JPS6045059B2 - Manufacturing method for unsaturated polyester resin copper-clad laminates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an unsaturated polyester resin copper-clad laminate.

Conventionally, in the production of unsaturated polyester resin copper-clad laminates, it has been necessary to use prepregs that are not sticky at room temperature in terms of storage and workability.

The present inventors prepared an unsaturated polyester resin by dissolving an unsaturated polyester mainly consisting of crystalline unsaturated polyester in a common liquid copolymerizable monomer such as styrene under heating. −ni−1 『■１'・を−
Ij, -ni-, T'Ah ire-! "9・■-, -72,
The 4-preg does not exhibit tackiness at room temperature, and the copper-clad laminate obtained from the prepreg and copper foil can be laminated without using an adhesive. It has been found that it has excellent adhesion between the plate and the copper foil, and has already been proposed (Japanese Unexamined Patent Publication No. 52-92288). The present inventors have conducted extensive research into the adhesion between laminates and copper foil, and have found that the prepreg that is bonded to the copper foil is a solid unsaturated material at room temperature. The present invention was achieved based on the discovery that the adhesion of a material impregnated with a polyester resin is significantly improved compared to that of a tipped strand mat.

In addition, molding machines such as multistage presses are generally used to industrially produce large quantities of copper-clad laminates, and it is strongly desired that these molding machines do not require molds or spacers.

The present inventors have worked hard to develop a method for manufacturing copper-clad laminates that can be molded using currently used molding machines such as multistage presses and general molding presses, and that do not require molds or spacers. As a result of repeated research, we have found that the prepreg that is bonded to the copper foil can be made of woven fabric, long-fiber nonwoven fabric, or filament fabric.
Chopped strands are mats impregnated with unsaturated polyester resin that is solid at room temperature.
The present invention was achieved by discovering that the adhesiveness is significantly improved compared to matte or the like. Furthermore, molding machines such as multi-stage presses are used to industrially produce large quantities of copper-clad laminates, and it is strongly desired that these molding machines do not require molds or spacers.

The present inventors have conducted extensive research into a method for manufacturing copper-clad laminates that can be formed using currently used molding machines such as multi-stage presses and general forming presses, and that do not require molds or spacers. As a result of stacking, the prepreg to be bonded to the copper foil is a woven fabric, long fiber nonwoven fabric, or filament mat impregnated with an unsaturated polyester resin that is solid at room temperature, and the copper foil is stacked on the prepreg. The present invention was achieved by discovering that the desired objective can be achieved by heating to a pressure equal to or lower than the contact pressure and then heat-molding and integrating under pressure. That is, the present invention impregnates a woven fabric, long-fiber nonwoven fabric, or filament mat with an unsaturated polyester resin that is solid at room temperature while heating, and coats at least one prepreg that is non-tacky at room temperature with copper foil. A method for manufacturing an unsaturated polyester resin copper-clad laminate, which is characterized by stacking the unsaturated polyester resin and molding them into one piece by heating and pressing.・At least one material that is impregnated into the mat and is not sticky at room temperature.
An unsaturated polyester resin copper cladding characterized by stacking copper foil on a sheet of prepreg, heating it under a pressure below the contact pressure, and then heating it under pressure to integrally mold it. This is a method for manufacturing a laminate.

According to the present invention, by using a woven fabric, long fiber nonwoven fabric, or filament mat as the fibrous base material, the adhesiveness between the laminate and the copper foil is improved compared to the case where a tip, strand, or mat is used. Significantly improved.

Further, even without using a mold or spacer, resin does not flow out from the fibrous base material due to heat and pressure, and a copper-clad laminate having a beautiful appearance and excellent performance can be obtained. In particular, when all the fibrous base materials of each prepreg in a laminate are woven fabrics, long-fiber nonwoven fabrics, or filament mats, and they are heat-treated under a pressure below the contact pressure and then heated and pressed to form one piece, Even without using molds or spacers,
A copper-clad laminate can be obtained that does not cause resin to flow out from the fibrous base material, has a more beautiful appearance, and has excellent adhesive strength between the laminated prepregs and between the copper foil and the laminate. The crystalline unsaturated polyester used in the present invention is an unsaturated polyester produced using as raw materials a dicarboxylic acid or a functional derivative thereof having a symmetrical molecular structure and a diol also having a symmetrical molecular structure.

