JPH0974273A - Copper plated laminated board for printed circuit board and adhesive agent used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To realize a copper-plated laminated board where an unroughened foil is used by a method wherein adhesive agent formed of various kinds of prescribed resins is used as adhesive ground represented by a specific formula on a copper foil. SOLUTION: An adhesive ground formed of silane coupling agent represented by a formula I (Q denotes a functional group which reacts with resin composition, R is a coupling group which couples Q with an Si atom, and X, Y, and Z denote a hydrolytic group or a hydroxyl group bonded to Si atom) or thiol coupling agent represented by a formula II (T is aromatic ring or the like, n denotes an integer of two or more) is formed on a copper foil. The copper foil is bonded to a laminated base material with adhesive agent formed of acrylic monomer, diallyl phthalate, peroxide curing resin composition of thermoplastic elastmer which contains ethylene butylene copolymer and styrene copolymer in a molecule, and polyvinyl butyral resin composition possessed of a side chain which contains unsaturated groups through the intermediary of the adhesive ground. The adhesive agent is turned into silanol groups through hydrolysis and reacts on the surface of the copper foil, whereby a copper plated laminated board can be obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a copper clad laminate for printed circuits.

[0002]

2. Description of the Related Art As a laminated base material for a copper clad laminate for a printed circuit, a paper base phenol resin prepreg in which paper is impregnated with phenol resin and a glass cloth base epoxy resin prepreg in which glass cloth is impregnated with an epoxy resin composition are used. Is commonly used.

Further, a glass cloth or aramid fiber cloth is impregnated with a polyimide resin, a bismaleimide resin, a special low dielectric constant modified epoxy resin or a fluororesin, and further, an insulating resin layer is formed on the surface of a metal plate such as an aluminum plate. The laminated base material on which is formed is also in practical use.

Furthermore, polyester films and polyimide films are also used as laminated base materials, and these are used for manufacturing flexible printed circuit boards, TAB tapes for mounting LSI, etc., which are required to be bendable.

The adhesive force between the copper foil for a copper-clad laminate and the laminated base material, or the copper foil for a copper-clad laminate and the adhesive depends on the secondary bonding force such as van der Waals force and hydrogen bond, and the anchor effect. It is said to be derived. The anchor effect is a phenomenon in which the resin mechanically adheres to the uneven structure on the surface of the copper foil, and the larger the unevenness, the higher the adhesive force. It is said that the secondary bonding force is not large and the contribution of the anchor effect is large.

The copper foil used for the copper-clad laminate is mainly an electrolytic copper foil. Since the electrolytic copper foil (unroughened foil) has a small unevenness on the surface and cannot obtain the necessary adhesive force, further roughening is performed to form finer particles (roughened particles) on the convex portions.

The roughened copper foil (roughened foil) is composed of a coating layer for the purpose of rust prevention such as chromate treatment and various alloys in order to satisfy various characteristics required for a printed circuit board. It is also practiced to form a coating layer. In addition,
The glossy surface is called the shiny surface (S surface), and the non-glossy surface that is bonded to the laminated base material is called the matte surface (M surface).

On the other hand, the rolled copper foil has less crystal grain boundaries and is more excellent in bending resistance than the electrolytic copper foil, so that it is mainly used for copper clad laminates for flexible printed circuit boards. Also, it is said that the one using oxygen-free copper is suitable for audio equipment because it has excellent electric characteristics, and a small amount of roughened one is used for glass cloth base material epoxy resin copper clad laminate. . However, since the rolled copper foil has smaller unevenness on the surface and lower adhesive strength than the electrolytic copper foil, the amount used for manufacturing the copper clad laminate is significantly smaller than that of the electrolytic copper foil.

Currently used thickness of 18 μm
With this copper foil, the pitch of circuit copper foil that can be industrially realized is 20
It is 0 μm and the line width is about 100 μm. This is because it takes a long time to remove the convex portions and the roughening particles buried in the laminated base material, and the etching becomes excessive. On the other hand, for the purpose of reducing the size and weight of electronic equipment, it is strongly desired to form a fine conductor circuit pattern. For example, 40μ in the field of TAB
A pitch of m is required.

Therefore, a copper foil having a surface roughness smaller than that of the conventional one has been proposed and partly put to practical use, but since the adhesive force between the copper foil and the laminated base material is low, it has been generally adopted. Not in. This is because the anchor effect derived from the unevenness of the copper foil is reduced. That is, the conventional adhesive technique based on the anchor effect is essentially incompatible with the adhesive force and the pitch.

It is known that the adhesive force between the copper foil and the laminated base material is increased by the treatment with the silane coupling agent. For example, Japanese Patent Publication No. 60-15654 discloses that a chromate-treated electrolytic copper foil is treated with a silane coupling agent. According to this, the silanol group generated by the hydrolysis of the silane coupling agent is condensed with the hydroxyl group on the surface of the chromate-treated layer to form a chemical bond.

On the other hand, a functional group such as an amino group of the silane coupling agent reacts with the laminated base material and the adhesive to form a chemical bond. That is, it is said that the treatment with the silane coupling agent indirectly forms a chemical bond with the copper foil, the laminated base material, and the adhesive to increase the adhesive force. Table 1 shows the evaluation results of the present inventors in this respect.

The center line average roughness specified in JIS-B-0601 is hereinafter referred to as surface roughness (Ra). Further, the peel strength defined in the test method JIS-C-6481 is the force required to peel the copper foil from the laminated base material and is a measure of the adhesive strength.

[0014]

[Table 1]

It can be seen that when the surface roughness is small, the silane coupling agent treatment has almost no effect. That is, it is clear that the unevenness of the surface is important for obtaining a sufficient adhesive force.

The reason why the effect of increasing the adhesive strength is small even though it is considered that the chemical bond is formed is that the amount of the generated chemical bond is insufficient or the toughness of the base resin at the adhesive interface is sufficient. I think it is because it is not. For example, an epoxy resin composition used for a laminated base material is a semi-cured product called B stage which is generally obtained by partially reacting a bisphenol A type epoxy resin and a curing agent, and reacts with a silane coupling agent. The number of epoxy groups is not large.

Further, the present inventors tried to measure the mechanical properties of a film prepared by curing an epoxy resin composition separated from a laminated base material, but there was almost no elongation.
The same applies to the butyral-phenol resin adhesive. That is, it is presumed that the cured products of these resin compositions have relatively high strength, but lack elongation and poor toughness, and as a result, strong adhesive strength cannot be obtained.

