenness of the inner layer circuit. Further, since the resin layer has a film forming ability, troubles such as cracking or missing of the resin in the steps of transporting, cutting, laminating and the like are reduced. In addition, during the formation of heat and pressure when used as an interlayer insulating material of a multilayer wiring board, it is possible to prevent the interlayer insulating layer from becoming thinner in the portion where the inner layer circuit is present, and to avoid a reduction in interlayer insulating resistance and occurrence of a short circuit. it can. In addition, since it has heat resistance and excellent adhesion to metal, it has high reliability, and has a low dielectric constant and a thin insulating property, so that it is suitable for use in a circuit board for high-speed signal processing.

[0030]

EXAMPLES <Polymer of Component (A-2)> (Polymer 1) polystyrene (Mw = 200,000) (Polymer 2) styrene-butadiene copolymer (Mw = 1)
(20,000, styrene: butadiene = 1: 3) (Polymer 3) Styrene-isoprene copolymer (Mw = 1
(20,000, styrene: isoprene = 1: 3) (Polymer 4) Styrene-butadiene-isoprene copolymer (Mw = 120,000, styrene: butadiene: isoprene = 1: 2: 1) <Component (A-1) Epoxidized copolymer> (Polymer 5) Epoxidized styrene-butadiene copolymer (Mw = 120,000, styrene: butadiene = 1: 3, epoxy equivalent 1800) (Polymer 6) Epoxidized styrene-butadiene copolymer (Mw = 120,000, styrene: butadiene = 1: 3, epoxy equivalent 1000) (Polymer 7) Epoxidized styrene-butadiene copolymer (Mw = 120,000, styrene: butadiene = 1: 3, epoxy equivalent 500) ( Polymer 8) Epoxidized styrene-isoprene copolymer (Mw = 120,000, styrene: isoprene = 1: 3, epoxy equivalent 1900) Combined 9) Epoxidized styrene-butadiene-isoprene copolymer (Mw = 120,000, styrene: butadiene:
(Isoprene = 1: 2: 1, epoxy equivalent: 2000) Polymers 5 to 7 were obtained by changing the epoxidation ratio of polymer 2 using peracetic acid, and polymer 8 was obtained by using polymer 3 to obtain a polymer. Epoxidation was carried out in the same manner as in Copolymer 5, and Polymer 9 was obtained by epoxidation in the same manner as in Polymer 5 using Polymer 4.