As a specific example, dicarboxylic acid raw materials include terephthalic acid, 1,4-naphphthalene dicarboxylic acid, 1,5-
Symmetrical aromatic dicarboxylic acids and their functional derivatives such as naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, their lower alkyl esters or chlorides, fumaric acid, maleic acid, their lower alkyl esters, anhydrides or chlorides. Symmetrically unsaturated aliphatic dicarboxylic acids and their functional derivatives such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol , neopentyl glycol, 2-butene-1,4-diol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-bis(2-hydroxyethoxy)cyclohexane, 1,4-bis(2- hydroxypropoxy)cyclohexane, 1,4-bis(2-hydroxyethoxy)
Benzene, 1,4-bis(2-hydroxypropoxy)
Examples include symmetrical diols such as benzene and baraxylylene glycol. As long as it does not significantly impair the crystallinity of the unsaturated polyester, it can be used in the production of amorphous unsaturated polyester to give ordinary liquid unsaturated polyester resin, along with the above-mentioned raw materials having molecular structure symmetry. A small amount of raw materials can be used together. Such raw materials include dicarboxylic acids and their functional derivatives, such as orthophthalic acid, isophthalic acid, tetrachloro- and tetrabromo-orthophthalic acid, succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, and 1,2-
Propanediol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 2,2,4-
Examples include diol raw materials such as trimethyl-1,3-pentanediol, bisphenols, hydrogenated bisphenols, and halogenated bisphenols adducts with ethylene oxide and propylene oxide. The general amount of these raw materials used in combination is 20 mol% or less of the total dicarboxylic acid component,
The diol component accounts for 40 mol% or less of the total diol component. Two or more kinds of crystalline unsaturated polyesters can be used in combination. A normal amorphous unsaturated polyester can also be used in combination with the crystalline unsaturated polyester within a range that does not impair the solidity of the unsaturated polyester resin at room temperature.

The proportion in which they are used together varies depending on the degree of crystallinity of the crystalline unsaturated polyester, the type and amount of the copolymerizable monomer, etc., but it is necessary to maintain the solidity of the unsaturated polyester resin at room temperature. , it is desirable that the amount is 5% or less based on the total unsaturated polyester.

In this case, two or more types of amorphous unsaturated polyesters can be used together. Next, the liquid copolymerizable monomers used in the present invention include styrene monomers such as styrene, monochlorostyrene, t-butylstyrene, α-methylstyrene, vinyltoluene, divinylbenzene, diallyl Examples include allylic monomers such as phthalate, diallyl isophthalate, diallyl terephthalate, diallyl fumarate, and diallyl adipate, acrylic ester monomers such as methyl or ethyl acrylate and methyl or ethyl methacrylate, vinyl acetate, and dibutyl fumarate.

Two or more of these copolymerizable monomers can be used in combination.

The blending amount of the copolymerizable monomer is 1 of the unsaturated polyester resin.
The amount of saliva is 0-6%.

If the blending amount exceeds 6%, the solidity of the unsaturated polyester resin at room temperature will not be sufficient, and at the same time,
It has drawbacks such as not losing flow resistance during molding and poor moldability. Furthermore, if the amount is less than 1% by weight, the physical properties of the cured molded product will be poor and the unsaturated polyester resin will not be able to exhibit sufficient performance. The crystalline unsaturated polyester can be mixed with the copolymerizable monomer to form an unsaturated polyester resin that is solid at room temperature.

