JPH03264349A - Copper clad laminate - Google Patents

Abstract

PURPOSE:To obtain copper clad laminate, which is excellent in rigidity, strength, soldering heat resistance and peel strength at elevated temperature, by a method wherein copper foil is laminated to side chain double bond type resin laminate through adhesive, which is prepared by mixing epoxy resin, poly(vinyl butyral) and phenol resin. CONSTITUTION:The copper clad laminate concerned is produced by laminating side chain double bond type resin laminate and copper foil to each otter through adhesive, which is prepared by mixing 10-300 pts.wt. of poly(vinyl butyral) and 5-100 pts.wt. of phenol resin with 100 pts.wt. of epoxy resin. Side chain double bond type resin is polymer consisting of main chain, which is made of trunk polymer containing vinyl monomer unit having functional group, and side chain, which is made of branched polymer having radical hardenable carbon-to-carbon double bond composed through the functional group in the main chain. As the adhesive, mixture prepared by melting and mixing epoxy resin, hardener, poly(vinyl butyral) and phenol resin with one another by proper solvent is used. As the copper foil, electrolytic copper foil or rolled copper foil, which is used for copper clad laminate for electric circuit, is used.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a copper-clad laminate used in electrical equipment, electronic equipment, communication equipment, etc.

[Conventional technology]

Conventionally, paper-phenol, glass-epoxy, and the like have been commonly used as copper-clad laminates. Here, the copper-clad laminate refers to a laminate having a wall thickness of 0.15 to 5 mm, which is used, for example, as a substrate for various electronic components.

[Problem to be solved by the invention]

However, when manufacturing paper-phenol laminates,
As the phenolic resin hardens, reaction by-products such as water are generated, and this reaction by-product has a negative effect on the physical properties of the laminate. It becomes necessary to apply pressure. moreover,
Paper-phenol laminates have the disadvantage of poor electrical properties such as dielectric constant, dielectric loss tangent, and tracking resistance. moreover,
When producing paper-phenolic or glass-epoxy laminates, the resin is usually dissolved in a solvent to form a solution, the solution is impregnated into a substrate, and the solvent is removed from the impregnated substrate to produce an intermediate called prepreg. A laminate was manufactured by forming a prepreg body and laminating the prepregs under high temperature and pressure. However, when a laminate is manufactured using such a prepreg method, there are problems in that raw material costs and equipment costs are high, and the process is complicated. In order to solve these problems, a paper-based laminate made of unsaturated polyester resin was proposed, but since unsaturated polyester resin inherently has poor heat resistance, the laminate also has poor heat resistance. There are problems such as low rigidity and insufficient strength.

In addition, epoxy resin adhesives have traditionally been used to attach copper foil to such resin laminates, but these adhesives do not have sufficient heat resistance and have low solder heat resistance. There is also the problem that the adhesive strength of the copper foil is not sufficient.

The present invention has been made in view of the above circumstances, and provides a copper-clad laminate that is manufactured without using the prepreg method and has good rigidity, strength, soldering heat resistance, peel strength of copper foil, and peel strength at high temperatures. The purpose is to provide the following.

[Means for Solving the Problem] As a result of various studies, the present inventors have developed an adhesive comprising 20 to 200 parts by weight of polyvinyl butyral and 5 to 100 parts by weight of phenolic resin to 100 parts by weight of epoxy resin. It has been discovered that the above object can be achieved by an allyl ester resin copper-clad laminate in which copper foil is laminated using copper foil, and the present invention has been completed. That is, the problems in manufacturing paper-phenol laminates and glass-epoxy laminates are solved by an allyl ester resin that can manufacture laminates without using the prepreg method, and moreover, the laminates are manufactured using this resin. As a result, it has higher physical properties than laminates manufactured using unsaturated polyester resin, better electrical properties than laminates manufactured using phenolic resin, and is also compatible with allyl ester resin laminates. By using a specific adhesive, it is possible to obtain a laminate with excellent solder heat resistance and copper foil peel strength.

Hereinafter, the content of the present invention will be explained in detail.