[Adhesive Composition Preparation Example 1] Epoxidized styrene butadiene isoprene copolymer 16 of polymer 9
0 parts by weight, 40 parts by weight of the polystyrene of the polymer 1, 252 parts by weight of the bismaleimide compound represented by the formula (c-1), and R represented by the formula (b-1) is a methyl group. 148 parts by weight of a compound (the molar equivalent of methylallyl group is 1.0 with respect to 1 molar equivalent of maleimide group)
Organic peroxide (product name: Perbutyl P, manufactured by NOF Corporation)
20 parts by weight, an epoxy-based silane coupling agent 25 parts by weight, and a silica filler (Arakawa Chemical Co., Ltd., average diameter 0.0
(5 μm) 150 parts by weight were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight. [Adhesive composition preparation example 2] 160 parts by weight of epoxidized styrene butadiene isoprene copolymer of polymer 9;
40 parts by weight of the polystyrene of the polymer 1 and the formula (c)
-1) a compound represented by the formula (b)
In the compound represented by -2), 105 parts by weight of a compound in which R is a methyl group (the molar equivalent of methylallyl group is 1.0 with respect to 1 molar equivalent of maleimide group), 20 parts by weight of an organic peroxide, and epoxy-based silane 25 parts by weight of a coupling agent and 150 parts by weight of a silica filler were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 3] Epoxidized styrene butadiene isoprene copolymer 16 of polymer 9
0 parts by weight, 40 parts by weight of polystyrene of the polymer 1, 206 parts by weight of the compound represented by the formula (c-2), and R in the compound represented by the formula (b-1) is a methyl group. 194 parts by weight of a compound (the molar equivalent of methylallyl group is 1.0 with respect to 1 molar equivalent of maleimide group)
And 20 parts by weight of an organic peroxide, 25 parts by weight of an epoxy-based silane coupling agent, and 150 parts by weight of a silica filler are added to tetrahydrofuran and sufficiently mixed and dissolved.
An adhesive composition varnish having a solid content of 40% by weight was obtained. [Adhesive composition preparation example 4] 160 parts by weight of the epoxidized styrene butadiene isoprene copolymer of the polymer 9;
40 parts by weight of the polystyrene of the polymer 1 and the formula (c)
-3 parts) of the compound represented by the formula (b)
-1) a compound in which R is a methyl group in the compound represented by -1) (molar equivalent of methylallyl group is 1.0 with respect to 1 mole equivalent of maleimide group), 20 parts by weight of organic peroxide, and epoxy silane. 25 parts by weight of a coupling agent and 150 parts by weight of a silica filler were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 5] Epoxidized styrene butadiene isoprene copolymer 16 of polymer 9
0 parts by weight, 40 parts by weight of the polystyrene of the polymer 1, and p in the compound represented by the formula (c-4) being 1
And 218 parts by weight of the compound represented by the formula (b-1) and the compound represented by the formula (b-1) wherein R is a methyl group.
1 part by weight (the molar equivalent of methylallyl group to 1 mole equivalent of maleimide group is 1.0), 20 parts by weight of organic peroxide, 25 parts by weight of epoxy silane coupling agent, and 150 parts by weight of silica filler in tetrahydrofuran And the mixture was sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight. [Adhesive Composition Preparation Example 6] 160 parts by weight of the epoxidized styrene butadiene isoprene copolymer of the polymer 9;
40 parts by weight of the polystyrene of the polymer 1 and the formula (c)
-4) 296 parts by weight of the compound represented by p in the compound represented by the formula (b) and 104 parts by weight of the compound represented by the formula (b-1) wherein R is a methyl group (based on 1 mole equivalent of the maleimide group). The molar equivalent of methylallyl group is 1.0), 20 parts by weight of organic peroxide, 25 parts by weight of epoxy silane coupling agent, and silica filler 1
50 parts by weight were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 7] Epoxidized styrene butadiene isoprene copolymer 16 of polymer 9
0 parts by weight, 40 parts by weight of polystyrene of the polymer 1, 246 parts by weight of the compound represented by the formula (c-5), and R is a methyl group in the compound represented by the formula (b-1). 154 parts by weight of a compound (the molar equivalent of methylallyl group is 1.0 with respect to 1 molar equivalent of maleimide group)
And 20 parts by weight of an organic peroxide, 25 parts by weight of an epoxy-based silane coupling agent, and 150 parts by weight of a silica filler are added to tetrahydrofuran and sufficiently mixed and dissolved.
An adhesive composition varnish having a solid content of 40% by weight was obtained. [Adhesive Composition Preparation Example 8] 160 parts by weight of the epoxidized styrene-butadiene copolymer of the polymer 5, 40 parts by weight of the polystyrene of the polymer 1, and 252 of the compound represented by the formula (c-1) Parts by weight of the compound represented by the formula (b-1) wherein R is a methyl group.
8 parts by weight (the molar equivalent of methylallyl group to 1.0 mole equivalent of maleimide group is 1.0), 20 parts by weight of organic peroxide, 25 parts by weight of epoxy silane coupling agent, and 150 parts by weight of silica filler in tetrahydrofuran And the mixture was sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 9] 160 parts by weight of the epoxidized styrene-butadiene copolymer of the polymer 6, 40 parts by weight of the polystyrene of the polymer 1, and the formula (c-1) 252 parts by weight of the compound, 148 parts by weight of the compound represented by the formula (b-1) wherein R is a methyl group (the molar equivalent of methylallyl group is 1.0 relative to 1 molar equivalent of maleimide group), 20 parts by weight of peroxide and epoxy silane coupling agent 2
5 parts by weight and 150 parts by weight of silica filler were added to tetrahydrofuran and mixed and dissolved sufficiently to obtain a solid content of 40 parts by weight.
% By weight of the adhesive composition varnish was obtained. [Adhesive Composition Preparation Example 10] 160 parts by weight of the epoxidized styrene butadiene copolymer of the polymer 7, 40 parts by weight of the polystyrene of the polymer 1, and 252 of the compound represented by the formula (c-1) 1 part by weight of a compound represented by the formula (b-1) wherein R is a methyl group.
48 parts by weight (the molar equivalent of methylallyl group to 1 mole equivalent of maleimide group is 1.0), 20 parts by weight of organic peroxide, 25 parts by weight of epoxy silane coupling agent,
150 parts by weight of a silica filler was added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 11] Polymer 8
160 parts by weight of the epoxidized styrene isoprene copolymer, 40 parts by weight of the polystyrene of the polymer 1, 252 parts by weight of the compound represented by the formula (c-1), and the compound represented by the formula (b-1) 148 parts by weight of the compound in which R is a methyl group (the molar equivalent of a methylallyl group is 1.0 with respect to 1 mole equivalent of a maleimide group), 20 parts by weight of an organic peroxide, and an epoxy silane coupling agent 2
5 parts by weight and 150 parts by weight of silica filler were added to tetrahydrofuran and mixed and dissolved sufficiently to obtain a solid content of 40 parts by weight.
% By weight of the adhesive composition varnish was obtained. [Adhesive Composition Preparation Example 12] 160 parts by weight of the epoxidized styrene butadiene isoprene copolymer of the polymer 9, 40 parts by weight of the polystyrene of the polymer 1, and the compound represented by the formula (c-1) 260 parts by weight, 140 parts by weight of the compound represented by the formula (b-1) wherein R is hydrogen (the molar equivalent of allyl group is 1.0 with respect to 1 molar equivalent of maleimide group), and an organic peroxide 20 parts by weight, 25 parts by weight of an epoxy-based silane coupling agent, and 150 parts by weight of a silica filler were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 13] The above polymer 5
160 parts by weight of the epoxidized styrene-butadiene copolymer, 40 parts by weight of the polystyrene of the polymer 1, 260 parts by weight of the compound represented by the formula (c-1), and the compound represented by the formula (b-1) 140 parts by weight of the compound in which R is hydrogen (the molar equivalent of an allyl group is 1.0 relative to 1 molar equivalent of a maleimide group), 20 parts by weight of an organic peroxide, and 25 parts by weight of an epoxy silane coupling agent. And 150 parts by weight of a silica filler were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight. [Adhesive Composition Preparation Example 14] 160 parts by weight of the epoxidized styrene isoprene copolymer of the polymer 8, 40 parts by weight of the polystyrene of the polymer 1, and 260 parts of the compound represented by the formula (c-1) Parts by weight of a compound represented by the formula (b-1) wherein R is hydrogen
Parts by weight (the molar equivalent of allyl group to 1.0 mole equivalent of maleimide group is 1.0), 20 parts by weight of organic peroxide, 25 parts by weight of epoxy silane coupling agent, and 150 parts by weight of silica filler are mixed in tetrahydrofuran. The mixture was sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 15] The above-mentioned polymer 9
Epoxidized styrene butadiene isoprene copolymer 1
60 parts by weight, 40 parts by weight of the polystyrene of the polymer 1, 306 parts by weight of the compound represented by the formula (c-1), and R in the compound represented by the formula (b-2) is hydrogen. 94 parts by weight of the compound (the molar equivalent of the allyl group is 1.0 relative to 1 molar equivalent of the maleimide group), 20 parts by weight of the organic peroxide, and the epoxy-based silane coupling agent 25
Parts by weight and 200 parts by weight of silica filler were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight. [Adhesive Composition Preparation Example 16] 160 parts by weight of the epoxidized styrene butadiene copolymer of the polymer 5, 40 parts by weight of the polystyrene of the polymer 1, and 306 of the compound represented by the formula (c-1) Parts by weight, 94 parts by weight of the compound represented by the formula (b-2) wherein R is hydrogen (the molar equivalent of allyl group is 1.0 with respect to 1 molar equivalent of maleimide group), and the organic peroxide 20 Parts by weight, 25 parts by weight of an epoxy-based silane coupling agent, and 150 parts by weight of a silica filler were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 17] The above polymer 5
160 parts by weight of the epoxidized styrene-butadiene copolymer, 40 parts by weight of the polystyrene of the polymer 1, 166 parts by weight of the compound represented by the formula (c-2), and the compound represented by the formula (b-1) 234 parts by weight (the molar equivalent of methylallyl group is 1.5 relative to 1 molar equivalent of maleimide group), 20 parts by weight of an organic peroxide, and an amine-based silane coupling agent 25.
Parts by weight and 150 parts by weight of an alumina filler (manufactured by Showa Denko KK, average diameter: 0.05 μm) were added to tetrahydrofuran and mixed and dissolved sufficiently to obtain an adhesive composition varnish having a solid content of 40% by weight. [Adhesive Composition Preparation Example 18] 160 parts by weight of the epoxidized styrene butadiene copolymer of the polymer 5, 40 parts by weight of the polystyrene of the polymer 1, and 272 of the compound represented by the formula (c-2) 1 part by weight of a compound represented by the formula (b-1) wherein R is a methyl group.
28 parts by weight (the molar equivalent of methylallyl group to 0.5 mole equivalent of maleimide group is 0.5), 20 parts by weight of organic peroxide, 25 parts by weight of amine-based silane coupling agent, and 150 parts by weight of alumina filler were mixed with tetrahydrofuran. The resulting mixture was sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 19] The above polymer 5
160 parts by weight of the epoxidized styrene butadiene copolymer, 40 parts by weight of the polystyrene of the polymer 1, 206 parts by weight of the compound represented by the formula (c-2), and the compound represented by the formula (b-1) 194 parts by weight of a compound in which R is a methyl group (the molar equivalent of a methylallyl group is 1.0 with respect to 1 mole equivalent of a maleimide group), 20 parts by weight of an organic peroxide, and an epoxy silane coupling agent 2
5 parts by weight were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight. [Adhesive Composition Preparation Example 20] 80 parts by weight of the epoxidized styrene butadiene copolymer of the polymer 5, 20 parts by weight of the polystyrene of the polymer 1, and 206 parts of the compound represented by the formula (c-2) Parts by weight of a compound represented by the formula (b-1) wherein R is a methyl group.
4 parts by weight (the molar equivalent of the methylallyl group to 1 mole equivalent of the maleimide group is 1.0), 16 parts by weight of the organic peroxide, and 20 parts by weight of the epoxy silane coupling agent are sufficiently added to tetrahydrofuran. The mixture was dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 21] Polymer 5
320 parts by weight of the epoxidized styrene-butadiene copolymer, 80 parts by weight of the polystyrene of the polymer 1, 206 parts by weight of the compound represented by the formula (c-2), and the compound represented by the formula (b-1) 194 parts by weight of the compound in which R is a methyl group (the molar equivalent of a methylallyl group is 1.0 with respect to 1 molar equivalent of a maleimide group), 26 parts by weight of an organic peroxide, and an epoxy silane coupling agent 3
2 parts by weight were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight. [Adhesive Composition Preparation Example 22] 200 parts by weight of the epoxidized styrene butadiene copolymer of the polymer 6, 206 parts by weight of the compound represented by the formula (c-2), and the formula (b-1) 194 parts by weight (the molar equivalent of methylallyl group to 1 mole equivalent of maleimide group is 1.0), 20 parts by weight of an organic peroxide, and an epoxy silane coupling agent. 2
5 parts by weight were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

