JPH06255027A - Metal foil-clad laminate for electricity - Google Patents

Abstract

PURPOSE:To obtain a laminate with a metal foil for electricity which dispenses with the use of a solvent on the occasion when a reinforcing material is impregnated with resin in a manufacturing process and which is excellent in heat resistance, water resistance, chemical resistance, electrical characteristics, etc., and can be bent. CONSTITUTION:A long-chain dibasic acid (a), multifunctional epoxy resin (b) and epoxy-containing (meta) acrylate (c) are made to react with one another, in the rate of the total sum of epoxy groups of (b) and (c) being 0.8 to 1.2 in an equivalent amount to 1 equivalent of an acid radical of (a) and in the equivalent ratio between an epoxy group of (b) and an epoxy group (c) being 2:1 to 1:2. A cured material of a thermosetting resin composition containing unsaturated ester thus obtained and a radical polymerization initiator is reinforced with a sheet-shaped fiber material. A metal leaf is laminated on at least one side of a fiber-reinforced resin layer thus prepared and is integrated therewith.

Description

Detailed Description of the Invention

[0001]

This invention relates to water resistance, electrical characteristics,
The present invention relates to a metal foil-clad laminate for electric use, which has excellent heat resistance and can be bent.

[0002]

2. Description of the Related Art A metal foil-clad laminate for electrical use, such as a printed wiring board, is impregnated with a reinforcing material such as paper, glass fiber, synthetic fiber, etc., with a phenol resin, an epoxy resin, an unsaturated polyester resin, etc. and cured. There are a hard type that uses a fiber reinforced plastic obtained as a base material and a flexible type that uses a film such as polyimide or polyester as a base material.

Since the rigid type laminated plate has high rigidity, it has a high degree of freedom in the type and number of electronic components that can be mounted, and has been widely used in the past. However, in response to the recent miniaturization of electronic devices, when trying to store a printed wiring board obtained from this rigid type laminated board in a limited space, it cannot be bent due to its high rigidity. Therefore, a complicated process of dividing the board and connecting the divided boards and an extra part for connecting the boards are required.

On the other hand, the flexible type laminated plate can be freely bent, so that the printed wiring board obtained from this type of laminated plate can be easily accommodated according to the shape of electronic equipment. it can. But,
Due to the extremely low rigidity, the flexible type laminate has a large restriction on the type and number of electronic components that can be mounted, and its application is also limited.

To solve the above problems, a base material obtained by dissolving an epoxy resin in a solvent once and impregnating the reinforcing material and then removing the residual solvent by drying is laminated and integrated with a copper foil. A workable metal foil-clad laminate has been proposed (Japanese Patent Laid-Open Nos. 59-184587 and 6-1986).
2-213193). However, as described above, this laminated board requires a solvent in order to impregnate the reinforcing material with the epoxy resin in the manufacturing process thereof, and after the impregnation, the solvent needs to be dried and removed. It is not preferable from the viewpoint of resource saving and energy saving.

Unsaturated polyester resins and vinyl ester resins are well known as resins that can be easily impregnated into a reinforcing material alone without using a solvent. Unsaturated polyester resin and vinyl ester resin are generally excellent in heat resistance, mechanical properties, electrical characteristics, water resistance, chemical resistance, etc., and are therefore used for hard type electrical metal foil-clad laminates. (JP-A-55-4838)
And Japanese Patent Laid-Open No. 60-84350).

[0007]

However, since the above-mentioned unsaturated polyester resin and vinyl ester resin have high rigidity, they cannot be applied to a metal foil-clad laminate for electric use which can be bent. Flexible unsaturated polyester resins and vinyl ester resins are also known, but these have poor water resistance and chemical resistance, poor electrical properties, and poor flame retardancy. It was difficult to use for a metal foil-clad laminate.

Therefore, in the present invention, it is not necessary to use a solvent in order to impregnate the reinforcing material with the resin in the manufacturing process, and therefore, the solvent removal treatment after the impregnation is not necessary, and the heat resistance, water resistance and chemical resistance are not required. It is an object of the present invention to provide a metal foil-clad laminate for electrical use, which has excellent properties and electrical characteristics and which can be bent.

[0009]

In order to solve the above problems, the inventors have made various studies. As a result, as a resin to be impregnated into the reinforcing material, a long-chain dibasic acid, an unsaturated ester obtained by reacting a polyfunctional epoxy resin and an epoxy group-containing (meth) acrylate at a predetermined equivalent ratio, which will be described in detail later, The present invention has been completed by confirming by experiments that a thermosetting resin composition containing a radical polymerization initiator as an essential component may be used.

Therefore, the metal foil-clad laminate for electrical use according to the present invention has a long-chain dibasic acid (a) in which the total number of carbon atoms other than those contained in the acid group is 12 or more per molecule,
An epoxy resin (b) having two or more epoxy groups in one molecule and a (meth) acrylate (c) having one epoxy group in one molecule are prepared from the epoxy groups of the above (b) and (c). The ratio in which the total is 0.8 to 1.2 equivalents per 1 equivalent of the acid group possessed by (a), and the equivalent ratio of the epoxy group possessed by (b) and the epoxy group possessed by (c) is 2 The cured product of the thermosetting resin composition containing the unsaturated ester (A) obtained by reacting at a ratio of 1: 1 to 1: 2 and the radical polymerization initiator (B) as essential components is in the form of a sheet. It has a fiber reinforced resin layer reinforced with a fiber material and a metal foil laminated on at least one side of the fiber reinforced resin layer and integrated with the fiber reinforced resin layer. Laminates may be abbreviated as “laminates”. ).