[0018]

In the conventional bonding of the copper foil and the laminated base material, the unevenness of the copper foil surface was indispensable. For this reason, in the printed circuit board using the copper clad laminate according to the related art, (1) it takes a long time to remove the protrusions and the roughening particles buried in the laminate substrate during the etching for forming the circuit. ,
Since etching becomes excessive, it is difficult to miniaturize to a pitch of 200 μm or less, which becomes a bottleneck for fine patterning.

(2) Due to the unevenness of the surface of the electrolytic copper foil, the energy loss and the waveform distortion are increased in a high frequency signal.

(3) Sufficient adhesive force cannot be obtained with rolled copper foil having small irregularities or electrolytic copper foil.

There are problems such as the above.

In the production of electro-deposited copper foil, a technique for controlling the shape of surface irregularities and a technique for controlling roughening particles have been developed, but (1) the work margin is narrowed and the productivity is reduced.

(2) Non-uniformity of thickness due to unevenness causes defects such as wrinkles and curls.

(3) Since the surface is rough due to unevenness, foreign matter is easily attached.

There are problems such as the above.

In view of the above technical background, the present inventors have made extensive studies on the bonding technique between the copper foil and the laminated base material. That is, since all of the above-mentioned problems are caused by the unevenness of the copper foil surface, the development of a high adhesive force not depending on such unevenness has been studied. According to the bonding method that does not require the concavo-convex structure, the unroughened copper foil which has not been used conventionally can be provided to the copper clad laminate for printed circuit boards.

Further, a rolled copper foil or an electrolytic copper foil having an extremely small surface roughness can be provided to the copper clad laminate, and it is not necessary to perform excessive etching, and the fine pattern can be easily formed. Further, an ultrathin copper foil having a thickness of 9 μm or 12 μm, or an ultrathin copper foil having an aluminum foil or a polyester film as a support can be used.

In order to obtain a high adhesive force without relying on the anchor effect, a strong chemical bond is essential between the copper foil and the base resin. However, the silane coupling agent treatment
Although it is said that such a chemical bond is formed, sufficient adhesive force has not been obtained. this is,
Actually, it is presumed that the chemical bond is not sufficiently formed and the toughness of the laminated base material and the adhesive is not sufficient.

Therefore, the inventors of the present invention can obtain a high adhesive force by using a tough resin having a large mechanical strength and a large elongation and being able to sufficiently form a chemical bond with the silane coupling agent. I thought.

An object of the present invention is to provide a copper clad laminate for a printed circuit, in which a copper foil and a laminate substrate are firmly adhered to each other with a tough and highly reactive adhesive.

Another object of the present invention is to provide an adhesive between a copper foil and a laminate of the above copper clad laminate for a printed circuit.

[0032]

Means for Solving the Problems The gist of the present invention for solving the above problems is as follows.

[1] A copper-clad laminate in which a copper foil is laminated and adhered to one side or both sides of a laminated base material: a. General formula [1] on the copper foil

[0034]

Embedded image QRSiXYZ [1] (wherein Q is a functional group that reacts with the following resin composition,
R is a linking group connecting Q and Si atoms, and X, Y and Z are S
represents a hydrolyzable group or a hydroxyl group bonded to an i atom)
Or a silane coupling agent represented by the general formula [2]

[0035]

Embedded image From a thiol-based coupling agent represented by T (SH) n ... [2] (where T is an aromatic ring, an aliphatic ring, a heterocycle, or an aliphatic chain, and n is an integer of 2 or more) Through an adhesive substrate that is (1) Acrylic monomer, methacrylic monomer, a polymer thereof or a copolymer with an olefin, (2) a diallyl phthalate, an epoxy acrylate or an epoxy methacrylate and a peroxide-curable resin composition of the oligomer thereof, (3) ethylene Peroxide curable resin composition of thermoplastic elastomer containing butylene copolymer and styrene copolymer in the molecule, (4) Resin composition of olefin copolymer containing glycidyl group, (5) Adhesion to a laminated base material with an adhesive composed of a resin composition of polyvinyl butyral resin having a side chain containing a saturated group, or (6) a resin composition of polyvinyl butyral resin, amino resin having spiroacetal ring and epoxy resin Or is directly bonded to the laminated base material that also functions as an adhesive for the resin composition. Printed circuit, characterized in Rukoto copper-clad laminate.

[2] On the adhesive surface of the copper foil, B, Al,
P, Zn, Ti, V, Cr, Mn, Fe, Co, Ni,
Ag, In, Zr, Sn, Nb, Mo, Ru, Rh, P
The print according to the above [1], which has a coating layer selected from metals, alloys, oxides, hydroxides and hydrates containing at least one element selected from d, Pb, Ta, W, Ir and Pt. Copper clad laminate for circuits.

[3] (1) Acrylic monomer, methacrylic monomer, polymer thereof or copolymer with olefin, (2) diallyl phthalate, epoxy acrylate or epoxy methacrylate and peroxide curable resin composition of those oligomers. (3) Peroxide curable resin composition of thermoplastic elastomer containing ethylene butylene copolymer and styrene copolymer in the molecule, (4) Resin composition of olefin copolymer containing glycidyl group Or (5) a resin composition of a polyvinyl butyral resin having a side chain containing an unsaturated group, or (6) a resin composition of a polyvinyl butyral resin, an amino resin having a spiroacetal ring, and an epoxy resin. An adhesive for a copper clad laminate for a printed circuit, which is composed of one kind.

[4] The polyvinyl butyral resin having a side chain containing an unsaturated group comprises (1) a condensation product of an unsaturated aldehyde and polyvinyl alcohol, and (2) an isocyanate compound containing an unsaturated group and polyvinyl alcohol. The adhesive for a copper clad laminate for a printed circuit according to the above [3], which is a condensation product or (3) a condensation product of a hydroxyl group-containing liquid polybutadiene, an isocyanate compound and polyvinyl alcohol.

[0039]

The thickness of the copper foil used in the present invention is preferably 3 to 500 μm. Preferably 5 to
150 μm is preferable. The type of copper foil may be roughened foil or unroughened foil, and the surface to be bonded may be the S surface or the M surface. Further, the rolled copper foil can be used as both a roughened product and a non-roughened product. Since any of them can be used to obtain a copper-clad laminate in which the copper foil and the laminated base material are firmly adhered to each other, the degree of freedom in selecting the copper foil is large.

However, the most effective effect of the present invention is application to an unroughened foil which has not been put to practical use in the past. The surface roughness of the unroughened foil is 0.10 to 0.3 on the S side.
It is 5 μm, and is 0.10 to 2.00 μm on the M plane. Also,
Both sides of the rolled copper foil are 0.10 to 0.15 μm. A printed circuit board used for a high frequency circuit is required to have a surface roughness of 0.35 μm or less, preferably 0.20 μm or less.