This mixing can be carried out by a screw type or stirring blade type method such as a Panbury mixer, a pump blender, a kneader, or a high-speed mixer. The mixing is generally performed under heating. The unsaturated polyester resin that is solid at room temperature used in the present invention contains a polymerization catalyst, but the amount thereof is generally 0 parts per 10 parts by weight of the unsaturated polyester resin.
．． It is contained in an amount of 3 to 3 parts by weight.

As the polymerization catalyst, a medium- or high-temperature decomposition type catalyst used for ordinary liquid unsaturated polyester resins may be used, but since the unsaturated polyester resin used in the present invention is solid at room temperature, the unsaturated polyester resin In order to achieve sufficient mixing during the production of a composition thereof or a composition containing fillers, pigments, flame retardants, thickeners, mold release agents, etc., it is necessary to knead it under heating. Therefore, it is necessary to select a polymerization catalyst that does not decompose under crosstalk conditions. Specific examples of such polymerization catalysts include methyl ethyl ketone peroxide, cyclohexane nonperoxide, t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-di hydroperoxide,
p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α5-bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethylno 2,5-di(benzoylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide,
Benzoyl peroxide, 7t-butylperoxy-2-ethylhexanoate, t-butylperoxylaurate, t-butylperoxybenzoate, Z-t
-butyldiperoxyphthalate, t-butylperoxymaleic acid, 1,1,3,3-tetramethylbutylhuperoxy-2-ethylhexanoate, and the like.

The unsaturated polyester resin used in the present invention, which is solid at room temperature, contains a polymerization inhibitor if necessary to adjust the gelation time, but the content is generally within the range of 100 parts by weight of the unsaturated polyester resin. contains 0.5 parts by weight or less.

As the polymerization inhibitor, those used for controlling the gelation time of ordinary unsaturated polyester resins may be used, and there are no particular limitations on the polymerization inhibitor. The above polymerization catalyst and polymerization inhibitor are generally added at the time when the crystalline unsaturated polyester is dissolved in the copolymerizable monomer, but they are necessary for the crystalline unsaturated polyester resin. It can also be added and mixed at the time of compounding ingredients such as fillers, pigments, flame retardants, thickeners, and mold release agents.

The unsaturated polyester resin that is solid at room temperature used in the present invention may optionally include calcium carbonate, calcium hydroxide, talc, clay, silica, calcium silicate, barium sulfate, magnesium carbonate, diatomaceous earth, silica sand,
Fillers such as glass, powder, and glass flakes; flame retardants such as antimony trioxide, phosphorus compounds, and nowagen compounds; thickeners such as magnesium oxide, magnesium hydroxide, calcium oxide, and calcium hydroxide; zinc stearate. , mold release agents such as calcium stearate, etc.
More than one compounding agent can be blended.

A common method for blending the above ingredients is to heat-knead the ingredients into a crystalline unsaturated polyester resin containing a polymerization catalyst and, if necessary, a polymerization inhibitor using a kneader, high-speed mixer, etc. .

The woven fabric, long-fiber nonwoven fabric, or filament mat used in the present invention includes inorganic fibers such as glass, asbestos, and
Natural fibers such as cotton yarn, rayon yarn, and polyamide,
Synthetic fibers such as polyester, polyacrylonitrile, polyvinyl chloride, polyvinylidene chloride, polyethylene, and polypropylene. Manufactured from fiber.

