JPH0469220A - Continuous preparation of laminated sheet - Google Patents

Abstract

PURPOSE:To prepare a highly heat-resistant laminated sheet with good productivity by a method wherein one or a plurality of continuous glass fiber base material impregnated with an allyl ester resin soln. are continuously dried; then, a plurality of the resin-impregnated base materials are made into a laminated condition; they are continuously pressed and heated by using a double belt press to cure them. CONSTITUTION:One or a plurality of continuous glass fiber base material 10 impregnated with an allyl ester resin soln. is continuously dried in a drying oven 13. Then, a plurality of the resin impregnated base materials 10 are made into a laminated condition and they are continuously pressed, heated and cured by using a double belt press 1 constituted of endless belts 3 having a substantially uniform pressure over the whole pressing zone to prepare economically and continuously a highly heat-resistant laminated sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for continuously manufacturing a laminated board suitable for various electrical insulations, printed circuit boards, etc., in particular.

[Prior art] A long base material such as kraft paper is impregnated with a thermosetting resin liquid such as unsaturated polyester resin, multiple sheets of this impregnated base material are layered, and the resin liquid is heated without pressure. It is conventional to produce laminates continuously by curing.

However, when curing under no pressure, a thermosetting resin layer is formed between the base materials, and the content of the base material in the resulting laminate is relatively low, resulting in poor mechanical properties such as strength and rigidity. There is a tendency for there to be a shortage. Furthermore, due to the characteristics of the unsaturated polyester resin, the resulting laminate does not have sufficient heat resistance.

On the other hand, paper or glass fiber cloth is used as a base material, and after being impregnated with a thermosetting resin liquid such as phenol resin liquid or epoxy resin and dried to form a prepreg sheet, it is pressurized and heated using a batch press to form paper. It has also been conventionally possible to manufacture phenolic resin-based laminates and glass-based epoxy resin laminates.

In particular, glass-based epoxy resin laminates are known to have excellent heat resistance due to the characteristics of the resin and the base material, but their productivity is inferior to that of continuous laminates. Therefore,
Attempts have been made to manufacture laminates by laminating long prepreg sheets and continuously pressurizing and heat-molding them, but due to the slow curing speed of epoxy resins and phenolic resins, the equipment tends to be too long. However, there was a drawback that air bubbles remained in the prepreg sheet and were likely to be mixed into the resulting laminate.

[Problems to be Solved by the Invention] Therefore, the present invention aims to solve the problems in the conventional manufacturing of laminates, and specifically, the problem is to The object of the present invention is to provide an economical continuous manufacturing method for a laminate with high heat resistance, in which a laminate is obtained by laminating and heating a plurality of glass fiber substrates under pressure.

[Means for Solving the Problems] The present inventors have discovered that when a resin-impregnated glass fiber base material is cured under pressure and heat, the allyl ester resin solution-impregnated base material is dried to form a prepreg, and the curing speed is fast. Pressure heating using a double belt press with substantially uniform pressure across the pressure zone.

The present invention was completed by focusing on the fact that there are substantially no residual air bubbles in the resulting laminate.

That is, the gist of the present invention is to continuously dry one or more elongated glass fiber substrates impregnated with an allyl ester resin solution, and then to stack the plurality of resin-impregnated substrates in a laminated state. A method of curing by continuously pressurizing and heating using a double belt press consisting of an endless belt with substantially uniform pressure over the entire area, in which case a method of overlapping metal foils at the same time or in a separate process,
Furthermore, there is a method in which pressurizing fluid is pressurized at 1 to 100 kg/crt+'' into a pressurizing chamber whose surface is an endless belt.

The invention will be described in detail below.

The long glass fiber base material used in the present invention may be a single long glass fiber woven fabric, or the outermost layer may be a glass fiber woven fabric, the center layer may be a glass fiber nonwoven fabric, cellulose-mixed glass fiber paper, etc. may be used in combination.