On the adhesive surface of the copper foil, B, Al, P, Z
n, Ti, V, Cr, Mn, Fe, Co, Ni, Ag,
In, Zr, Sn, Nb, Mo, Ru, Rh, Pd, P
A coating layer containing one or more elements selected from b, Ta, W, Ir and Pt can be formed. The above-mentioned coating layer may contain the above-mentioned metals or their alloys, or oxides, hydroxides and hydrates. Also,
The coating layer may be a composite layer composed of two or more layers.

As the alloy forming the coating layer, for example, Cu--Zn, Ni--Zn, Ni--Sn, Ni--C are used.
u, Pd-P, Ni-P, Zn-Mo, Ni-Co-M
o, Sn-Zn, Zn-W, Zn-Cr, Cr-Mo,
There are various alloys composed of combinations of metal elements such as Co-Mo and In-Zn.

In the case of an alloy containing Cu, the Cu content is 1 to 95% by weight, preferably 60 to 95% by weight. In the case of an alloy containing Ni, the Ni content is 1 to 9
5% by weight, preferably 60 to 95% by weight.

In the copper foil used for the high frequency circuit, the metal forming the coating layer is preferably a non-magnetic metal, for example, P
d, or an alloy of Pd and an element other than Pd (for example, P), having a Pd content of 1 to 99% by weight, preferably 60 to
95% by weight is preferred. Furthermore, a composite metal layer is used as the alloy layer, and in this case, it is preferable that the base side is a Pd-P alloy and the surface side is a Cu-Zn alloy.

A coating layer made of Cr oxide, hydroxide or hydrate may be formed by the chromate treatment disclosed in JP-B-60-15654.

The thickness of these coating layers formed on the surface of the copper foil is 5 μm or less, preferably 0.01 to 5 μm. These can be formed by electroplating, chemical plating, vapor deposition plating, sputtering, immersion treatment, or the like.

The inventors have used the silane coupling agent represented by the general formula [1] or the thiol-based coupling agent represented by the general formula [2] as a resin used as the copper foil and the adhesive of the present invention. It was found that a strong bond was formed with both of the compositions, and the copper foil and the adhesive layer were firmly bonded.

That is, in the silane coupling agent, a hydrolyzable group such as a methoxy group and an ethoxy group becomes a silanol group (Si-OH) by hydrolysis, and this reacts with the surface of the copper foil to form a strong bond. That is, the functional group Q is bonded to the resin composition which is an adhesive. Incidentally, in the olefin copolymer containing a glycidyl group, although forming a bond directly with the silane coupling agent, other resin composition containing no glycidyl group,
That is, in the peroxide-curable resin composition, a bond is formed between the resin composition and the silane coupling agent by the action of radicals generated by thermal decomposition of the peroxide.

Further, in the thiol-based coupling agent, the thiol group is firmly bonded like the copper foil and the resin composition of the present invention.

Examples of the silane coupling agent represented by the general formula [1] include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4).
-Epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ
-Glycidoxypropylmethyldiethoxysilane, γ-
Glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β- ( Aminoethyl) -γ-aminopropylmethyldimethoxysilane,
N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,
There are N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, vinyltriacetoxysilane, and the like. Can be used.

In the silane coupling agent, the size and chemical structure of the bonding group R for bonding the functional group Q and the silicon atom have little influence on the adhesive force, but the carbon number of R is preferably 2-30. The silane coupling agent is selected based on the solubility, workability, reactivity with the adhesive, etc.

In addition, a commercially available silane coupling agent primer may be used. These include X-12-413, X-12-41
4 (Shin-Etsu Chemical Co., Ltd.), AP-133, Y-5106, Y
-5254, APZ-6601 (Nippon Unicar) and the like.

The method of adding the silane coupling agent or the primer includes a surface coating method and an internal addition method. In the surface coating method, a silane coupling agent or a primer is dissolved in water or an organic solvent and coated on the copper foil surface and dried (80
~ 120 ° C). The amount of the silane coupling agent or primer added was 0. 0 with respect to water or an organic solvent.
It is preferred to use from 01 to 5% by weight.

In the internal addition method, a silane coupling agent or a primer is added to and mixed with the adhesive. In this method, it is preferable to add 1 to 5% by weight to the resin.

The thiol-based coupling agent represented by the general formula [2] is a compound having two or more thiol groups in the molecule and forms a bond with a peroxide curable resin in addition to the thiol groups. It may have a functional group.

From the viewpoint of reactivity, those having a structure in which a thiol group is directly bonded to a triazine ring are preferable. That is,
Since the thiol group bonded to the aliphatic hydrocarbon is highly reactive, there is a problem in storage stability. In addition, it is difficult to introduce a plurality of thiol groups into the aromatic ring, which is extremely expensive.

Examples of such thiol coupling agents include, for example, 2,4,6-trimercapto-1,3,5-
Triazine, 2,4-dimercapto-6-methylamino-1,3,5-triazine, 2,4-dimercapto-6-
Ethylamino-1,3,5-triazine, 2,4-dimercapto-6-propylamino-1,3,5-triazine,
2,4-dimercapto-6-isopropylamino-1,
3,5-triazine, 2,4-dimercapto-6-butylamino-1,3,5-triazine, 2,4-dimercapto-6-isobutylamino-1,3,5-triazine, 2,
4-dimercapto-6-dimethylamino-1,3,5-triazine, 2,4-dimercapto-6-diethylamino-1,3,5-triazine, 2,4-dimercapto-6-
Dipropylamino-1,3,5-triazine, 2,4-dimercapto-6-diisopropylamino-1,3,5-triazine, 2,4-dimercapto-6-dibutylamino-1,3,5-triazine, 2,4-dimercapto-6-
Allylamino-1,3,5-triazine, 2,4-dimercapto-6-phenylamino-1,3,5-triazine,
2,4-dimercapto-6-p-tolylamino-1,3,
5-triazine, N, N'-bis (2,4-dimercapto-
1,3,5-triazinyl) ethylenediamine, 2,4-dimercapto-6-hydroxyethylamino-1,3,5-
Examples include triazine, 2,4-dimercapto-6-bis (hydroxyethyl) amino-1,3,5-triazine and 2,4-dimercapto-6-acrylamino-1,3,5-triazine.

In place of the above compounds, metal salts such as monosodium salt or monopotassium salt may be used. These thiol coupling agents are used similarly to silane coupling. Although there is no great advantage or inferiority in these, a thiol coupling agent is a metal itself, that is, a coating layer of copper or various metals or alloys, and a silane coupling agent is a metal oxide such as a chromate treatment used as an anticorrosion coating layer. It is suitable for adhesion to coating layers containing oxides, hydroxides and hydrates.