Woven fabrics include plain weave, twill weave, satin weave, open plain weave, and gauze weave, and long fiber nonwoven fabrics include nonwoven fabrics manufactured from spun bonds and filaments using adhesives.
These woven fabrics, long-fiber nonwoven fabrics, or filament mats are available in a wide variety of combinations of weaving methods, counts used, densities, etc., and the optimal one can be used depending on the purpose. Further, the woven fabric, long fiber nonwoven fabric, or filament mat may be used alone or in combination of two or more types. As a woven fabric, the thickness is approximately 1.00Tm
Below, a woven fabric with a weight of about 500 q/d or less is used,
Particularly preferred is a woven fabric having a thickness of about 0.5 mm or less and a weight of about 300 y/d or less. On the other hand, as the long fiber nonwoven fabric or filament mat, one with a thickness of about 1.50 Tr$L or less and a weight of about 300 Da/771' or less is used. It is preferably about 200 q/d or less. Generally speaking, the thinner the layer and the lighter the weight, the easier it is to use, but it becomes necessary to stack a large number of layers. As long as the formability during lamination molding is not impaired, the prepreg to be bonded to the copper foil can be used in combination with the prepreg containing a fibrous base material other than the woven fabric, long fiber nonwoven fabric, or filament mat used in the present invention. can do. Examples of such fibrous base materials include linter paper, rayon paper, kraft paper, asbestos paper, short fiber nonwoven fabric, chopped strand mat, and the like. The copper foil used in the present invention has a thickness of 10 to 10
0μ copper foil, generally unsaturated polyester resin,
Any material used for copper-clad laminates, such as phenol resin or epoxy resin, may be used.

Copper foil coated with various adhesives may be used, but the copper-clad laminate of the present invention has the great feature of exhibiting excellent adhesiveness even when copper foil is not coated with adhesive. . Metal foils other than copper foil may be used as well. In the method of the present invention, the fibrous base material is first impregnated with the crystalline unsaturated polyester resin or a resin composition containing additives as necessary while maintaining fluidity under heating, and then allowed to cool to room temperature. By doing so, a prepreg with no tackiness at room temperature is produced.

In this case, it is particularly preferred that the content of the woven fabric, long fiber nonwoven fabric or filament mat in the prepreg is about 60% by weight or less.

If the amount exceeds about 6%, not only will the adhesion to the copper foil not be sufficient, but the base material may become white or embossed. Methods for impregnating woven fabrics, long-fiber nonwoven fabrics, or filament mats with resin include the squeeze method, contact method, immersion-squeeze method, dipping method, and coater method. It is preferable to adopt it.

The prepreg thus obtained is dry at room temperature and has no tackiness.

In this case, the prepreg may be coated with a film of polyester, polypropylene, polyethylene, polybutadiene, polyvinylidene chloride, polyvinyl chloride, or the like. In the method of the present invention, a copper-clad laminate is then manufactured by stacking at least one sheet of prepreg and copper foil, heating and pressing them, and molding them into one piece.

In this case, the prepreg to be bonded to the resin must necessarily be a prepreg containing woven fabric, long fiber nonwoven fabric, or filament mat. The prepreg to be bonded to the copper foil may contain two or more types of the above-mentioned woven fabric, long-fiber nonwoven fabric, or filament mat at the same time. Further, the prepreg to be bonded to the copper foil may contain two or more sheets of woven fabric, long fiber nonwoven fabric, or filament mat. Furthermore, two or more prepregs to be bonded to the copper foil may be stacked and bonded to the copper foil. In particular, when using thin prepregs, it is more preferable to overlap two or more sheets of prepregs and adhere them to the copper foil. As the fibrous base material contained in the prepreg, any of the above-mentioned fibrous base materials can be selected and used, but in terms of performance, it is best to use a glass base material. In addition to the prepreg that is bonded to the copper foil, prepregs using various fibrous base materials can be used by combining and laminating them depending on the purpose. Moreover, one prepreg can also be made by using two or more sheets of one or more types of fibrous base materials. The molding conditions for copper-clad laminates vary depending on the composition of the crystalline unsaturated polyester used, the type and amount of the polymerization catalyst, the composition of the crystalline unsaturated polyester resin composition, etc., but generally the molding temperature is 70 to 70°C. 2
00'C, molding pressure 10-200k9/D, molding time 5
It is molded using a molding machine such as a multistage press or a general molding press.

In order to perform molding using currently used molding machines such as multi-stage presses and general molding presses without the need for molds or spacers, the following molding conditions must be followed.