[Adhesive Composition Preparation Example 23] The above polymer 5
150 parts by weight of the epoxidized styrene-butadiene copolymer, 50 parts by weight of the styrene-butadiene copolymer of the polymer 2, 206 parts by weight of the compound represented by the formula (c-2), and the compound represented by the formula (b- In the compound represented by 1), R
Is a methyl group in an amount of 194 parts by weight (the molar equivalent of the methylallyl group is 1.
0), 20 parts by weight of an organic peroxide, and 25 parts by weight of an epoxy-based silane coupling agent were added to tetrahydrofuran and mixed and dissolved sufficiently to obtain an adhesive composition varnish having a solid content of 40% by weight. Was. [Adhesive Composition Preparation Example 24] 60 parts by weight of the epoxidized styrene butadiene copolymer of the polymer 5, 100 parts by weight of the epoxidized styrene butadiene copolymer of the polymer 7, and 40 parts of the polystyrene 40 of the polymer 1 Parts by weight, 206 parts by weight of the compound represented by the formula (c-2), and 194 parts by weight of the compound represented by the formula (b-1) wherein R is a methyl group (1 mole equivalent of a maleimide group) The molar equivalent of a methylallyl group to the compound was 1.0), 20 parts by weight of an organic peroxide, and 25 parts by weight of an epoxy-based silane coupling agent were added to tetrahydrofuran, mixed and dissolved sufficiently, and the solid content was 40 parts by weight. % Of the adhesive composition varnish was obtained.