The acrylic monomers, methacrylic monomers, polymers thereof or copolymers of them with olefins include acrylic acid and esters of acrylic acid with monohydric or polyhydric alcohols.

Examples of these compounds are acrylic acid, allyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, acrylic acid (2-ethylhexyl), dimethylamino acrylate. Ethyl ester, diethylene glycol ethoxylate acrylate, alkyl modified dipentaerythritol acrylate, ε-caprolactone modified dipentaerythritol acrylate, caprolactone modified tetrahydrofurfuryl acrylate, caprolactone modified hydroxypivalic acid neopentyl glycol ester diacrylate, diglycidyl bisphenol A Diacrylate, dipentaerythritol monohydroxy acrylate, n-stearyl acrylate, tetrahydr Furfuryl acrylate,
Trimethylolpropane triacrylate, neopentyl glycol hydroxypivalate diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 1,4-butanediol diacrylate, 2-propenoic acid [2-
[1,1-Dimethyl-2- (1-oxo-2-propenyloxy) ethyl] -5-ethyl-1,3-dioxan-5-yl] methyl ester, pentaerythritol triacrylate, lauryl-tridecyl (mixed) There are acrylates.

Methacrylic monomers include methacrylic acid and esters of methacrylic acid with monohydric or polyhydric alcohols.

Examples of these compounds are methacrylic acid, allyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate and methacrylic acid (2-ethylhexyl). ), Octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, lauryl methacrylate-tridecyl methacrylate, tridecyl methacrylate, cetyl-stearyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, tridecyl methacrylate, methacrylate (2-hydroxyethyl), diethylaminoethyl methacrylate, t-butylaminoethyl methacrylate, methacrylate (2-hydroxypropyl), dimethylaminoethyl methacrylate, glycidyl methacrylate, methacryl Acid tetrahydrofurfuryl, ethylene dimethacrylate, diethylene glycol dimethacrylate,
Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, ethylene glycol dimethacrylate, decaethylene glycol dimethacrylate,
Pentadeca ethylene glycol dimethacrylate, ethylene dimethacrylate, pentacontahector ethylene glycol dimethacrylate, 1,3-butylene dimethacrylate, allyl methacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, dimethacrylate. Examples include methacrylic acid diethylene glycol.

Further, reaction products of acrylic acid or methacrylic acid with various polyisocyanate compounds can also be suitably used. In addition, polyisocyanate compounds and polyhydric alcohols, the reaction product of polybasic acid acrylic acid,
It may be reacted with methacrylic acid. Furthermore, these compounds may be reacted simultaneously. These reaction products are generally called urethane acrylate or urethane methacrylate, and depending on the molar ratio of the raw material compounds,
The viscosity, softening point, and mechanical properties of the cured product can be controlled.

As the polyisocyanate compound, there are toluylene diisocyanate, methanediphenyl isocyanate, hexamethylene diisocyanate, etc., and the polybasic acid is phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid. Acid, oxalic acid,
Examples include succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanedicarboxylic acid, and methylcyclohexanedicarboxylic acid.

The diallyl phthalates include diallyl terephthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, etc., all of which are used as oligomers by stopping the polymerization reaction at a relatively low molecular weight. You can

As the epoxy acrylate or epoxy methacrylate, there are reaction products of various epoxy compounds having two or more epoxy groups in the molecule with acrylic acid or methacrylic acid, and various epoxy compounds include bisphenol A diglycidyl ether, An oligomer which is composed of bisphenol A diglycidyl ether and bisphenol A and has epoxy groups at both ends of the molecule can be mentioned.

The above-mentioned monomers, oligomers, polymers and copolymers can be used alone or in combination. Further, various resins such as polyvinyl butyral, polyolefin, styrene-butadiene copolymer, styrene-acrylonitrile copolymer, PPO resin, and allyl-modified PPO resin may be mixed.

A phenol novolac resin can be added to the olefin copolymer containing a glycidyl group. However, it is not preferable to use a peroxide because the effect of the peroxide is hindered. In particular, this method is recommended when the softening point of the resin composition is low and the handleability of the copper foil coated with the resin composition is impaired. In addition, it is also possible to improve the softening point of the resin composition and improve the handleability by a method such as heat curing or ultraviolet curing after coating.

The ethylene butylene copolymer and the styrene copolymer are produced by hydrogenating the double bond remaining in the block copolymer of styrene and dienes. The diene used is isoprene, butadiene, piperylene,
Examples include cyclopentadiene, ethylidene norbornene, cyclohexadiene, norbornadiene.

By using these resins, not only a resin composition having a low viscosity which is difficult to be applied as it is and an appropriate viscosity is provided, the coating operation is facilitated, and the formed coating film is tough. And improve the properties of the copper clad laminate.

In particular, when a paper base phenol resin is used as the base material, it is preferable to use a polyvinyl acetal resin as a mixture. Polyvinyl acetal resin is a resin obtained by acetalization reaction of polyvinyl alcohol with aldehydes such as acetaldehyde and butyraldehyde, and has excellent mechanical strength. The resin composition combined with phenol resin or epoxy resin uses paper-based phenol resin. It is commonly used as an adhesive for copper clad laminates.

The polyvinyl acetal resin used in the present invention is not limited to one using a saturated aldehyde such as acetaldehyde or butyraldehyde as an aldehyde, and one using an unsaturated aldehyde such as crotonaldehyde and having an unsaturated bond in its side chain is also preferable. Used for.

In the polyvinyl acetal resin having an unsaturated bond, the reactivity with the monomers is higher than that of the saturated one, and the obtained cured product is more uniformly crosslinked, so that the heat resistance is improved. To do.

A compound having an unsaturated group introduced by reacting a polyvinyl acetal resin with a compound having a highly reactive unsaturated bond in the molecule such as isocyanate ethyl methacrylate and the like, The terminal isocyanate type liquid polybutadiene obtained by the reaction of the terminal hydroxyl group type liquid polybutadiene and the diisocyanate compound may be used by reacting with the polyvinyl acetal resin.

Such a terminal isocyanate type liquid polybutadiene includes poly bd H produced by Idemitsu Petrochemical Co., Ltd.
There is TP-9. Incidentally, the polyvinyl acetal resin does not cure by itself, and it is common to use a curing agent.