First, the prepreg layered with copper foil is heated to a pressure lower than the contact pressure.

The heating temperature and heating time in this case vary depending on the composition of the crystalline unsaturated polyester resin used for prepreg production, the composition of the composition, the type and amount of the polymerization catalyst and polymerization inhibitor contained, but generally speaking Typically, the heating temperature is 70 to 200°C, and the heating time is several 1 to several 1.
It is 0 minutes. Next, the prepreg layered with copper foil is heated under pressure to obtain a copper-clad laminate. The pressure in this case is generally 10-200k9/c! t, and the heating temperature is 70
~200°C, and the heating time is several minutes to several hours. Both the heating time under pressure below the contact pressure and the heating time under pressure become shorter as the heating temperature becomes higher. If heating is not carried out under pressure below the contact pressure, whitening or embossment of the woven fabric, long-fiber nonwoven fabric, or filament/mat substrate will occur, and the adhesion between the laminated prepregs will be insufficient, resulting in poor adhesion of the copper foil. Power becomes insufficient. If necessary, the obtained copper-clad laminate may be post-treated by heating it to any temperature under any pressure or no pressure. The method of the present invention can also be directly applied to the production of other laminated products such as copper-clad laminates, laminated tubes, laminated cylinders, laminated rods, and molded laminated products. The unsaturated polyester resin copper-clad laminate of the present invention is used in fields such as printed wiring boards after undergoing secondary processing steps such as punching and etching.

The present invention will be explained in more detail below using examples. In the examples, "part" means part by weight, and "%" means weight %.

The adhesion between the copper foil and the laminate was evaluated based on the peel strength (JISO648l) of the copper foil.・Reference example (manufacture of unsaturated polyester) Terephthalic acid 1.
00 (molar ratio), ethylene glycol 2.10 (mol.
ratio) and terephthalic acid, 0.01 mol% potassium titanyl oxalate and 0.03 mol% triethylamine were added, and the gauge pressure was 3.0k9/C! under a pressure of 220
After reacting for 3 hours at a reaction temperature of ~230°C, the pressure was returned to normal pressure.

Next, 1.00 (molar ratio) of fumaric acid was added and reacted at a reaction temperature of 205 to 210'C under normal pressure and a nitrogen stream to obtain an unsaturated polyester (4) with an acid value of 12. Next, using the raw materials shown in Table 1 below, unsaturated polyesters (B) to (
1) was manufactured.

In Table 1, (4) to (G) are crystalline unsaturated polyesters, and (H) and (■) are amorphous unsaturated polyesters. Example 1 Crystalline unsaturated polyester (CA) season part was dissolved in 30 parts of styrene under heating to obtain an unsaturated polyester resin, and further 0.0 parts of hydroquinone was added. Totobe and 1 part of t-butyl peroxybenzoate were added and mixed well to obtain an unsaturated polyester resin that was solid at room temperature.

The obtained unsaturated polyester resin was heated to maintain its fluidity, and was then heated using a 50d x 50CTn glass cloth (E
After impregnating one sheet of HlOOlN (manufactured by Nippon Glass Fiber), the prepreg was allowed to cool to room temperature to obtain a non-tacky prepreg (glass content: about 40%).

In the same manner as in Table 1, unsaturated polyester (B) - Example 2 In the same manner as in Example 1, an unsaturated polyester resin which was solid at room temperature was obtained from a crystalline unsaturated polyester.

Using this unsaturated polyester resin, glass cloth-containing prepregs having different glass contents shown in Table 3 were obtained in the same manner as in Example 1. Separately, a prepreg containing tip, strand, and mat was obtained from crystalline unsaturated polyester (E) in the same manner as in Example 1 (glass content: 5
0%).