The allyl ester resin solution referred to in the present invention is a solution in which an allyl ester resin having an allyl ester group at at least one end of a polyester composed of a polybasic acid and a polyhydric alcohol is dissolved in a solvent. Examples of basic acids include dibasic acids such as orthophthalic acid, orthophthalic anhydride, isophthalic acid, phthalic acids such as terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, and methylendomethylenetetrahydrophthalic acid. , hydrophthalic acids such as hexahydrophthalic acid, methylhexahydrophthalic acid and their lanoic anhydrides, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, and adipic acid, tetrabromophthalic acid, and tetrachlorophthalic acid. acid,
Examples include halogenated dibasic acids such as chlorendic acid and their acid anhydrides, and examples of trifunctional or higher functional polybasic acids include trimellitic acid, pyromellitic acid, and their acid anhydrides.

These polybasic acids can be used alone or in combination.

In addition, polyhydric alcohols include ethylene glycol,
1,2-propylene glycol, 1. Dihydric alcohols containing aliphatic, alicyclic or aromatic compounds such as 4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexane dimetatool, paraxylene glycol, and HO -(-CHCH,-0-)n-H (R is hydrogen or a chain alkyl group, n is an integer of 2 to 10) Addition reaction of alkylene oxides such as ethylene oxide and propylene oxide Examples include dihydric alcohols obtained by

Examples of the trihydric or higher polyhydric alcohol include aliphatic trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric or higher alcohols such as pentaerythritol and nlupitol.

In addition, aliphatic compounds containing halogen atoms, such as dibrome neopentyl glycol and tetrabrome bisphenol A adducts of ethylene oxide and propylene oxide,
Examples include alicyclic and aromatic halogenated polyhydric alcohols. These can be used alone or in combination.

The method for producing the allyl ester resin is not particularly limited, and may be any known method such as the method proposed in Japanese Patent Application No. 63-262217.

For example, there is a method in which diallyl ester of a dibasic acid such as diallyl terephthalate and the above polyhydric alcohol are charged into a reactor together with a transesterification catalyst and reacted while distilling off allyl alcohol. In addition, as an industrially more effective method, instead of diallyl terephthalate, a dialkyl ester of a dibasic acid such as dimethyl terephthalate and allyl alcohol are charged into a reactor together with a polyhydric alcohol and an ester conversion catalyst, and alcohols such as methanol are produced. A method is used in which the reaction is carried out while distilling off. Additionally, depending on the reaction temperature, a polymerization inhibitor such as hydroquinone may be added to the reaction solution.

They may coexist inside.

In this way, an allyl ester resin having an allyl group at at least one end of the polyester is produced.

This allyl ester resin may be used alone or in combination of two or more types.

In addition, by selecting various types of polybasic acids and polyhydric alcohols, the type of allyl ester resin can be varied, and from among these various allyl ester resins, the most suitable one can be selected. By manufacturing a laminate using this, it is possible to obtain a laminate with good electrical properties, dimensional stability, moisture resistance, flame retardancy, and machinability while maintaining heat resistance.

The above allyl ester resin is generally solid or
Since it is a viscous liquid, it is difficult to impregnate the base material as it is. Therefore, in the present invention, the allyl ester resin is used as a solution dissolved in a solvent.

Such a solvent is preferably one that evaporates at a relatively low temperature, and is not particularly limited as long as it dissolves the allyl ester resin, although it varies depending on the type of the allyl ester resin.

Examples include hydrocarbons such as EVA, cyclohexane, benzene, toluene, and xylene, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, esters such as methyl acetate, ethyl acetate, butyl acetate, and lactone, methyl butyl ether, and dioxane. and ethers such as tetrahydrofuran. These solvents may be used alone or in combination of two or more.

As a method for dissolving the allyl ester resin in a solvent, for example, it may be dissolved by continuing stirring at room temperature, or the temperature may be raised above room temperature to increase the rate of dissolution.

Further, a crosslinking monomer may be added to the above solution as necessary. The crosslinking monomer preferably has a boiling point higher than the boiling point of the solvent, such as diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, diaryl orthophthalate, diallyl isophthalate, diallyl terephthalate, diaryl orthophthalate, diallyl isophthalate, diallyl terephthalate, diaryl orthophthalate, diallyl isophthalate, diallyl terephthalate, diaryl orthophthalate, diallyl isophthalate, diallyl terephthalate, diaryl orthophthalate, diallyl isophthalate, diallyl terephthalate, diaryl orthophthalate, diallyl isophthalate, diallyl terephthalate, diaryl orthophthalate, diallyl isophthalate, diallyl terephthalate.