First, the side chain double bond type resin laminate according to the present invention will be explained. This side chain double bond type resin laminate is composed of a side chain double bond type resin. This side chain double bond type resin is a polymer composed of a main chain and a side chain, where the main chain is composed of a backbone polymer containing a vinyl monomer unit having a functional group, and the side chain is a main Refers to a polymer consisting of branches with radically curable carbon-carbon double bonds formed through functional groups in the chain. Vinyl monomers having a functional group constituting the main chain include acrylic acid, methacrylic acid, maleic anhydride, maleic acid monoester, vinyl monomers having a carboxyl group as a functional group, glycidyl methacrylate, glycidyl acrylate, etc. Vinyl monomers having a glycidyl group as a functional group, as well as allyl alcohol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydro-bovine dipropyl methacrylate, 2-hydroxypropyl acrylate,
Typical examples include vinyl monomers having an upper hydroxyl group as a functional group, such as N-methylolacrylamide, and acrylic acid and methacrylic acid are most preferably used.

The above-mentioned vinyl monomer unit having a functional group can be present as an active functional group when the main chain is formed by polymerization, or it can be polymerized by reacting the side chain described below with the functional group of the monomer in advance. It refers to a type of vinyl monomer unit that has a functional group that serves to form a side chain into the main chain, regardless of whether the main chain is formed by forming a side chain.

Examples of vinyl monomers without functional groups include styrene,
α-methylstyrene, chlorostyrene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl bromide, acrylonitrile, ethylene, propylene, butadiene, acrylic ester, methacrylic ester, vinyl acetate, vinyl propionate, diester maleate, ethyl vinyl Examples include benzene.

The weight average molecular weight of the main chain composed of these vinyl monomer units is 5000 to 400.000, preferably 10.000. (+(+(+) to 200.000. This value is appropriately selected depending on the type of side chain.

This molecular weight affects the physical properties and impregnation properties of the laminate, and
If it is less than 000, the mechanical properties of the cured laminate will be insufficient, and if it exceeds 400,000, the resin impregnation into the base material (paper etc.) will be poor, both of which are not preferred.

The amount of monomer units having functional groups in the main chain is related to the density of the side chains, and since it affects the curing reactivity between the side chains, an appropriate ratio is selected, but the side chain density in 1000 g of the main chain is 0. .1
-2 mol is preferable, and 0.4-1.5 mol is more suitable.

In addition, side chains refer to those that have a double bond at the end or in the middle that becomes >C=C, and that form branches on the main chain via the functional groups, but typical examples include: can be exemplified as a general formula such as u g l 1 (hereinafter referred to as the margin).

(I) In the formula, R1-R3 are hydrogen or a methyl group, n represents an integer of O to 5, (n) In the formula, R4 is hydrogen or a methyl group, and Ll
and represents -〇- or -NH-, Xl and X,
represents a Ct to C0 hydrocarbon group or a hydrocarbon group connected by an ether bond;

The carbon atoms bonded to the adjacent oxygens are primary or secondary carbons, and B is an aliphatic, alicyclic or aromatic hydrocarbon group up to C1°.

(III) In the formula, R6 is hydrogen or a methyl group.

Note that the side chains of the side chain double bond type resin according to the present invention are not limited to these, and any type of side chain that can form a crosslink between side chains by a radical reaction using a crosslinking vinyl monomer can be used.

Through the functional groups of the trunk polymer constructed in this way,
Various methods can be employed to introduce a branch having a radically curable carbon-carbon double bond. Some examples are as follows.

(a) When introducing via the carboxyl group of the backbone polymer, one epoxy group of an epoxy compound such as bisphenol glycidyl ether type epoxy is reacted with (meth)acrylic acid, and the remaining epoxy group and the backbone polymer are introduced. React the carboxyl groups of the coalesce.

(a) Reacting the carboxyl group of the backbone polymer with glycidyl meth)acrylate.

(1) Reacting the glycidyl group of the backbone polymer with (meth)acrylic acid.

(1) When introducing via the hydroxyl group of the backbone polymer, one incyanate group of the diisocyanate compound is reacted with 2-hydroxyethyl (meth)acrylate, and the remaining incyanate group and the hydroxyl group of the backbone polymer are reacted. Make it react.

(e) When introducing via the acid anhydride group of the backbone polymer,
A vinyl monomer having a hydroxyl group such as 2-hydroxy-ethyl (meth)acrylate is reacted with an acid anhydride group of the backbone polymer.

In the exemplified method, the main chain was polymerized first, but of course in the case of (a) and (1), one epoxy group or one incyanate group and (meth)acrylic acid or 2-hydroxyethyl (Meth)acrylate is first reacted to form part of the branches, and then polymerized to form a trunk polymer, and finally the epoxy group or incyanate group possessed by the branches of the trunk polymer and (meth)acrylic acid Alternatively, the order of the reaction may be changed, such as by reacting with 2-hydroxyethyl (meth)acrylate to obtain a side chain double bond type resin.