Next, in the same manner as in Example 1, one sheet of prepreg containing glass cloth was layered on top of two sheets of prepreg containing chipped strand mat, and one sheet of copper foil was layered on top of that, followed by heating and pressing to form a copper clad laminate. Created a board. Table 3 shows the measurement results of the peel strength of copper foil when using glass cloth-containing prepregs with varying glass content. Example 3 The marked portion of crystalline unsaturated polyester (B) was dissolved in 40 parts of styrene under heating to obtain an unsaturated polyester resin, and 0.0 parts of hydroquinone was further added. The mixture and 1 part of di-t-butyl peroxide were added and mixed well to obtain an unsaturated polyester resin that was solid at room temperature.

This unsaturated polyester resin was heated to maintain its fluidity, and a 50cm x 50cm glass cloth (EHL
3OIN, manufactured by Nippon Glass Fibers), both sides were covered with polyester film and allowed to cool to room temperature to obtain a non-tacky prepreg (glass content: about 35%).
Separately, you can use roping cloth (WR
Roping cloth-containing prepregs shown in Table 4 were obtained using the unsaturated polyesters (B) to (1) shown in Table 1 in the same manner except that 57OB-100 (manufactured by Nittobo Co., Ltd.) was used.

None of the prepregs exhibited tackiness at room temperature and had a glass content of approximately 35%. Next, one sheet of the above-mentioned glass cloth-containing prepreg is layered on top of the two roping cloth-containing prepregs obtained, and one layer of copper foil is placed on top of that.
The sheets were stacked and heated under a pressure of 100 k9/d at 150° C. using a mold of 5007 T$L x 500 wt to produce a copper-clad laminate.

Table 4 shows the measurement results of the peel strength of copper foil when the prepreg containing roping cloth was used together with the prepreg containing glass cloth. For comparison, the measurement results of the peel strength of the copper foil without using the glass cloth-containing prepreg are also listed in Table 4 as a comparative example. Example 4 75 parts of crystalline unsaturated polyester (D) and 25 parts of styrene
0.05 part of hydroquinone and 1 part of dicumyl peroxide were added and mixed well to obtain an unsaturated polyester resin that was solid at room temperature.

This unsaturated polyester resin was heated with a glass cloth (E
HlOOlN, supra) was impregnated into one sheet, and then allowed to cool to room temperature to obtain a non-tacky prepreg (glass content: approx.
0%) In the same manner, prepregs containing woven fabrics, long fiber nonwoven fabrics, or filament mats shown in Table 5 were obtained.

None of the prepregs exhibited tackiness at room temperature, and the glass content was 45-50%. l Separately, a chopped strand mat (EM3OO-G-1, manufactured by Nippon Glass Fiber) was prepared using crystalline unsaturated polyester (4).
A prepreg with no tackiness at room temperature was obtained in the same manner as above except for using the above method (glass content: about 50%).

Next, on top of the obtained three pieces of chopped strand mat-containing prepreg, one piece of woven fabric, long fiber nonwoven fabric, or filament mat proprietary prepreg shown in Table 5 (two pieces in the case of thin prepreg: (see table) and then copper on top? (Previously) Stack one sheet, 500TnIn×
Using a 500Tf0n mold, pressure 100kg/CF
A copper-clad laminate was produced by heating the powder at 140° C. under lf.

Table 5 shows the results of measuring the peel strength of copper foil when using woven fabric, long fiber nonwoven fabric, or prepreg containing filament/matte.

For comparison, the case where only prepreg containing chipped strands and mats is used is also shown. Example 5 In the same manner as in Example 1, the same various glass cloth-containing prepregs as in Example 1 were obtained from the unsaturated polyester particles (1) in Table 1.

Separately, a crystalline unsaturated polyester (E) part is dissolved in styrene (9) parts under heating to obtain an unsaturated polyester resin, and further hydroquinone 0.0? and 1 part of t-butyl peroxybenzoate were added and mixed well to obtain an unsaturated polyester resin that was solid at room temperature.