First, the thermosetting resin composition used in the present invention will be described below. This thermosetting resin composition constitutes a fiber reinforced resin layer by reinforcing the cured product with a sheet-shaped fiber material. This thermosetting resin composition contains an unsaturated ester (A) and a radical polymerization initiator (B) as essential components.

The unsaturated ester (A) is a long-chain dibasic acid (a) having a total of 12 or more carbon atoms per molecule other than those contained in the acid group, and two epoxy groups in one molecule. It is obtained by reacting the epoxy resin (b) having the above and the (meth) acrylate (c) having one epoxy group in one molecule in a predetermined equivalent ratio described below. A long-chain dibasic acid (a) used as one of the raw materials of the unsaturated ester (A) and having a total of 12 or more carbon atoms per molecule other than those contained in the acid group (hereinafter referred to as "long (Abbreviated as "chain dibasic acid (a)") has two acid groups in one molecule, and the total number of carbon atoms other than those contained in these acid groups is 12 or more per molecule. Which is a compound having a long-chain molecular structure. This long-chain dibasic acid (a)
Is used to form a soft segment portion in the molecular structure of the unsaturated ester (A), which imparts bendability (flexibility) to the laminate. If the total number of carbon atoms other than those contained in the acid group is less than 12 per molecule, the flexibility of the laminate becomes insufficient,
It is not preferable because the laminate cannot be bent arbitrarily. Further, it is possible to use a compound having 3 or more acid groups in one molecule in combination, but if the amount of this compound used is too large, the flexibility of the laminate decreases and the unsaturated ester (A) is produced. At times, a gelled product is formed, which is not preferable.

The long-chain dibasic acid (a) may be linear or may have a branch or a substituent. The substituent is not particularly limited, for example, an alkyl group, an alkenyl group, a cycloalkyl group,
Examples thereof include cycloalkenyl group, phenyl group and nitrile group. The number of carbon atoms constituting the main chain of the long-chain dibasic acid (a) molecule (excluding those contained in the acid group) is 10
The above is preferable.

The long chain dibasic acid (a) may have an acid group at the end of the molecule or may have a side chain. The acid group contained in the long-chain dibasic acid (a) is not particularly limited, and examples thereof include a carboxyl group, a sulfone group, a sulfin group, a sulfene group, a thiocarboxyl group, and a dithiocarboxyl group. The two acid groups of the long-chain dibasic acid (a) may be the same or different in type. Among the above acid groups, the long-chain dibasic acid (a) having a carboxyl group is preferable because it is easily available.

Specific examples of the long-chain dibasic acid (a) are not particularly limited, but for example, tetradecanedioic acid, hexadecanedioic acid, eicosanedioic acid, 1,16-
(6-Ethylhexadecane) -dicarboxylic acid, 1,18
-(7,12-octadecadiene) -dicarboxylic acid,
1,12- (6-ethynyldodecane) -dicarboxylic acid,
1,18- (7-Ethynyloctadecane) -dicarboxylic acid, 1,14- (7,8-diphenyltetradecane)-
Dicarboxylic acid, 5- (7-carboxyheptyl) -2-
Hexyl-3-cyclohexenecarboxylic acid may be mentioned. In addition, dimer acid and hydrogenated dimer acid obtained from linoleic acid and the like (also referred to as hydrogenated dimer acid), further both ends carboxyl group-containing liquid butadiene-acrylonitrile copolymer, both ends carboxyl group-containing liquid polybutadiene, Examples include polybutyl acrylate having carboxyl groups at both ends. Among these, the use of dimer acid or hydrogenated dimer acid is particularly preferable from the viewpoint of the physical property balance of the laminate. The long-chain dibasic acid (a) is used alone or in combination of two or more.

An epoxy resin (b) having two or more epoxy groups in one molecule, which is one of the raw materials for the unsaturated ester (A) (hereinafter referred to as "multifunctional epoxy resin (b)").
Is used to form a hard segment portion that imparts various properties such as heat resistance, water resistance, chemical resistance, and electrical characteristics to the laminate in the molecular structure of the unsaturated ester (A). The polyfunctional epoxy resin (b) has a molecular weight of 14
0 to 3000 range, epoxy equivalent 70 to 1500
The range of (g / equivalent) is preferable.

The polyfunctional epoxy resin (b) is not particularly limited, but for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin. , Epoxidized polybutadiene, tetraglycidyl diaminodiphenylmethane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and the like. Among these, aromatic epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, and cresol novolac type epoxy resin are preferable. In particular, when a polyfunctional epoxy resin having a bromine-substituted bisphenol A skeleton is used, a bromine atom is introduced into the molecular skeleton of the cured product of the thermosetting resin composition to improve the flame retardancy of the cured product, It is preferable because high flame retardancy is imparted to the laminated plate.