The side chain double bond type resin used in the present invention has a well-balanced thermoplastic resin-like property due to the characteristics of its skeletal structure and rigidity resulting from the three-dimensional crosslinking of the side chain double bonds, and is unique to unsaturated polyester resins. It has excellent impact resistance that cannot be achieved. Furthermore, other physical properties are not inferior to unsaturated polyester resins.

In producing a laminate in the present invention, a crosslinking vinyl monomer capable of radical polymerization may be mixed with the side chain double bond type resin and used. The crosslinking vinyl monomer crosslinks the unsaturated groups at the end of the side chain of the side chain double bond type resin, and it can be any of those used in ordinary unsaturated polyester resins, and among them, styrene is often used. It will be done. Other examples include α-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene, acrylic esters, methacrylic esters, diallylphthalate, and triatulcyanurate.

Naturally, the invention is not limited to this, and depending on the required physical properties, for example, to impart flexibility, an epsilon-caprolactone adduct of 2-hydroxyethyl methacrylate may be used. good. Also,
It is also possible to use mixtures of each.

The side chain double bond type resin in the present invention can be cured using a general-purpose organic peroxide, and together with the organic peroxide or alone, it can be cured with a polymerization initiator that is sensitive to light, radiation, and electron beams. Known polymerization initiators such as polymerization initiators can also be used.

Examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, 1,1-bis(t-butylperoxy) 3,3. ．． 5-trimethylcyclohegyusan, n
-Peroxyketals such as butyl-4,4-bis(t-butylperoxy)valerate, t-butyl hydroperoxide, cumene hydroperoxide, p-
Hydroperoxides such as menthane hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, Diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, peroxydicarbonate such as di-1so-propyl peroxydicarbonate, similisyl peroxydicarbonate, and bis(4-t-butylcyclohexyl)peroxydicarbonate. Carbonates, peroxy esters such as t-butylperoxypivalate, t-butylperoxy-2-ethyl hexa7ate, and t-butylperoxypenzoate are mentioned. These can be used in one type or in a mixture of two or more types depending on the type of resin and curing conditions.

In addition, flame retardants, fillers, reinforcing materials, mold release agents, colorants, curing accelerators, stabilizers, etc. may be added to the above-mentioned side chain double bond type resin to further enhance the performance of the laminate. It is also possible. In particular, in copper-clad laminates, the proportion of flame retardant grades used is high, and appropriate use of flame retardants is effective. The flame retardant used here is mainly a halogen-based flame retardant, and the type and addition ratio are determined according to the requirements for flame retardation of the laminate.

Representative examples include tetrabromo phthalic anhydride, tetrachlorophthalic anhydride, Hett's acid, dibromophenyl glycidyl ether, 2,3-dibromopropanol, 2
．． 3-1 chloropropatol, dibromoneopentyl glycol, bromobenzene, decabromodiphenyl ether, pentabromodiphenyl ether, tetrafluorobisphenol A1 hexabromocyclododecane, perchlorocyclopentadecane, chlorinated halafine,
and y) acids. In addition, when curing the side chain double bond type resin, it is also a useful method to chemically react the resin and a flame retardant component to cure the resin and simultaneously achieve flame retardancy. The advantage of this method is that since it is a reactive method, there is no migration of flame retardant components from the cured resin. The flame retardant component used in such cases has one or more unsaturated groups in its structure, for example, 2°3
- Synthesized by reacting combinations such as dibromopropanol with maleic anhydride, epichlorohydrin with acrylic acid or methacrylic acid, dibromoneopentyl glycol with acrylic acid or methacrylic acid.

A side chain double bond type resin or a resin composition mainly composed of the side chain double bond type resin can be used for producing a copper-clad laminate according to a known method. That is, a base material is impregnated with the above-mentioned resin composition, a plurality of impregnated base materials are laminated, a copper foil coated with an adhesive as described below is layered on one or both sides, and heated and cured without pressure or under pressure. A copper-clad laminate can be manufactured by molding. Of course, it is also possible to first form a laminate and then laminate it with copper foil coated with an adhesive.

The above base material can be the same as the base material used for conventional laminates, such as glass base materials such as glass fiber cloth and glass nonwoven fabric, cellulose base materials such as kraft paper, linter paper, cotton paper, etc. Refers to paper base materials, inorganic fiber-based sheet-like or band-like base materials, etc.