In the above conventional copper-clad laminate, in the adhesive using a phenolic resin, the methylol group of the phenolic resin easily reacts with the residual hydroxyl group of the polyvinyl acetal resin to cause a cross-linking reaction, so that the polyvinyl acetal resin Since it gives a tough cured product that is integrated with the phenol resin, there are few reliability problems at high temperatures.

However, since the phenol resin is easily carbonized and has a problem in tracking resistance, an epoxy resin is used in place of the phenol resin in applications requiring tracking resistance. However, the epoxy resin and the polyvinyl acetal resin are used. Since no reaction between the and can be expected, melamine resin is added. However,
Although the melamine resin has less deterioration in tracking resistance than the phenol resin, it is not preferable.

However, the addition of the melamine resin is beneficial because it is expected that the properties at high temperature will be improved by the crosslinking reaction of the polyvinyl acetal resin with the methylol group.

CTU, a compound similar to melamine resin
The guanamine resin is an amino resin having a spiroacetal ring in the molecule, has less deterioration in tracking resistance than the melamine resin, and does not deteriorate other properties, and therefore can be preferably used. However, the amount used is preferably 20% or less in terms of solid content with respect to the polyvinyl acetal resin.
When the amount of addition is large, an excessive crosslinking reaction proceeds in the step of applying the adhesive to the copper foil, which lowers the adhesiveness to the base material and also lowers the tracking resistance.

As the peroxide used in the peroxide-curable resin composition of the present invention, an organic compound that generates radicals by thermal decomposition at the pressing temperature is used. The generated radicals crosslink between the molecules, and become a three-dimensionalized insoluble and infusible cured product. A preferable peroxide has a temperature at which half of the peroxide decomposes in 1 minute (half-minute temperature for 1 minute) of 150 to 18
0 ° C., for example, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne, benzoyl peroxide, 2,4-dichlorodibenzoyl peroxide, t-butyl hydroperoxide, 1,1 -Bis-t-butylperoxy-3,3,5-trimethylcyclohexane, n-butyl-4,4'-bis-t-butylperoxyvalerate, di- (t-butylperoxy) -m
There is di-isopropylbenzene or the like, and 1 to 5 parts by weight may be added to 100 parts by weight of the peroxide curable resin.

As the glycidyl group-containing olefin copolymer, a copolymer of a glycidyl group-containing vinyl compound such as glycidyl acrylate and glycidyl methacrylate and various olefins such as ethylene, propylene and butene can be used. is there. In addition to these, styrene, α-methylstyrene, vinyl acetate, various acrylic monomers, various methacrylic monomers and the like may be copolymerized.

Further, a compound having an unsaturated bond in the main chain or side chain may be oxidized with air or peroxide to introduce an epoxy group. In the olefin copolymer containing a glycidyl group, it is not necessary to add a peroxide, but the addition of the peroxide improves the characteristics.

The above resin compositions may be used alone or in combination, and various monomers may be added and used. For example, various maleimide compounds such as N, N'-m-phenylenebisimide, triallyl isocyanurate, trimetaallyl isocyanurate, triallyl cyanurate, triacryl formal, trisepoxypropyl isocyanurate, N, N'-methylene. Bisacrylamide, N, N'-m-phenylenebisacrylamide, N-
Methylol acrylamide etc. are mentioned.

Further, various liquid rubbers such as liquid polybutadiene can be added. The blending amount of these is 0.1 to 50 parts by weight with respect to 100 parts by weight of the main compound. Especially when the unsaturated bond such as ethylene butylene copolymer and styrene copolymer is not contained in the molecule,
Monomers, oligomers and polymers, which cure easily with peroxides but also have suitable unsaturated bonds, can be added.

As the solvent for dissolving the various resin compositions of the present invention, various organic solvents used in general paint varnishes are preferably used, and various aromatic compounds such as toluene and xylene, acetone, methyl ethyl ketone and methyl are used. There are various ketones such as isobutyl ketone and cyclohexanone, various alcohols such as methanol, ethanol and isopropanol, acetic acid esters such as butyl acetate and amyl acetate, and various cellosolves such as methyl cellosolve and ethyl cellosolve. Selected from sex.

With regard to solubility, it is desirable that the nonvolatile content in the varnish is at least 10% by weight, and that a dry coating film having a thickness of at least 1 μm, preferably 10 μm or more can be obtained by applying 100 μm or less.

From the viewpoint of drying property, the drying temperature is 12
It is desirable to obtain a non-greasy coating film at a temperature of 0 ° C. or less and a drying time of 10 minutes or less.

Within a range that does not impair the effects of the present invention,
As a filler, alumina, attapulgite, kaolin clay, carbon black, graphite, fine silicic acid,
Calcium silicate, diatomite, magnesium oxide, titanium oxide, iron oxide, magnesium hydroxide, aluminum hydroxide, slate powder, serinite, quartz powder, hydrous silica,
Fused silica, boron nitride, calcium carbonate, magnesium carbonate, talc, feldspar powder, molybdenum dioxide,
An inorganic filler such as barite, vermiculite, whiting, mica, wax clay, gypsum or the like, or an organic filler such as phenol resin micro balun, polyimide micro baln, wood powder or organic fiber powder can be added.

Further, carbon fibers, metal fibers, whiskers, boron fibers, glass fibers, ceramic fibers, polyester fibers, vinylon fibers and polyamide fibers can be used. These are filaments, filament yarns,
It may be arranged in the laminated base material in the form of chopped fiber, staple fiber, pulp, spanned yarn, cloth, non-woven fabric or the like.

Various pigments, petroleum-based paraffin oils, naphthenic oils, aromatic oils and other softening agents, as well as aluminum hydroxide, hydrated gypsum, zinc borate, alumite, red phosphorus powder, halogens. A flame retardant such as a mixture of a fluorinated organic compound and antimony trioxide can be added.

In the copper clad laminate of the present invention, the laminate base is adhered to the surface of the adhesive base of the copper foil formed of the silane coupling agent or the thiol coupling agent by an adhesive, or The layer structure is not particularly limited as long as it has a structure in which a laminated base material that also serves as an adhesive is adhered.

Further, a conductor circuit may be formed in the insulating substrate. This conductor circuit may be formed from the copper foil used in the present invention or may be a conductor circuit manufactured by a conventional method.

Furthermore, a stainless steel foil is used for the copper clad laminate,
A resistance layer such as an aluminum foil or a nickel foil may be provided, and the resistance layer may be laminated and adhered to the insulating layer by using the adhesion method used in the present invention.

In addition, a silicon substrate, a gallium substrate,
An insulating substrate made of glass substrate, ceramic substrate, beryllia, graphite, boron nitride, paper, etc., or metal substrate such as iron plate (silicon steel plate, stainless steel plate), aluminum plate, titanium plate, etc. also forms an insulating layer. Can be used.