[Adhesive Composition Preparation Example 25] "Epofriend A1010" (Styrene.
Epoxidized butadiene / styrene block copolymer: butadiene / styrene weight ratio;
0 parts by weight, 40 parts by weight of polystyrene of the polymer 1, 206 parts by weight of the compound represented by the formula (c-2), and R in the compound represented by the formula (b-1) is a methyl group. 194 parts by weight of a compound (the molar equivalent of methylallyl group is 1.0 with respect to 1 molar equivalent of maleimide group)
And 20 parts by weight of an organic peroxide (trade name: Parloyl L, manufactured by NOF CORPORATION), and an amine-based silane coupling agent 25
Parts by weight were added to tetrahydrofuran and sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight. [Adhesive Composition Preparation Example 26] 160 parts by weight of "Epofriend A1010" from Daicel Chemical Industries, 40 parts by weight of polystyrene of the polymer 1, and 155 parts by weight of the compound represented by the formula (c-2) And a compound represented by the formula (b-1), wherein R is a methyl group.
45 parts by weight (molar equivalent of methylallyl group to 1 mole equivalent of maleimide group is 1.0), 32 parts by weight of epoxy resin and Epicoat 828 manufactured by Yuka Shell Epoxy, phenol resin manufactured by Showa Kogyo Co., Ltd., and BRG- 555, 18 parts by weight, 20 parts by weight of an organic peroxide (trade name: Parloyl L, manufactured by NOF CORPORATION), and 25 parts by weight of an amine silane coupling agent are mixed with tetrahydrofuran and MEK (= 2: 1). The resulting mixture was sufficiently mixed and dissolved to obtain an adhesive composition varnish having a solid content of 40% by weight.