When paper is used as the base material, from the viewpoint of impregnability and quality, paper mainly composed of cellulose fibers, such as kraft paper, having an air-dried density of 0.3 to 0.7 g/cm' is preferable.

Before impregnating these base materials with the impregnating resin composition, N
- It is also possible to improve the electrical properties by impregnating and drying with a methylol compound, phenol resin, silane coupling agent, etc.

Next, the adhesive used in the present invention will be explained.

The epoxy resin herein is a compound that has two or more oxirane rings in one molecule and becomes three-dimensional by using a curing agent. Although there are many types and various types can be used, glycidyl type epoxy resin is preferred among them. Further, among the glycidyl type epoxy resins, it is particularly preferable in the present invention to use a mixture of bisphenol A diglycidyl ether and novolac polyglycidyl ether in an appropriate ratio, but the invention is of course not limited thereto. In this case, the mixing ratio of bisphenol A diglycidyl ether and novolac polyglycidyl ether is preferably 40 to 90% by weight of the former and 10 to 60% by weight of the latter.

There are many types of curing agents used. The types of polyamines include diethylenetriamine,
triethylenetetramine, tetraethylenepentamine,
Linear aliphatic polyamines such as diethylaminopropylamine, menthendiamine, infrondiamine, N-
Aminoethylpiperazine, 3.9-bis(3-aminopropyl), ~2.4,8.10-tetraoxyspiro(
5゜5) Undecane adduct, bis(4-amino-3~
Alicyclic polyamines such as methylcyclohexyl)methane and bis(4-aminocyclohexyl)methane, aromatic polyamines such as m-xylene diamine, diaminodiphenylmethane, m-phenylenediamine, and diaminodiphenylsulfone, various polyamides Examples of acid anhydrides include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and dodecyl succinic anhydride. Acid, chlorendic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimate), methylcyclohexenetetracarboxylic anhydride, trimellitic anhydride, polyazelaic anhydride, etc. Others include phenol novolacs, polymercaptans, and polysulfides. The above are classified as polyaddition type, but as those classified as catalytic type, the anionic polymerization type is classified as 2.4.
6-) Lis(dimethylaminomethyl)phenol, various imidazoles, and cationic polymerization types include BF and monoethylamine complexes.

In addition, dicyandiamide may be mentioned as a latent curing agent. The present invention is not limited to these, and appropriate selection can be made depending on the purpose.

The polyvinyl butyral used preferably has a composition ratio of vinyl butyral groups in the molecular chain of 78% by weight or more and an average degree of polymerization of 500 to 5,000. If the composition ratio is less than 75% by weight or the average degree of polymerization is less than 500, problems will occur in the heat resistance of the adhesive, and if the average degree of polymerization is less than 500, problems will occur.
,000, the solubility in solvents deteriorates.

The blending ratio of polyvinyl butyral to 100 parts by weight of epoxy resin is preferably 10 to 300 parts by weight, and 20 to 300 parts by weight.
200 parts by weight is preferred. If it is less than 10 parts by weight, the beer strength of the copper foil will be low, and if it exceeds 300 parts by weight, the solder heat resistance will be poor.

The phenol resin used is a product obtained by reacting phenols with formaldehyde, and examples of the phenol resins include phenol, cresol, and phenol. For the present invention, resol type resins produced using alkaline catalysts are preferably used, but are not limited thereto. The blending ratio of this phenol resin is 5 to 100 parts by weight per 100 parts by weight of the epoxy resin. If it is less than 5 parts by weight, no improvement in heat resistance will be obtained, and if it exceeds 100 parts by weight, flexibility will be insufficient and it will become brittle.

The epoxy resin, curing agent, polyvinyl butyral, and phenolic resin are mixed and dissolved using a suitable solvent to form an adhesive formulation. Depending on the type of curing agent, for example, dicyandiamide may be used in a dispersed state. Therefore, the type of solvent is not limited, and is appropriately selected depending on the purpose, coating process, etc.

It is also possible to add fillers, reinforcing materials, coloring agents, hardening accelerators, anti-aging agents, stabilizers, etc. to this adhesive formulation as required.