The above-mentioned conditions for lamination adhesion are usually 100 to 100.
It is preferable to select from conditions of 250 ° C., 1 to 30 MPa, and 5 to 90 minutes, but it is not limited thereto.

The resin used as the adhesive in the present invention is a tough resin having high mechanical strength and large elongation, and as a result of realizing an adhesive interface capable of following deformation by external force, adhesive force is obtained. Of.

The present invention can provide a copper clad laminate for a printed circuit for various purposes.

In the present invention, the strong adhesion between the copper foil and the laminated base material is not caused by one kind of material, but by one kind of material.
This is due to the synergistic effect of the resin forming the copper foil, the silane coupling agent or the thiol coupling agent, and the adhesive.

The silane coupling agent or thiol coupling agent reacts with the copper foil to form an adhesive base. Adhesive force is obtained by forming a chemical bond between the base and the olefin copolymer constituting the adhesive. As a result, a strong adhesive force can be imparted to the unroughened foil and the rolled copper foil, so that roughening of the copper foil is not particularly required. As a result, the manufacturing process can be shortened and the yield of copper foil manufacturing can be improved.

Further, copper residue due to roughening particles at the time of forming a circuit by etching a printed circuit board as in the prior art is eliminated, and it is possible to contribute to an improvement in the yield of printed circuit board production.

Further, even when the adhesive is applied, since it can be applied on the smooth surface of the copper foil, the thickness of the coating film can be reduced to 1/2 of the conventional thickness.
It can be reduced to 1/5. Further, with the smoothing of the copper foil, the adhesion of foreign matter, the generation of wrinkles and curls during manufacturing are reduced, and it is possible to provide a high-quality copper foil that is easy to use.

The limit line width in the circuit formation by etching the printed circuit board can be 40 μm pitch (18 μm thickness) in comparison with the conventional copper foil 200 μm pitch, which can greatly contribute to the fine patterning of the printed circuit board.

Further, the resin of the present invention is essentially excellent in insulation, has a low dielectric constant, and is excellent in tracking resistance. In particular, a copper clad laminate using a rolled copper foil having smooth surfaces on both sides has a small waveform distortion of a high frequency signal,
Excellent as a high frequency circuit board.

[0104]

EXAMPLES The present invention will be described more specifically with reference to examples.

[Conventional Examples 1 to 4] Copper was deposited on a titanium rotating cathode by electrolysis of an aqueous solution of copper sulfate, and a thickness of 3 was obtained.
A 5 μm copper foil (unroughened foil) was produced. Next, a roughening treatment was performed to deposit fine copper particles (roughened particles) on the M surface of the unroughened foil to obtain a roughened foil. The precipitation of the roughened particles was performed by electrolyzing an aqueous solution of copper sulfate at a limiting current density or higher.

The above work was carried out using an actual machine, and the surface roughness (Ra μm) of the M side was 1.0 for the unroughened foil and 1.6 for the roughened foil.
Met.

Then, the roughened foil and the unroughened foil were subjected to chromate treatment. That is, in a dichromic acid aqueous solution, the treated surface was faced to the anode at a current density of 0.15 A / dm for 4 seconds, washed with water, and immediately dried with hot air at 60 ° C. for 10 minutes. Moreover, the silane coupling agent treatment dissolves 1 g of S-330 (manufactured by Chisso Petrochemical: γ-aminopropyltriethoxysilane) which is a silane coupling agent in pure water 11 without drying the chromate-treated copper foil. After immersing in the above solution for 10 seconds, it was dried with hot air at 60 ° C. for 10 minutes without washing with water.

A copper clad laminate was produced using the copper foil produced through the above steps. Unroughened foil (copper foil A) and roughened foil (copper foil B) that have been treated with a silane coupling agent, unroughened foil (copper foil C) and roughened foil that have not been treated with a silane coupling agent (copper foil C) It is a copper foil D). Butyral-phenolic resin adhesive varnish on copper foil M surface (Hitachi Kasei Polymer VP-6
7) was applied to a thickness of 100 μm, dried at room temperature for 1 hour, and then heated at 120 ° C. for 3 minutes before use. The adhesive film thickness was 27 μm.

A paper-based phenolic resin prepreg (made by Hitachi Chemical Co., Ltd .: 437F, thickness: 0.2 mm) was used as the laminated base material, and 8 laminated base materials and 1 copper foil were laminated at 168 ° C. and 15 M.
It was pressed at Pa for 1 hour and integrated to obtain a copper clad laminate. However, it was formed so that the adhesive-coated surface of the copper foil faces the laminated base material.

The peel strength of the above copper clad laminate was measured according to JIS-
It measured according to C6481. Table 2 shows the measurement results of the peel strength in the normal state and after heating (standing in a hot air dryer at 180 ° C. for 48 hours).

The normal peel strength of the roughened foil (copper foil D) which was not treated with the silane coupling agent was 2.1 kN / m. On the other hand, it is 1.1 kN / m when the unroughened foil (copper foil C) is used, and the unroughened foil (copper foil A) is 1.3 kN even when the silane coupling agent is used.
It can be seen that the adhesive strength is N / m and the adhesive strength is not practical, and roughening is indispensable.

[0112]

[Table 2]

[Example 1] 5 g of Diabeam UK-6038 (manufactured by Mitsubishi Rayon), which is a urethane-modified acrylic monomer, and polyvinyl butyral resin (abbreviated as PVB,
Denka product number 6000C) 5 g was dissolved in a solvent 30 g in which methyl ethyl ketone and ethanol were mixed at a ratio of 6/4 (weight ratio), and peroxide Perbutyl P (manufactured by NOF Corporation) was added in an amount of 0.05 g. An adhesive varnish was created.

Using this varnish instead of the butyral-phenol resin adhesive varnish used in the above-mentioned conventional example, it was applied to copper foil A to a thickness of 100 μm, dried at 120 ° C. for 10 minutes, and then processed in the same manner as in the conventional example. To produce a copper clad laminate.

Table 3 shows the measurement results of the peel strength. Peeling strength is 2.1kN / m in normal condition, 2.0kN / m after heating
Then, an adhesive force equivalent to that when the roughened foil was used was obtained.

Example 2 A copper clad laminate was produced in the same manner as in Example 1 except that 0.15 g of peroxide was used. Table 3 shows the measurement results of the peel strength. As in the case of Conventional Example 1, a strong adhesive force was obtained.