The polyfunctional epoxy resin (b) is used alone or in combination of two or more. Unsaturated ester (A)
(Meth) acrylate (c) having one epoxy group in one molecule, which is one of the starting materials (hereinafter referred to as "epoxy group-containing (meth) acrylate (c)". In the description, "(meth) acrylate" means acrylate and / or methacrylate.)
Is used to give the unsaturated ester (A) a carbon-carbon unsaturated double bond. The epoxy group-containing (meth) acrylate (c) is not particularly limited, but examples thereof include glycidyl acrylate, glycidyl methacrylate, -3,4-epoxybutyl acrylate,
Methacrylic acid-3,4-epoxybutyl, methacrylic acid-4,5-epoxypentyl, acrylic acid-6,7-epoxypentyl, 2-methylglycidyl acrylate,
2-Methylglycidyl methacrylate and the like can be mentioned.
Among these, glycidyl acrylate and glycidyl methacrylate are particularly preferable. The epoxy group-containing (meth) acrylate (c) is used alone or in combination of two or more.

In the reaction of the long-chain dibasic acid (a), the polyfunctional epoxy resin (b) and the epoxy group-containing (meth) acrylate (c), the total of the epoxy groups of (b) and (c) is (a). 0.8) per 1 equivalent of the acid group of
The ratio is 1.2 equivalents, and the equivalent ratio of the epoxy group of (b) to the epoxy group of (c) is 2: 1 to
It is carried out using these (a), (b) and (c) in a ratio of 1: 2. If the reaction is carried out in an amount used outside of the above-mentioned ratio, the crosslink density of the cured product of the thermosetting resin composition becomes too low or too high, and the bending workability of the laminate, heat resistance, and water resistance. This is because the balance of physical properties such as chemical resistance and electric properties is impaired, which is not preferable.

The number average molecular weight of the unsaturated ester (A) is not particularly limited, but it is 800 to 10
The range of 000 is preferable. When the molecular weight is less than the above range, the crosslink density of the cured product of the thermosetting resin composition becomes too high and the bending workability of the laminate is reduced, and when the molecular weight exceeds the above range, the thermosetting resin composition This is because the cross-linking density of the cured product becomes too low, and the heat resistance, water resistance, chemical resistance, electrical characteristics, etc. of the laminated plate deteriorate.

The unsaturated ester (A) may be obtained by using (meth) acrylic acid in addition to (a), (b) and (c) as a reaction raw material (this specification). In the description, "(meth) acrylic acid" means acrylic acid and / or methacrylic acid). (Meth) acrylic acid optimizes the cross-linking interval of the unsaturated ester (A) in order to balance the bending workability, heat resistance, water resistance, chemical resistance, and electrical characteristics of the laminate. Used for the purpose. When (meth) acrylic acid is used, (meth) acrylic acid has an equivalent ratio of an acid group of (meth) acrylic acid to an acid group of long-chain dibasic acid (a) of 0.
It is used by replacing part of the long-chain dibasic acid (a) with (meth) acrylic acid so as to be in the range of 5 or less, preferably 1/99 to 1/2.

The method for producing the unsaturated ester (A) by carrying out the above reaction is not particularly limited, but the production method I described below is preferable. The manufacturing method I is a method including the following two steps I-1 and I-2. (I-1) Using an organic acid salt of zinc as an esterification catalyst, by subjecting a long-chain dibasic acid (a) and an epoxy group-containing (meth) acrylate (c) to an esterification reaction,
A step of obtaining an acid group-containing (meth) acrylate.

(I-2) selected from the group consisting of amines, acid addition products of amines, quaternary ammonium salts, amides, imidazoles, pyridines, phosphines, phosphonium salts and sulfonium salts. A step of esterifying the acid group-containing (meth) acrylate and the polyfunctional epoxy resin (b) using at least one compound as an esterification catalyst.

The manufacturing method I is characterized in that the above two steps I-1 and I-2 are divided in time series. The reaction between the long-chain dibasic acid (a) and the epoxy group-containing (meth) acrylate (c) in Step I-1 is performed by reacting the long-chain dibasic acid (a) with an epoxy group-containing (meth) acrylate (c) per one equivalent of the epoxy group. The basic acid (a) has an acid group of 1.25
It is preferable to carry out the treatment so that the ratio is about 3.75 equivalents. When the equivalent weight of the acid group of the long-chain dibasic acid (a) is below the above range, it becomes difficult to design the physical properties of the resin based on the molecular skeleton of the polyfunctional epoxy resin (b) introduced in the step (I-2). Further, if the equivalent weight of the acid group of the long-chain dibasic acid (a) exceeds the above range, the crosslink density of the cured product will decrease, and the physical properties of the resin will decrease.

In the production method I, an organic acid salt of zinc is used as a catalyst for the esterification reaction in step I-1. The organic acid salt of zinc is used here to promote the esterification reaction without causing gelation even when the epoxy group-containing (meth) acrylate (c) coexists. The organic acid salt of zinc that can be used is not particularly limited, and examples thereof include zinc octylate, zinc naphthenate, zinc laurate, zinc ricinoleate, zinc benzoate, zinc salicylate, zinc paraoxybenzoate, and cresothin. Examples thereof include zinc acid and zinc 2,3-oxynaphthoate. These are used alone or in combination of two or more. Here, the organic acid is zinc that is soluble in the long-chain dibasic acid (a), the polyfunctional epoxy resin (b), the epoxy group-containing (meth) acrylate (c), and the reaction product, which are raw materials. Any organic acid that forms a salt may be used.

The amount of the organic acid salt of zinc used is, for example, in terms of metallic zinc, the reaction product, that is, the long-chain dibasic acid (a).
The ratio is preferably 0.005 to 3.0% by weight based on the total weight of the epoxy group-containing (meth) acrylate (c). This is because if it exceeds this range, the physical properties of the cured resin may be deteriorated, and if it is below this range, the esterification reaction rate may be slow and the target product may not be substantially obtained.