Furthermore, the copper foil used in the present invention refers to copper foil generally used for copper-clad laminates for electric circuits, that is, electrolytic copper foil and rolled copper foil. , a blade coater, a wire bar coater, or the like may be selected as appropriate. The copper foil coated with the adhesive is preferably heat-treated to remove the solvent and to be used in a partially cured state.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples unless it departs from the gist of the present invention. Throughout this specification, all temperatures are in degrees Celsius, and parts and percentages are by weight unless otherwise specified.

〔Example〕

Production example Production of resin liquid mainly composed of side chain double bond type resin Separable flask (3000 mC
), methacrylic acid (30 g, 0.41 mol), methyl ethyl ketone (400 g), styrene monomer (80 g,
0 g, 7.7 mol), azobisisobutyronitrile (5
, 0g) and dodecyl mercaptan (12g),
Polymerization was carried out at 75 to 80° C. for 10 hours under a nitrogen atmosphere. Hydroquinone (0.5 g') was added to inhibit polymerization. The polymerization rate of the styrene monomer is 76% and the polymerization rate of methacrylic acid is 93%, and a polymer-containing liquid containing a styrene-methacrylic acid copolymer having a weight average molecular weight of about 50,000 is obtained.

In addition, another reactor with the same configuration as above was installed with "Epicoat 82".
7J (trade name of epoxy resin, manufactured by Yuka Shell Epoxy Co., Ltd.) (360 g, 1 mol), methacrylic acid (138 g
, 1.6 mol), benzyldimethylamine (1.2 g)
, prepared rosebenzoquinone (0.12g) and heated to 120℃.
The mixture was reacted for 3 hours under a nitrogen atmosphere. After the reaction, the acid value became almost zero, and a vinylation reagent containing an epoxy resin containing an unsaturated phase was obtained.

Add the entire amount of the previously prepared polymer-containing group to the vinylation reagent, add triphenylphosphine (5 g) and rosebenzogynone (0.10 g) and heat to distill off the methyl ethyl ketone solvent at a boiling point of 110 ° C. 5 at the same temperature
Allowed time to react.

After the reaction, the unsaturated group-containing epoxy resin is about 1
It became 5%. While styrene monomer (10100O) was added intermittently, heating evaporation was continued at 30 to 50 mmHg.Methyl ethyl ketone detected in the distillate was 0.
．． The operation was terminated when it became 1% or less. The thus obtained resin liquid containing the curable prepolymer is mainly composed of the side chain double bond type resin having side chains of the type (I), and has a viscosity of 6.2% with a non-volatile content of 52% by weight. Poise (
It was a yellowish brown liquid at a temperature of 25°C.

Next, an example using the obtained resin liquid will be described.

Examples 1 to 5 and Comparative Examples 1 to 3 Kraft paper with a tsubo j of 1155 g/m'' and a thickness of 300 um was soaked in a water-methanol solution of melamine resin (5305 manufactured by Nippon Carbide Co., Ltd.), air-dried, and then dried at 120°C for 30 minutes. The amount of melamine resin adhered to 100 parts by weight of kraft paper was 18 parts by weight.This paper base material was immersed in the blended solution of the resin composition shown in Table 2 to impregnate it with the resin solution.
Seven sheets were stacked one on top of the other, a copper foil coated with the adhesive shown in Table 2 was stacked on one side, and a 50 μm polyester film was stacked on both sides, followed by heating and pressure molding with a press machine. The conditions are 140'C - 10 minutes - 20kg/c
m”. After pressing, it was heated at 150°C in a hot air drying oven.
Heating was performed for 5 hours to obtain a copper-clad laminate with a thickness of 1.6 mm. Table 3 shows the results of measuring the physical properties of the copper-clad laminate.

As is clear from the results in Table 2, the copper-clad laminate of the present invention has excellent solder heat resistance and also has high peel strength of the copper foil at room temperature and when heated.

〔Effect of the invention〕

The copper-clad laminate of the present invention can be manufactured without using the prepreg method, and has advantages such as excellent rigidity, strength, soldering heat resistance, and peel strength of copper foil at room temperature and when heated. be able to.

Claims (2)

[Claims] (1) The side chain double bond type resin laminate and the copper foil contain 10 to 3 parts by weight of polyvinyl butyral per 100 parts by weight of the epoxy resin.
A copper-clad laminate laminated using an adhesive containing 0.00 parts by weight and 5 to 100 parts by weight of a phenolic resin. (2) The above epoxy resin contains 40 to 90% by weight of bisphenol A type epoxy resin and 1 part of novolak type epoxy resin.
The copper-clad laminate according to claim 1, comprising 0 to 60% by weight.