Calcium carbonate (NSlOO, manufactured by Nitto Funka Kogyo) was added to this unsaturated polyester resin 7 (2) and mixed thoroughly using a high-speed mixer under heating to form a solid unsaturated polyester resin at room temperature. I got something. The resulting unsaturated polyester resin composition was impregnated into two 50 cm x 50 CTL chip strand mats (MC38OA, manufactured by Nitto Boseki) while maintaining its fluidity under heating, and then allowed to cool to room temperature. A non-sticky prepreg was obtained (
Glass content: approx. 40%). Next, the obtained tip●
A copper-clad laminate was created in the same manner as in Example 1 by overlaying one sheet of the above glass cloth-containing prepreg on one sheet of strand matte-containing prepreg, and then overlaying one sheet of copper foil (described above) on top of that. .

Table 6 shows the measurement results of the peel strength of copper foil when using various glass cloth-containing prepregs. For comparison, a case where only the chipped strand mat was used is also shown. Example 6 Crystalline unsaturated polyester (4) prepared in the same manner as in Example 1
～(1) and a 50cm wide glass cloth (EHlOOl
A glass cloth-containing prepreg was obtained.

The obtained prepregs were each cut into pieces of 50 cm x 50 cm, and copper foil (1 above) was layered on top of the same prepreg 1 layer. Next, a press plate heated to 140'C was heated to 1.0-1. Heat for a while, then 100 ml
A copper-clad laminate was obtained by heating at 140° C. for 3 minutes under a pressure of k9/d. Table 7 shows the tensile strength of the copper foil of the various copper-clad laminates obtained.

The peeling strength of the copper foil of the copper-clad laminate is also shown in Table 7 as a comparative example when the copper foil is heated immediately under pressure without being heated under contact pressure. As is clear from Table 7, when forming without using a mold, the peeling strength of the copper foil of a copper-clad laminate is relatively small if heated under pressure immediately, but after heating under contact pressure. Heat treatment under pressure increases the peel strength of copper foil. Comparative Example 1 50crrL width tip strand mat (C
Prepregs using various unsaturated polyesters (4) to (G) which are not sticky at room temperature were obtained in the same manner as in Example 1, except that M45OA (mentioned above) was used.

The glass content of each prepreg was approximately 45%. A copper-clad laminate was formed in the same manner as in Example 6 by laminating two sheets of each prepreg cut into 50 cm x 50 cm and overlaying one sheet of copper foil (described above), but the resin flowed out from the glass base material. Remarkably, only copper-clad laminates with extremely poor appearance could be obtained.

Example 7 An unsaturated polyester resin that was solid at room temperature was obtained from the crystalline unsaturated polyester resin (4) in the same manner as in Example 1.

Using this unsaturated polyester resin, in exactly the same manner as in Example 6, prepregs containing glass cloths having different glass contents as shown in Table 8 and having no tackiness at room temperature were obtained. Next, copper-clad laminates were obtained in exactly the same manner as in Example 6 using prepregs with different glass contents.

Table 8 shows the peel strength of the copper foil of the obtained copper-clad laminate. Example 8 The crystalline unsaturated polyester (D) marked part was dissolved in 40 parts of styrene under heating to obtain an unsaturated polyester resin, and further hydroquinone (0.0%) was obtained. ? After adding 1 part of di-t-butyl peroxide to the mixture and mixing well, the mixture was allowed to cool to room temperature to obtain a solid unsaturated polyester resin.

This unsaturated polyester resin was impregnated with various 50C7y1 width woven fabrics, long fiber nonwoven fabrics, and filament mats shown in Table 9 while maintaining fluidity under heating, and then allowed to cool to room temperature and become sticky. A genderless prepreg was obtained.

The base material content of the prepreg was 45 to 50%. Each of the obtained prepregs was cut into pieces of 50 cm x 50 cm, and 5 to 1 layers were scattered on top of which one sheet of copper foil (described above) was further laminated.