The esterification reaction in step I-1 is carried out, for example, in an inert solvent such as toluene or xylene, if necessary, and more preferably as a component of the resin composition as it is unnecessary to remove after completion of the reaction. In the presence of a radical polymerization inhibitor such as air, hydroquinone or benzoquinone in the radical polymerizable unsaturated monomer (C) described below such as styrene, vinyltoluene, methyl (meth) acrylate, diallyl phthalate, etc. , 70-130
It is performed under the condition of a temperature range of ° C. This reaction is preferably carried out until the epoxy groups are substantially disappeared.

By this esterification reaction, an acid group-containing (meth) acrylate is obtained. This acid group-containing (meth) acrylate has one acid group and one (meth) acryloyl group in one molecule.
In step I-2, the acid group-containing (meth) acrylate and the polyfunctional epoxy resin (b) are subjected to an esterification reaction.
In the step I-2, (meth) acrylic acid may be further used to cause an esterification reaction between the (meth) acrylic acid and the acid group-containing (meth) acrylate and the polyfunctional epoxy resin (b). included.

As the reaction catalyst in step I-2, amines, acid addition products of amines, quaternary ammonium salts, amides, imidazoles, pyridines, phosphines,
At least one compound selected from the group consisting of phosphonium salts and sulfonium salts is used.
Specific examples of these compounds are as follows. The amines are not particularly limited, but for example, triethylamine, N, N-dimethylaniline, dimethylbenzylamine, triethanolamine, tributylamine, dimethyllaurylamine, tripropylamine, diethylaminoethyl methacrylate, hexamethylenediamine, 1 , 8-diazabicyclo (5,4,0) undecene-7, tris (dimethylaminomethyl) phenol, and the like, and these may be used alone or in combination of two or more.

The amine acid addition products are not particularly limited as long as one or both of an organic acid and an inorganic acid are added to the amine, and examples thereof include dimethylamine hydrochloride, diethylamine hydrochloride, Examples include triethylamine hydrochloride, dimethylamine acetate, diethylamine acetate, triethylamine acetate, etc.
Used alone or in combination of two or more.

The quaternary ammonium salt is not particularly limited, and examples thereof include tetramethylammonium chloride, tetramethylammonium bromide, trimethyldodecyl ammonium chloride, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, and the like. They may be used alone or in combination of two or more.

The amides are not particularly limited, but include, for example, formamide, N-methylformamide, N-ethylformamide, acetamide, benzamide, N, N-dimethylformamide, N, N-diethylacetamide, N, N-. Dimethyl acrylamide and the like can be mentioned, and these can be used alone or in combination of two or more.

The imidazoles are not particularly limited, but for example, 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-1-vinylimidazole, 2 -Ethyl-5-methylimidazole and the like can be mentioned, and these can be used alone or in combination of two or more.

The pyridines are not particularly limited, and examples thereof include pyridine, pyridine hydrochloride, vinyl pyridine, p-dimethylaminopyridine, γ-picoline and the like, and these may be used alone or in combination of two or more. used. The phosphines are not particularly limited, and examples thereof include triphenylphosphine, tri (2-methylphenyl) phosphine, tri (3-methylphenyl) phosphine, tri (4-methylphenyl) phosphine, and the like. They may be used alone or in combination of two or more.

The phosphonium salts are not particularly limited, and examples thereof include triphenylmethylphosphonium iodide, trimethylphenylphosphonium bromide, triphenylmethylphosphonium bromide, trimethylbenzylphosphonium bromide, and the like.
These are used alone or in combination of two or more. The sulfonium salts are not particularly limited, but include, for example, triphenylsulfonium chloride, trimethylsulfonium chloride, dimethylphenylsulfonium chloride, etc. These may be used alone or in combination of two or more.

The amount of the reaction catalyst used in step I-2 is, for example, the total weight of the reactants, that is, the acid group-containing (meth) acrylate and the polyfunctional epoxy resin (b) (when using (meth) acrylic acid, Weight is added), and 0.
The ratio is preferably 005 to 3.0% by weight. This is because if it exceeds this range, the physical properties of the cured resin may be deteriorated, and if it is below this range, the esterification reaction rate may be slow and the desired product may not be substantially obtained.

In step I-2, the acid group-containing (meth) acrylate and polyfunctional epoxy resin (b), or the acid group-containing (meth) acrylate and (meth) acrylic acid and polyfunctional epoxy resin (b) are For example, an acid group of the acid group-containing (meth) acrylate (when using (meth) acrylic acid, the total of acid groups of the acid group-containing (meth) acrylate and (meth) acrylic acid) and a polyfunctional epoxy resin ( The equivalent ratio with the epoxy group of b) is 0.8: 1 to
It is preferable to be subjected to the esterification reaction in the range of 1.2: 1. When (meth) acrylic acid is used in combination, the ratio of the polyfunctional epoxy resin (b) and the (meth) acrylic acid may be, for example, (1 equivalent of the epoxy group of the polyfunctional epoxy resin (b)) The carboxyl group of (meth) acrylic acid is in the range of 0.5 equivalent or less, preferably in the range of 0.01 to 0.5 equivalent, and the molecular weight distribution of the target unsaturated ester (A) and the crosslink density of the cured product are obtained. It is arbitrarily selected according to the degree of.