Examples 1-26 Adhesives after drying each adhesive composition varnish obtained in the above adhesive composition preparation examples 1-26 were dried on one side of a 38 μm-thick PET film. The coating was applied so that the thickness of the layer became 50 μm, and the coating was dried at 140 ° C. for 5 minutes in a hot air circulating drier to prepare a circuit laminate of the present invention. Further, the obtained circuit laminated material is superimposed on the inner layer circuit on both sides of a double-sided copper-clad inner layer circuit board having a thickness of 0.1 mm and a thickness of 18 μm of copper foil on which a predetermined circuit is formed, and further peeled off. Peel the conductive film to a thickness of 18
A μm copper foil was overlaid and molded at 200 ° C. for 2 hours under a pressure of 20 kg / cm ² to prepare a multilayer copper-clad laminate having an inner circuit. [Example 27] The adhesive composition varnish obtained in the adhesive composition preparation example 19 was applied to one surface of a copper foil having a thickness of 18 µm so that the thickness of the adhesive layer after drying was 50 µm. It was dried at 140 ° C. for 5 minutes in a hot-air circulation type dryer to prepare a circuit laminate of the present invention. Further, the adhesive layer of the obtained circuit laminate material is applied to the inner layer circuit on both sides of a double-sided copper-clad inner layer circuit board having a thickness of 0.1 mm and a thickness of 18 μm of copper foil, on which a predetermined circuit is formed. Pile facing each other, 200 ℃ 2
A multilayer copper-clad laminate containing an inner layer circuit was formed by molding at a pressure of 20 kg / cm ² for a time.