Next, it was placed on a press plate heated to 130°C and heated for 2.5 to 3.5 minutes while maintaining a distance of about 1wn from the upper plate of the press, and then heated at 130'C under a pressure of 80 kg/cl for 4 minutes. A copper-clad laminate was obtained by heating the mixture. Table 9 shows the peel strength of the copper foil of the various copper-clad laminates obtained. For comparison,
Is the distance between the upper part of the bracelet about 1? It also shows the case where the product is heated immediately under pressure without being heated at a constant temperature. Comparative Example 2 50CWL width tip ● Strand ● Mat (EM
A prepreg with no tackiness at room temperature was obtained in the same manner as in Example 8, except that 3OO-G-1, supra) was used.

The glass content was approximately 50%. This prepreg is 5
0CTfLX50c! A copper-clad laminate was formed in the same manner as in Example 8 by laminating 3 sheets cut to size n, and then layering 1 sheet of copper foil (described above) on top of it. Only copper-clad laminates with poor appearance could be obtained. Example 9 In the same manner as in Example 1, prepregs containing the various woven fabrics, long fiber nonwoven fabrics, and filament mats shown in the first example were obtained from the unsaturated polyester shown in the first example.

The obtained prepregs are each 50cm x 50C! It was cut into pieces and laminated as shown in the first section.

A layer of copper foil (described above) was further placed on top of the laminated prepreg, and then contacted on a press plate heated to 140°C. 1.0-1. under pressure. Intermittent heating followed by 80kg/c! l
Two powders were heated at 140° C. under pressure of 1, and then the heating temperature was raised to 160° C. and one powder was heated. The peeling strength of the copper foil of the obtained copper-clad laminate is shown in the first graph.

The peeling strength of the copper foil of the copper-clad laminate when it is not heated under contact pressure but immediately heated under pressure is also listed in the first cough as a comparative example. Example 10 Crystalline unsaturated polyester (C) (1) part is styrene 4
0 parts under heating to obtain an unsaturated polyester resin,
Furthermore, hydroquinone 0. The mixture was mixed with 1 part of dicumyl peroxide and then allowed to cool to room temperature to obtain a solid unsaturated polyester resin.

Calcium carbonate (N
S2OO (manufactured by Nitto Funka Kogyo Co., Ltd.) was added and thoroughly mixed using a high-speed mixer while heating to obtain an unsaturated polyester resin composition that was solid at room temperature. This unsaturated polyester resin composition was heated for 5 minutes while maintaining its fluidity.
A glass cloth (EMH25O3, described above) having a width of 0C7r1 was impregnated with the mixture and then allowed to cool to room temperature to obtain a prepreg with no stickiness at room temperature.

The glass content of this prepreg was approximately 50%. Similarly, unsaturated polyester resins (B) to (
1) to obtain various glass cloth-containing prepregs shown in Table 11.

The obtained prepregs were each cut into pieces of 50 cm x 50 cm, and five sheets of the same prepreg were laminated.

Two sheets of prepreg using the crystalline unsaturated polyester (4) obtained in Example 1 were layered on top of this, and one sheet of copper foil (described above) was layered on top of that, and molded in exactly the same manner as in Example 9. A copper-clad laminate was obtained. Table 11 shows the peel strength of the copper foil of the obtained copper-clad laminate.

Claims (1)

[Claims] 1. Impregnating a woven fabric, long-fiber nonwoven fabric, or filament mat with an unsaturated polyester resin that is solid at room temperature under heating, and overlaying a copper foil on the resulting prepreg that is not sticky at room temperature, A method for producing an unsaturated polyester resin copper-clad laminate, which is characterized by integral molding by heating and pressing. 2. A woven fabric, long-fiber nonwoven fabric, or filament mat is impregnated with unsaturated polyester resin that is solid at room temperature under heating, and the resulting prepreg, which is non-tacky at room temperature, is overlaid with copper foil and heated under a pressure below the contact pressure. 1. A method for producing an unsaturated polyester resin copper-clad laminate, which comprises heating the unsaturated polyester resin to a temperature of 100.degree.