The esterification reaction in step I-2 is carried out, for example, in an inert solvent such as toluene or xylene, if necessary, and more preferably in the same manner as in the esterification reaction in step I-1, styrene or vinyl. In a radical-polymerizable unsaturated monomer (C) such as toluene, methyl (meth) acrylate or diallyl phthalate described below, in the presence of a radical polymerization inhibitor such as air or hydroquinone or benzoquinone at 70 to 130 ° C. It is performed under the condition of temperature range.

The esterification reaction in step I-2 gives the unsaturated ester (A). This unsaturated ester (A) has two or more (meth) acryloyl groups in one molecule. According to the manufacturing method I described above,
It becomes easy to introduce not only the hard segment derived from the polyfunctional epoxy resin (b) but also the soft segment derived from the long-chain dibasic acid (a) into the resulting unsaturated ester (A), which results in unsaturated The degree of freedom in the molecular design of the ester (A) is increased. Further, when (meth) acrylic acid is also used in the step I-2, the degree of freedom in the molecular design of the unsaturated ester (A) is further increased. Therefore, according to the production method I, the unsaturated ester (A) having desired physical properties is obtained.
Can be easily obtained.

The radical polymerization initiator (B) contained in the thermosetting resin composition used in the present invention is not particularly limited, but examples thereof include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; Hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide; Diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; 1,1-
Peroxyketals such as bis (t-butylperoxy) -3,3,5-trimethylcyclohexanone; peroxyesters such as t-butylperoxybenzoate and t-butylperoxyoctate; dicumyl peroxide and the like Dialkyl peroxides; peroxydicarbonates such as dimyristyl peroxydicarbonate and the like are used. The radical polymerization initiator (B) is
They may be used alone or in combination of two or more.

Further, if necessary, a promoter such as a cobalt salt or a tertiary amine may be used in combination. The content of the radical polymerization initiator (B) in the thermosetting resin composition is
Although not particularly limited, the unsaturated ester (A) (when the radical-polymerizable unsaturated monomer (C) described later is used, the total of this (C) and the unsaturated ester (A)) is 0.
The range of 05 to 5% by weight is preferable. When the content of the initiator (B) is less than the above range, the curing is incomplete, and the laminate cannot exhibit desired physical properties. When the content of (B) exceeds the above range, (B) is cured. This is because they remain in the product and cause deterioration of the physical properties of the laminate.

The thermosetting resin composition used in the present invention may further contain a radically polymerizable unsaturated monomer (C), if necessary. The radically polymerizable unsaturated monomer (C) refers to a compound that has at least one vinylically unsaturated group in one molecule and is liquid at room temperature. When this monomer (C) is used, it acts as a solvent, making it easier to impregnate the fiber material with the thermosetting resin composition, and the monomer (C) is Since it is incorporated into the crosslinked structure of the cured product when the curable resin composition is cured, it is not necessary to remove it and the crosslink density of the cured product is increased, which is preferable.

Specific examples of the radically polymerizable unsaturated monomer (C) are not particularly limited, but for example, aromatic vinyl compounds such as styrene, vinyltoluene, divinylbenzene, α-methylstyrene and chlorostyrene. Vinyl esters such as vinyl acetate and adipic acid divinyl ester; diallyl phthalate; (meth) acrylic acid; methyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, diethylene glycol di (meth) acrylate, 2- Examples thereof include (meth) acrylic acid esters such as hydroxyethyl (meth) acrylate. Among these, styrene is particularly preferable because of its solvent performance, polymerization reactivity and the like. The radical polymerizable unsaturated monomer (C) is used alone or in combination of two or more.

When the radical-polymerizable unsaturated monomer (C) is contained in the thermosetting resin composition, the content thereof is not particularly limited, but the unsaturated ester (A) and the monomer (C 5) to 50% by weight based on the total of When the content of the monomer (C) is less than the above range, the viscosity of the thermosetting resin composition increases depending on the molecular weight of the unsaturated ester (A), and the fibrous material is impregnated with the thermosetting resin composition. When the content of the monomer (C) exceeds the above range, the physical properties based on the structure of the unsaturated ester (A) are difficult to be exhibited.

The thermosetting resin composition contains, in addition to the above-mentioned components, various additives contained in the conventional unsaturated polyester resin composition, such as aluminum hydroxide, clay and talc, if necessary. A filler, a silane coupling agent such as acrylic silane, a pigment or a colorant, a flame retardant or a flameproofing agent, an antifoaming agent, a wetting agent and the like. Further, if desired, a thermoplastic resin, an elastomer and the like can be blended within a range that does not impair the achievement of the object of the present invention.

The fiber-reinforced resin layer of the laminate according to the present invention is formed by reinforcing the cured product of the above-mentioned thermosetting resin composition with a sheet-shaped fiber material. The sheet-shaped fiber material used as the reinforcing material is not particularly limited, but for example, a non-woven fabric or a woven fabric obtained by using glass fiber, natural fiber, synthetic fiber or the like alone or by using two or more kinds of these fibers in combination. Is used. The thickness of the sheet-shaped fiber material is preferably in the range of 0.05 to 1.0 mm.
The sheet-shaped fiber material is usually a combination of a plurality of sheets,
The total thickness of the fiber reinforced resin layer is, for example, 0.1 to 2.0 mm
To be laminated. However, not limited to this,
Only one sheet of fiber material may be used. In addition,
When a plurality of sheet-shaped fiber materials are used, the plurality of fiber materials may be of the same type or may be a mixture of different types.