Example 3 A copper clad laminate was produced in the same manner as in Example 1 except that UK-6039 was used instead of UK-6038. Table 3 shows the measurement results of the peel strength. As in the case of Conventional Example 1, a strong adhesive force was obtained.

Example 4 A copper clad laminate was produced in the same manner as in Example 3 except that 0.15 g of peroxide was used. Table 3 shows the measurement results of the peel strength. As in the case of Conventional Example 1, a strong adhesive force was obtained.

[0119]

[Table 3]

Example 5 The same procedure as in Example 1 was carried out except that 0.5 g of DiaBeam UK-6105 (manufactured by Mitsubishi Rayon Co., Ltd.), which is a vinyl ester, was used in place of UK-6038 and was applied to a thickness of 200 μm. A copper clad laminate was prepared.

Table 4 shows the measurement results of the peel strength. However, as a base plating layer for chromate treatment on copper foil, N
i-Mo-Co ternary plating was applied. The peel strength was 2.1 kN / m in the normal state and 2.0 kN / m after heating, and the adhesive strength equivalent to that when the roughened foil was used was obtained.

Example 6 A copper clad laminate was produced in the same manner as in Example 5 except that 1 g of UK-6105 was used. Table 4 shows the measurement results of the peel strength. As in the case of Conventional Example 1, a strong adhesive force was obtained.

[Example 7] 1.5 g of UK-6105
A copper clad laminate was produced in the same manner as in Example 5 except that the copper clad laminate was used. Table 4 shows the measurement results of the peel strength. As in the case of Conventional Example 1, a strong adhesive force was obtained.

Comparative Example 1 A copper clad laminate was produced in the same manner as in Example 5 except that UK-6105 was not used.
Table 4 shows the measurement results of the peel strength. Only a low adhesion of 1.2 kN / m was obtained.

[0125]

[Table 4]

Example 8 10 g of DAP K (Daiso: diallyl phthalate prepolymer), which is a diallyl phthalate resin, was dissolved in 10 g of methyl ethyl ketone, and 0.1 g of perbutyl P, a peroxide, was added to form an adhesive varnish. It was made.

This varnish was used as a substitute for the butyral-phenolic resin-based adhesive varnish of the above-mentioned conventional example, and a copper foil 10
It was applied to a thickness of 0 μm and dried at 120 ° C. for 10 minutes to prepare a copper clad laminate in the same manner as in the conventional example. Table 5 shows the measurement results of the peel strength. However, for the copper foil, 1 g of 2,4,6-trimercapto-1,3,5-triazine (manufactured by Sankyo Kasei: Disnet F) was subjected to THF without chromating the unroughened foil used in the conventional example. 1 in 1 liter of treated solution
It was immersed for 0 seconds and treated with a thiol-based coupling agent. Peeling strength is 3.1kN /
m, and after heating, a strong adhesive force of 2.8 kN / m was obtained.

Example 9 A copper clad laminate was produced in the same manner as in Example 8 except that 0.3 g of peroxide was used. Table 5 shows the measurement results of the peel strength. Similar to Example 8, a strong adhesive force was obtained.

[Example 10] A copper clad laminate was produced in the same manner as in Example 8 except that Isodap IK was used instead of DappK. Table 5 shows the measurement results of the peel strength. Similar to Example 8, a strong adhesive force was obtained.

Example 11 A copper clad laminate was produced in the same manner as in Example 10 except that 0.3 g of peroxide was used.

Table 5 shows the measurement results of the peel strength. Similar to Example 8, a strong adhesive force was obtained.

[0132]

[Table 5]

Example 12 Hydrogenated styrene-butadiene copolymer (manufactured by Japan Synthetic Rubber: DYNARON: E46
00P) pellets (40 g) and peroxide perbutyl P (0.8 g) were mixed in a mixer set at 120 ° C. to form a uniform lump. A film-like adhesive having a thickness of 50 μm was obtained by using a two-roll mill set at 120 ° C.

Copper foil and eight paper-based phenolic resin prepregs were laminated through the film-like adhesive, and a copper-clad laminate was prepared in the same manner as in Conventional Example 1. However, the copper foil used was the Ni-Mo-Co ternary-plated copper foil used in Example 5, and the M surface was made to face the adhesive. Table 6 shows the measurement results of the peel strength. A strong adhesive force was obtained as in Example 1.

[Comparative Example 2] A copper clad laminate was produced in the same manner as in Example 12 except that the peroxide was not used. Table 6 shows the measurement results of the peel strength. It was found that the adhesive strength was lower than that when the peroxide was used.

Example 13 A copper clad laminate was produced in the same manner as in Example 12 except that a hydrogenated styrene-isoprene copolymer was used instead of the hydrogenated styrene-butadiene copolymer. Table 6 shows the measurement results of the peel strength. Example 1
As with No. 2, a strong adhesive force was obtained.

[Comparative Example 3] A copper clad laminate was produced in the same manner as in Example 13 except that the peroxide was not used. Table 6 shows the measurement results of the peel strength. It was found that the adhesive strength was lower than that when the peroxide was used.

[0138]

[Table 6]

Example 14 A hydrogenated styrene-isoprene copolymer was replaced with a glycidyl methacrylate-ethylene copolymer (manufactured by Nippon Petrochemical Co., Ltd., Nisseki Lexpearl, brand: RA3050) and a peroxide was used. A copper clad laminate was produced in the same manner as in Example 12 except that the copper clad laminate was not used. Table 7 shows the measurement results of the peel strength. Similar to Example 12, a strong adhesive force was obtained.

Example 15 A copper clad laminate was produced in the same manner as in Example 14 except that 0.8 g of peroxide was used.
Table 7 shows the measurement results of the peel strength. A stronger adhesive strength than that of Example 14 was obtained.

Example 16 A copper clad laminate was produced in the same manner as in Example 15 except that 0.8 g of the co-crosslinking agent was used.
Table 7 shows the measurement results of the peel strength. A stronger adhesive strength than that of Example 14 was obtained.

Example 17 A copper clad laminate was produced in the same manner as in Example 14 except that Bondfast (Sumitomo Chemical Co., Ltd., product type 2A) was used instead of Nisseki Lexpearl. Table 7 shows the measurement results of the peel strength. Strong adhesive strength was obtained as in Example 14.

[0143]

[Table 7]

Example 18 Vinyl ester V
R-91 (Showa High Polymer) 3g, Denka polyvinyl butyral resin 6000C 3g, toluene / methyl ethyl ketone / methanol 7/1/2 (weight ratio)
An adhesive varnish was prepared by dissolving in 30 g of the solvent mixed in above and adding 0.06 g of peroxide Perbutyl P.