Example 28 Preparation Example 3 of the Adhesive Composition
The adhesive composition varnish obtained in 1) was applied to one surface of a copper foil having a thickness of 18 μm so that the thickness of the resin base material layer after drying was 50 μm, and the coating was dried at 140 ° C. in a hot air circulation type dryer at 5 ° C. After drying for a minute, a circuit laminate of the present invention was prepared. Further, the adhesive layer of the obtained circuit laminate material is applied to the inner layer circuit on both sides of a double-sided copper-clad inner layer circuit board having a thickness of 0.1 mm and a thickness of 18 μm of copper foil, on which a predetermined circuit is formed. Pile up to face each other,
It was molded at 200 ° C. for 2 hours under a pressure of 20 kg / cm ² to prepare a multilayer copper-clad laminate containing an inner layer circuit. [Example 29] The adhesive composition varnish obtained in the above adhesive composition preparation example 19 was applied to one surface of a 42 alloy having a thickness of 18 µm such that the adhesive layer after drying had a thickness of 50 µm. Dry at 140 ° C for 5 minutes in a hot air circulation type dryer,
A circuit laminate of the present invention was made. Further, the adhesive layer of the obtained circuit laminate is provided on both sides of a double-sided copper-clad inner circuit board having a thickness of 0.1 mm and a thickness of 42 μm of a 42-alloy foil on which a predetermined circuit has been formed. Pile up to face each other,
It was molded at 200 ° C. for 2 hours under a pressure of 20 kg / cm ² to prepare a multilayer 42 alloy-clad laminate having an inner layer circuit.

[Comparative Example 1] 200 parts by weight of the epoxidized styrene-butadiene copolymer of the polymer 5 was added to the compound of the formula (c)
-2) 400 parts by weight of the compound, 20 parts by weight of an organic peroxide (perbutyl P), an epoxy-based silane coupling agent, and 150 parts by weight of a silica filler are dissolved and mixed in tetrahydrofuran, and the solid content is determined. A multilayer copper-clad laminate containing an inner circuit was prepared in the same manner as in Example 1 except that a resin composition of 40% was used. Comparative Example 2 A comparative adhesive composition was prepared in the same manner as in the above adhesive composition preparation example 1 except that the components (A-1) and (A-2) were replaced with an acrylonitrile butadiene copolymer. A varnish was prepared. Using the obtained adhesive composition varnish, the same operation as in Example 1 was performed to prepare a multilayer copper-clad laminate having an inner layer circuit. [Comparative Example 3] An adhesive for comparison was prepared in the same manner as in Adhesive Composition Preparation Example 1 except that 200 parts by weight of styrene-butadiene-isoprene copolymer of Polymer 4 was used instead of Polymer 9 and Polymer 1. A varnish was obtained. Next, a multilayer copper-clad laminate containing an inner layer circuit was obtained in the same manner as in Example 1.

[Evaluation] Examples 1 to 29 and Comparative Example 1
Solder heat resistance and electrical reliability by PCBT were measured for the laminates of Nos. 1 to 3. Further, the surface of the adhesive layer of the circuit laminate was visually observed to evaluate its uniformity. The relative permittivity and peel strength were measured for the circuit laminates of Examples 1 to 26 and Comparative Examples 1 to 3. The curing condition of the adhesive layer is 200 ° C. for 2 hours. [Dielectric constant] Measure the capacitance of the cured adhesive layer according to JISC
6481 (relative permittivity and dielectric loss tangent), and measured at a frequency of 1 MHz. [Peel strength] JIS C6481 (peeling strength)
It measured according to. [Solder heat resistance] JIS C6481 (Solder heat resistance)
The measurement was carried out according to the above-mentioned method, and the presence or absence of abnormal appearance at 260 ° C. was examined. [PCBT (Pressure Cooker Biased Test)] A pattern having a line interval of 100 μm is formed on the outer copper foil of the laminate by etching, and the circuit laminate obtained in the examples and comparative examples having a thickness of 0.1 mm is formed on the pattern. The test pieces were prepared by laminating and heating and pressing at 20 ° C. for 2 hours at 20 kg / cm ² .
The test piece was subjected to PCBT under the conditions of 5 V application, 130 ° C., 85%, and 336 hours, and the presence or absence of a short circuit between patterns was examined. [Uniformity of adhesive layer] The surface of the adhesive layer of the circuit laminate was magnified with a loupe and visually observed.