The weight ratio of the cured product of the thermosetting resin composition and the sheet-shaped fiber material constituting the fiber reinforced resin layer is 9
The range of 5: 5 to 50:50 is preferable. When this weight ratio is below the above range (when the weight ratio of the above-mentioned cured product is too low), the dimensional stability as a laminate decreases, and when it exceeds the above range (when the above-mentioned weight ratio of the above-mentioned cured product is too high). This is because the bending workability of the laminated plate is reduced.

The total thickness of the fiber reinforced resin layer is 0.1 to 2.0.
The mm range is preferred. This is because if it is less than this range, the rigidity of the laminate becomes too low, which causes a problem when components are mounted on the laminate, and if it exceeds the above range, the bending workability of the laminate deteriorates. The material of the metal foil laminated on the fiber reinforced resin layer and integrated with the fiber reinforced resin layer is not particularly limited, but examples thereof include copper and aluminum. The metal foil may be laminated only on one side of the fiber reinforced resin layer or may be laminated on both sides of the fiber reinforced resin layer. The thickness of the metal foil is 5-1
The range of 00 μm is preferable. When the thickness of the metal foil is less than the above range, the strength of the metal foil is reduced, and the metal foil is likely to have a defect during the bending process of the laminated plate. When the thickness exceeds the above range, the bending resistance of the laminated plate is increased, This is because it is not preferable.

The method for producing the laminated plate of the present invention is not particularly limited, but for example, the following method can be adopted. A sheet of fibrous material is impregnated with a thermosetting resin composition by a dipping method or the like to laminate a predetermined number of impregnated bodies (prepregs) on a metal foil, or heat curing on a metal foil After spraying the thermosetting resin composition, by placing a sheet-like fiber material on it and impregnating the fiber material with the thermosetting resin composition (if necessary, further laminating a metal foil thereon). May be used), such as a method of obtaining a laminate composed of a sheet-shaped fiber material impregnated with a thermosetting resin composition and a metal foil, and then curing and integrating the laminate at a predetermined temperature. Batch manufacturing method. In this method, the raw material metal foil and the sheet-shaped fibrous material may be cut in advance to a predetermined size, or the laminate may be set to a predetermined size after curing and integration of the laminate. You may make it cut.

The fibrous material is continuously impregnated with the thermosetting resin composition by a dipping method or the like while feeding the fibrous material from a sheet-shaped roll of the fibrous material, and then the obtained impregnated body is formed into a desired composition. (It may consist of only one sheet-shaped fibrous material impregnated with the thermosetting resin composition, or may be a laminate of a plurality of such fibrous materials, and a metal foil roll body may be provided on one or both sides thereof. After continuously laminating the metal foil fed from the, the fibrous material impregnated with the thermosetting resin composition, and to obtain a laminate consisting of the metal foil continuously, this laminate is continuously at a predetermined temperature A continuous manufacturing method such as a method of curing and integrating the materials.

In the above method, the laminate comprising the fibrous material impregnated with the thermosetting resin composition and the metal foil may be, if necessary, before curing, between two rolls at a predetermined interval. It may be adjusted to a predetermined thickness by pressurizing it by a method of passing through. Further, the thermosetting resin composition used in the present invention does not need to contain a volatile component such as a solvent,
Moreover, since the curing is fast, the continuous method is more advantageous and preferable than the batch method as the method for producing the laminated plate.

[0052]

The long-chain dibasic acid (a), the polyfunctional epoxy resin (b) and the epoxy group-containing (meth) acrylate (c) are reacted at a predetermined equivalent ratio as raw materials for the cured resin of the fiber-reinforced resin layer of the laminate. Unsaturated ester (A) obtained by
When a thermosetting resin composition containing, and a radical polymerization initiator (B) as an essential component is used, when the resin composition is impregnated into the fiber material, the resin composition is applied to the fiber material without a diluting solvent. Since it can be easily impregnated,
It is not necessary to use a solvent for impregnating the fiber material, and the solvent removal treatment after impregnation is also unnecessary. As a result, there are no disaster prevention problems and resource and energy savings.

The unsaturated ester (A) contained in the thermosetting resin composition is derived from the long-chain dibasic acid (a), and has a soft segment imparting bending workability (flexibility),
Derived from polyfunctional epoxy resin (b), it has heat resistance, water resistance,
It has a molecular structure that also has a hard segment that imparts various properties such as chemical resistance and electrical properties. Therefore, when the resin composition containing the unsaturated ester (A) is used as a cured resin raw material for the fiber-reinforced resin layer of a laminate, it is difficult to use a conventional unsaturated polyester resin or vinyl ester resin for the laminate. That is, it is possible to impart the bending workability and various performances such as heat resistance, water resistance, chemical resistance, and electrical characteristics together. Further, since the fiber-reinforced resin layer of the laminated board is reinforced by the sheet-shaped fiber material,
Since sufficient rigidity is imparted to the laminated plate, it becomes possible to mount electric / electronic components on the laminated plate with almost no limitation on the type or number of the electric / electronic components.

[0054]

EXAMPLES Next, examples of the present invention and comparative examples will be described, but the present invention is not limited to the following examples. In the following examples, "parts" and "%" generally mean "parts by weight" and "% by weight", respectively. Synthesis of Unsaturated Esters Unsaturated esters used in Examples and Comparative Examples described later were synthesized by the following synthesis examples.