A copper clad laminate was produced in the same manner as in Example 1 using this varnish. The solder heat resistance and the peel strength at high temperature were measured for this. The solder heat resistance was measured by floating a test piece molded into a 25 mm square on a solder bath at 260 ° C. with the copper foil surface facing downward, and measuring the time until destruction. The peeling strength was 150 ° C. The results are shown in Table 8.

Example 19 Table 8 shows the evaluation results of test pieces produced in the same manner as in Example 1 except that BY-515 manufactured by Denka was used instead of 6000C as the polyvinyl butyral resin.

The average degree of polymerization of BY-515 is 2
The value is 500, which is equivalent to 6000C, except that 30% of the butyraldehyde used for acetalization is replaced with crotonaldehyde and an unsaturated bond is introduced into the side chain.

Example 20 Table 8 shows the evaluation results of test pieces produced in the same manner as in Example 18, except that 0.4 g of CTU-100 manufactured by Fuji Chemical Co., Ltd. which is a CTU-guanamine resin was added.

[Comparative Example 4] MW-22 manufactured by Sanwa Chemical Co., Ltd., which is a melamine resin, in place of CTU-guanamine resin was used.
Table 8 shows the evaluation results of the test pieces produced in the same manner as in Example 18 except that 4 g was added.

[0150]

[Table 8]

[0151]

The present invention cannot be used conventionally because a strong adhesive force can be obtained by the adhesive base formed by the chemical bonding of the coupling agent and the copper foil and the various resins described above. A copper clad laminate using an unroughened foil can be provided.

Further, a strong adhesive force can be imparted even to a rolled copper foil which is difficult to roughen, and the rolled copper foil can be used for a copper clad laminate. Since there are few wrinkles, it is possible to provide a high quality copper clad laminate.

Further, unlike the prior art, copper residue is eliminated when the printed circuit board is formed with a circuit by etching, so that the inspection process can be simplified and the yield can be improved and a fine pattern can be greatly contributed.

Furthermore, by using a non-roughened copper foil having a small surface undulation, it is possible to obtain a copper-clad laminate excellent in high frequency characteristics as compared with the conventional roughened copper foil, which is extremely useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09J 133/06 JDB C09J 133/06 JDB 163/00 JFN 163/00 JFN (72) Inventor Ryoichi Narushima Shimodate, Shimodate, Ibaraki 1226 Japan Electrolysis Co., Ltd.Shimodate factory (72) Inventor Takuya Iida 1226 Shimoeden, Shimodate, Ibaraki Shimodate Japan Shimodate factory (72) Inventor Yasuhiro Endo Shimodate, Ibaraki Shimoeren 1226 Japan Electrolysis Company Shimodate Factory

Claims (7)

[Claims] 1. A copper-clad laminate in which a copper foil is laminated and adhered to one side or both sides of a laminated base material, comprising: a. General formula [1] QRSiXYZ ... [1] (where Q is a functional group that reacts with the following resin composition:
R is a linking group connecting Q and Si atoms, and X, Y and Z are S
represents a hydrolyzable group or a hydroxyl group bonded to an i atom)
Or a silane coupling agent represented by the general formula [2]: T (SH) n ... [2] (wherein T is an aromatic ring, an aliphatic ring, a heterocycle or an aliphatic chain, and n Is an integer of 2 or more) via an adhesive base consisting of a thiol-based coupling agent, b. (1) Acrylic monomer, methacrylic monomer, a polymer thereof or a copolymer with an olefin, (2) a diallyl phthalate, an epoxy acrylate or an epoxy methacrylate and a peroxide-curable resin composition of the oligomer thereof, (3) ethylene Peroxide curable resin composition of thermoplastic elastomer containing butylene copolymer and styrene copolymer in the molecule, (4) Resin composition of olefin copolymer containing glycidyl group, (5) Adhesion to a laminated base material with an adhesive composed of a resin composition of polyvinyl butyral resin having a side chain containing a saturated group, or (6) a resin composition of polyvinyl butyral resin, amino resin having spiroacetal ring and epoxy resin Or is directly bonded to the laminated base material that also functions as an adhesive for the resin composition. Printed circuit, characterized in Rukoto copper-clad laminate. 2. B, Al, P, Z on the adhesive surface of the copper foil
n, Ti, V, Cr, Mn, Fe, Co, Ni, Ag,
In, Zr, Sn, Nb, Mo, Ru, Rh, Pd, P
The copper for printed circuit according to claim 1, which has a coating layer selected from metals, alloys, oxides, hydroxides and hydrates containing at least one element selected from b, Ta, W, Ir and Pt. Upholstered laminate. 3. The polyvinyl butyral resin having a side chain containing an unsaturated group is (1) a condensation product of an unsaturated aldehyde and polyvinyl alcohol, and (2) a condensation product of an isocyanate compound containing an unsaturated group and polyvinyl alcohol. Or a (3) hydroxyl group-containing liquid polybutadiene, an isocyanate compound, and a condensation product of polyvinyl alcohol, the copper clad laminate for a printed circuit according to claim 1. 4. The copper clad laminate for a printed circuit according to claim 1, wherein the resin composition containing a polyvinyl butyral resin having a side chain containing an unsaturated group contains an amino resin having a spiroacetal ring in the molecule. . 5. (1) Acrylic monomers, methacrylic monomers, polymers thereof or copolymers with olefins,
(2) Peroxide curable resin composition of diallyl phthalate, epoxy acrylate or epoxy methacrylate and their oligomers, (3) thermoplastic elastomer containing ethylene butylene copolymer and styrene copolymer in the molecule. Oxide-curable resin composition, (4) glycidyl group-containing olefin copolymer resin composition,
At least one selected from (5) a resin composition of a polyvinyl butyral resin having a side chain containing an unsaturated group, or (6) a resin composition of a polyvinyl butyral resin, an amino resin having a spiroacetal ring, and an epoxy resin. An adhesive for a copper-clad laminate for a printed circuit, which comprises 6. The polyvinyl butyral resin having a side chain containing an unsaturated group is (1) a condensation product of an unsaturated aldehyde and polyvinyl alcohol, and (2) a condensation product of an isocyanate compound containing an unsaturated group and polyvinyl alcohol. The adhesive for a copper clad laminate for a printed circuit according to claim 5, wherein the adhesive is a condensation product of (3) liquid polybutadiene having a hydroxyl group, an isocyanate compound and polyvinyl alcohol. 7. The copper clad laminate for a printed circuit according to claim 5, wherein the resin composition containing a polyvinyl butyral resin having a side chain containing an unsaturated group contains an amino resin having a spiroacetal ring in the molecule. Adhesive for.