[0048]

[Table 1]

From Table 1, it can be seen that the circuit laminate of the present invention has a low relative dielectric constant, does not cause swelling of the copper foil even with solder heat resistance, has sufficient adhesive strength, and has high electrical reliability. I understand. Further, the adhesive layer was uniform and excellent in layer formation. On the other hand, in the laminate of Comparative Example 1, the copper foil swelled due to the heat resistance of the solder, and the relative dielectric constant was high. The laminated material of Comparative Example 2 had a higher relative dielectric constant than Comparative Example 1. Comparative Example 3
The surface of the adhesive layer was not uniform, and the formability of the adhesive layer was difficult.

[0050]

The circuit laminate using the adhesive composition of the present invention has a low relative dielectric constant, sufficient peel strength, and excellent heat resistance and electrical reliability. It is suitable for the circuit lamination of the above. In particular, since the relative dielectric constant of the adhesive layer after curing can be reduced to 3.4 or less, it is possible to cope with miniaturization of an internal circuit and can be suitably used for a high-density multilayer laminate.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) // C09J 4/06 C09J 4/06 (72) Inventor Masaharu Kobayashi 3rd Yomunechocho, Shizuoka City, Shizuoka Prefecture No. 1 In the electronic material division of the Hamakawa Paper Mill Co., Ltd. (72) Inventor Osamu Osamu 3-1, Yomune-cho, Shizuoka-shi, Shizuoka Prefecture F-term in the electronic material division of the Hamakawa Paper Mill Co., Ltd. 4F100 AA19 AA32E AB01C AB17D AB17E AB31D AB31E AB33E AH02A AH02E AH03A AH06E AK12A AK12E AK28A AK28E AK29A AK29E AK33A AK42 AK49A AK49E AK53A AK53E AK80A AL01A AL01E AL05D AT00B BA03 BA05 BA07 BA10B BA10C CB10A CC00 CC00E DE04A GB43 JG04 JG05A JJ03 JL11 JL14B YY00A 4J040 DC092 EB031 EB032 EC001 EC002 EC201 EC202 EC211 EC212 FA011 FA012 FA191 FA192 GA02 HA026 HA136 HA156 HA196 HA306 HA356 HB07 HB41 HC23 HD32 HD35 HD36 HD37 JB10 KA03 KA16 KA17 KA42 LA01 LA02 LA09 MA02 NA20

Claims (12)

[Claims] 1. An epoxidized copolymer comprising at least two components selected from the group consisting of styrene, butadiene and isoprene, and a component (B) having a compound having an allyl group or a methylallyl group. And (C) a curable resin component. 2. The composition according to claim 1, further comprising, as the component (A-2), a homopolymer of styrene, butadiene or isoprene, or a copolymer of two or more monomers selected from these. 2. The adhesive composition according to 1. 3. The composition according to claim 1, wherein the component (A-1) is a copolymer having at least a styrene monomer, and the styrene copolymerization ratio is 5 to 90 mol%. The adhesive composition as described in the above. 4. The adhesive composition according to claim 1, wherein the component (B) is a compound represented by the following formula (b-1) or (b-2). Embedded image (In the formula, R is a hydrogen atom or a methyl group.) 5. The adhesive composition according to claim 1, wherein the curable resin component (C) is one of an epoxy resin, a phenol resin, and a compound having a maleimide group. 6. The adhesive composition according to claim 1, further comprising a reaction accelerator as the component (D). 7. The adhesive composition according to claim 1, further comprising a coupling agent as the component (E). 8. Further, as the component (F), an average particle size of 1 μm is used.
m or less of a filler.
The adhesive composition as described in the above. 9. The adhesive composition according to claim 1, wherein the dielectric constant after curing is 3.4 or less. 10. A circuit laminate comprising an adhesive layer containing the adhesive composition according to claim 1 and a peelable film. 11. A circuit laminate comprising an adhesive layer containing the adhesive composition according to claim 1 and a metal layer. 12. The adhesive layer after curing has a relative dielectric constant of 3.4 or less.
The described circuit laminate.