-Synthesis Example 1-In a reaction vessel equipped with a thermometer, a reflux condenser, a blow-in tube and a stirrer, 1,16- (6-ethylhexadecane) -dicarboxylic acid and 1,12- (6-ethyldodecane) were added. ) -Dicarboxylic acid mixture "SB-20" (Okamura Oil Co., acid value 3
14) 714 parts, hydrogenated dimer acid "Versadim 5
2 ”(Henkel Hakusui, acid value 195) 1150 parts, glycidyl methacrylate 568 parts, styrene 964 parts, hydroquinone 1.5 parts and zinc octylate (zinc content 15%) 4.8 parts were charged, while blowing air. ,
The mixture was stirred and reacted at 110 ° C. for 5 hours. At the end of this reaction, the acid value of the reaction product was 67.

Next, 1420 parts of a tetrabrominated bisphenol type epoxy resin "ESB340" (Sumitomo Chemical Co., Ltd., epoxy equivalent: 355) and 14.5 parts of triphenylphosphine were added, and the mixture was allowed to react at 120 ° C. for 6 hours to be unsaturated. Ester compound (1) (acid value 3.
A styrene solution of 4) (hereinafter, this solution is referred to as resin (1)) was obtained.

-Synthesis Example 2-In a reaction vessel similar to that used in Synthesis Example 1, dimer acid "Versadim 288" (manufactured by Henkel Shiramizu, acid value 19)
6) 1717 parts, 284 parts of glycidyl methacrylate,
Charge 1291 parts of styrene, 1.0 part of methylhydroquinone and 6 parts of zinc naphthenate (zinc content 8%),
While blowing air, the mixture was stirred and reacted at 100 ° C. for 8 hours. At the end of this reaction, the acid value of the reaction product was 70.

Next, 1291 parts of a tetrabrominated bisphenol type epoxy resin "YDB400" (manufactured by Tohto Kasei Co., epoxy equivalent 400), 72 parts of acrylic acid and 13 parts of triethylamine were added, and the mixture was reacted at 120 ° C. for another 6 hours. Saturated ester compound (2)
A styrene solution having an acid value of 8.0 (hereinafter, this solution is referred to as a resin (2)) was obtained.

-Synthesis Example 3-In a reaction vessel similar to that used in Synthesis Example 1, hydrogenated dimer acid "Versadim 52" (manufactured by Henkel Shiramizu, acid value 1
95) 2302 parts, glycidyl methacrylate 568
, Vinyltoluene 1118 parts, hydroquinone monomethyl ether 3.0 parts and zinc laurate (zinc content 14%) 8.5 parts were charged, while blowing air,
The mixture was stirred and reacted at 110 ° C. for 5 hours. At the end of this reaction, the acid value of the reaction product was 58.

Next, 1600 parts of a tetrabrominated bisphenol type epoxy resin "YDB400" (manufactured by Tohto Kasei Co., epoxy equivalent 400) and 17 parts of triphenylphosphonium iodide were added, and the mixture was reacted at 110 ° C. for 8 hours to be unsaturated. Ester compound (3)
A vinyltoluene solution having an acid value of 2.7 (hereinafter, this solution is referred to as a resin (3)) was obtained.

-Synthesis Example 4-In a reaction vessel similar to that used in Synthesis Example 1, dimer acid "Versadim 228" (manufactured by Henkel Shiramizu, acid value 19)
4) 2312 parts, 568 parts of glycidyl methacrylate,
Charge 1050 parts of styrene, 1.6 parts of hydroquinone and 8.5 parts of zinc laurate (zinc content 14%),
While blowing air, the mixture was stirred and reacted at 120 ° C. for 4 hours. At the end of this reaction, the acid value of the reaction product was 59.

Then, 370 parts of bisphenol type epoxy resin "Epototo-Y-127" (manufactured by Tohto Kasei, epoxy equivalent 185) and bisphenol type epoxy resin "Epototo-YD-011" (Toto Kasei, epoxy equivalent 475) 950 And 13 parts of triethylbenzylammonium chloride were added, and the mixture was reacted at 120 ° C. for 5 hours to give a styrene solution of the unsaturated ester compound (4) (acid value 3.2) (hereinafter, this solution was referred to as resin (4)). It is obtained).

-Synthesis Example 5-A tetrabrominated bisphenol type epoxy resin "YDB-700" was placed in a reaction vessel similar to that used in Synthesis Example 1.
(Toto Kasei Co., Ltd., epoxy equivalent 700) 3500 parts, acrylic acid 378 parts, styrene 1662 parts, hydroquinone 1.5 parts and triethylamine 11 parts were charged, stirred while blowing air, and reacted at 110 ° C. for 8 hours, Styrene solution of flame-retardant vinyl ester (acid value 3.7) (hereinafter this solution is referred to as comparative resin (1))
Got

-Synthesis Example 6-In a reaction vessel equipped with a thermometer, a partial condenser, a blow-in tube and a stirrer, 1840 parts of adipic acid, 529 parts of maleic anhydride and 2003 parts of diethylene glycol were charged and stirred while blowing air, While removing the condensation water, the reaction was carried out at 210 ° C. for 10 hours, and when the acid value of the reaction product reached 12, after cooling to 100 ° C. or lower,
By adding 0.5 parts of hydroquinone and 1350 parts of styrene, a styrene solution of a soft unsaturated polyester (hereinafter, this solution is referred to as a comparative resin (2)) was obtained. Manufacture of Laminated Plates- Examples 1 to 4 and Comparative Examples 1-2- 100 parts of each of the resins (1) to (4) and comparative resins (1) to (2) obtained in Synthesis Examples 1 to 6 above. , Acrylic acid 2 parts, aluminum hydroxide 20 parts, antimony trioxide 1
0 parts and 1,1-bis (t-butylperoxy)-
1 part of 3,3,5-trimethylcyclohexanone was blended to obtain a thermosetting resin composition.

The obtained thermosetting resin composition was applied to a polyester nonwoven fabric "OL-11K" (manufactured by Japan Vilene, thickness 0.35 mm) and a glass cloth "WE03102".
(Manufactured by Nitto Boseki, thickness 0.03 mm). Next, copper foil for electrical laminates (JT, JT
C, a thickness of 35 μm), a polyester non-woven fabric impregnated with the thermosetting resin composition and a glass cloth are laminated one by one in this order on the treated surface, and further on the thermosetting resin composition. Another polyester nonwoven fabric impregnated with the product was laminated and the upper surface thereof was covered with a tetron film to obtain a laminate.

This laminated body was cured at 100 ° C. for 15 minutes and then at 130 ° C. for 20 minutes to be integrated to obtain a laminated plate having a thickness of 0.8 mm. Evaluation of Physical Properties of Laminated Plate Regarding the laminated plates obtained in the above Examples and Comparative Examples,
The minimum bending diameter, surface resistance, insulation resistance, PCT solder heat resistance, peel (peel) strength, and flame retardancy were evaluated by the following test methods. The results are shown in Table 1 below.

The minimum bending diameter is obtained by cutting a laminated plate from which a copper foil has been removed by etching into 25 mm × 150 mm, and then winding it around a steel rod having various radii by a quarter of the circumference. The evaluation was made by the radius of the smallest steel rod in which the generation of fine cracks was not recognized. The surface resistance, insulation resistance and peel strength were in accordance with JIS-C6481. PCT
For soldering heat resistance, laminates from which copper foil was removed by etching were cut into 40 mm x 40 mm pieces, which were immediately forcibly absorbed by an autoclave at 133 ° C for 60 minutes, and immediately afterwards 260
The test piece was dipped in a solder bath at ℃, and the time (seconds) from the start of this dipping until the occurrence of blistering was evaluated.

The flame retardancy was in accordance with UL Subject 94V method and 94HB method.

[0069]

[Table 1]

As shown in Table 1, the laminates of the examples are superior to the laminates of the comparative examples in bending workability, and also excellent in electrical characteristics, water resistance, heat resistance, and flame retardancy. It was confirmed that was also given.

[0071]

The electrical metal foil-clad laminate according to the present invention is excellent in various properties such as heat resistance, water resistance, chemical resistance, and electrical characteristics. Further, since it has sufficient rigidity, it is possible to mount electric and electronic parts with almost no restrictions on the type or number of parts. Since this metal foil-clad laminate for electric use can be bent, it can be accommodated in a limited space in response to downsizing of electronic devices.

This metal foil-clad laminate for electric use does not require the use of a solvent when the thermosetting resin composition is impregnated into the reinforcing material in the manufacturing process thereof, and therefore does not require a solvent removal treatment after the impregnation. Therefore, it is preferable in terms of disaster prevention, resource saving, and energy saving.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hideshi Makino 1048, Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works Co., Ltd. Resin Technology Laboratory (72) Inventor Teruhisa Nagashima 5-8 Nishimitabicho Suita City Osaka Prefecture Japan Catalyst Resin Technology Laboratory Co., Ltd.

Claims (4)

[Claims] 1. A long-chain dibasic acid (a) in which the total number of carbon atoms other than those contained in the acid group is 12 or more per molecule, 1.
The epoxy resin (b) having two or more epoxy groups in the molecule and the (meth) acrylate (c) having one epoxy group in one molecule are the total of the epoxy groups having the above (b) and (c). Is 0.8 to 1.2 equivalents per 1 equivalent of the acid group contained in (a), and the equivalent ratio of the epoxy group contained in (b) to the epoxy group contained in (c) is 2: A sheet-shaped fiber of a cured product of a thermosetting resin composition containing an unsaturated ester (A) obtained by reacting at a ratio of 1 to 1: 2 and a radical polymerization initiator (B) as essential components. A metal foil-clad laminate for electrical use, comprising a fiber reinforced resin layer reinforced with a material and a metal foil laminated on at least one side of the metal foil and integrated with the fiber reinforced resin layer. 2. The unsaturated ester (A) further comprises (meth) acrylic acid as a reaction raw material, and the equivalent ratio of the acid group of (meth) acrylic acid to the acid group of the long-chain dibasic acid (a) is The metal foil-clad laminate for electrical use according to claim 1, which is obtained by replacing a part of the long-chain dibasic acid (a) with (meth) acrylic acid so as to be in a range of 0.5 or less. . 3. The thermosetting resin composition further contains a radically polymerizable unsaturated monomer (C), and the content of this monomer (C) is equal to that of the unsaturated ester (A). The amount is 5 to 50% by weight based on the total of the monomer (C).
Or the metal foil-clad laminate for electric use according to 2. 4. The metal foil-clad laminate for electrical use according to claim 1, wherein the epoxy resin (b) has a bromine-substituted bisphenol A skeleton.