Vinylbenzene, 2-ethylhexyl acrylate, 2-ethyl methacrylate, bovine syl, lauryl acrylate, lauryl methacrylate, and the like.

The amount of the crosslinkable monomer to be added is appropriately such that the dried resin-impregnated base material (prepreg) after impregnating the base material with the solution, removing the solvent, and drying the base material does not become too sticky.

It is necessary to add a radical curing catalyst for curing the 7lyl ester resin to the solution of the allyl ester resin obtained in this manner, and an organic peroxide is used as the radical curing catalyst.

Examples of organic peroxides include cyclohexanone peroxide, ketone peroxides such as methyl ethyl ketone peroxide, 111-bis(t-butylperoxy)3,3.5-trimethylcyclohexane,
1.1-bis(t-butylperoxy)cyclohexane, 2.2-bis(t-butylperoxy)octane, 2
．． Peroxyketals such as 2-bis(t-butylperoxy)butane, n-butyl-4,4-bis(t-butylperoxy)valerate, etc., di-1SO-propylbenzene hydroperoxide, p-menthane Hydroperoxide, 1,1゜3.3-tetramethylbutyl hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, kinimene hydroperoxide, t-butyl hydroperoxide, etc. Hydroperoxides, dicumyl chloride, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, α, α'-bis.

(1-Butylperoxy-m-isopropyl)benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-
butyl peroxide) hexine-3, etc., octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, succinic aracid peroxide, acetyl peroxide, m-toluoyl peroxide, Diacyl peroxides such as benzoyl peroxide, cumylperoxycyontate, t-butylperoxylaurate, t-butylperoxy-3,5,5-trimethylhexanate, t-butylperoxycyamotate,
Examples thereof include peroxy esters such as -butyl dibenzoate, di-t-butyl dipero-cow dibenzoate and di-t-butyl dipero-cow 15O-phthalate, and peroxycarbonates such as t-butylperoxyallyl carbonate and 1-butylpero+7-iso-propyl carbonate.

These organic peroxides can be used alone or in combination of two or more depending on the type of resin and curing conditions. Furthermore, although such organic peroxides are suitable as curing catalysts, the present invention is not limited thereto, and other curing catalysts may be used.

Furthermore, fillers such as flame retardants, colorants, mold release agents, and various inorganic powders can be added to the solution as necessary.

In particular, flame retardancy is important when manufacturing laminates due to their uses, and there are other flame retardant methods that use allyl ester resins made of halogenated saturated polybasic acids and halogenated saturated polyhydric alcohols for the skeleton. , flame retardant may be made using an additive type flame retardant.

Examples of such additive flame retardants include phosphorus-based flame retardants such as trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, triphenyl phosphite, and tris(chloroethyl) phosphate, chlorinated paraffin, decabromidiphenyl ether, and tetrachloride. Examples include halogen flame retardants such as bromodiphenyl ether, antimony compounds such as antimony trioxide and antimony pentoxide, zinc borate and aluminum hydroxide.

In the method for producing a laminate of the present invention, first, a resin solution is prepared that includes an allyl ester resin, a solvent, a radical curing catalyst, and a crosslinkable monomer and filler added as necessary. The viscosity of this solution is usually preferably 0.05 to 50 poise. If it exceeds 50 poise, impregnating the base material becomes poor and bubbles tend to remain in the resulting laminate, while if it is less than 0.05 poise, the liquid retention of the base material becomes poor.

Then, the long glass fiber base material is impregnated with such a resin solution. This impregnation is done by roll coating method.
This is carried out by appropriately selecting a known method such as a seed soaking method. In addition, in order to make the base material content in the dry impregnated base material a predetermined amount, the solution concentration,
The amount of solution impregnation is adjusted.

The long glass fiber base M impregnated with the resin solution in this manner is dried in a known drying oven such as a hot air circulation oven or a radiant oven. The drying conditions vary depending on the allyl ester resin used, the type of curing catalyst and solvent, and the concentration of the resin solution, but it is preferable that the dried substrate be in a cured state in which it is not too sticky and the resin exhibits appropriate fluidity in the subsequent pressurization and heating step. In addition, this drying can be carried out using a single resin solution-impregnated base material, and the resulting dry impregnated base material can be wound up into a roll and then fed to the pressure and heating process in a roll state, or multiple sheets can be It may be dried at the same time and supplied continuously.

The long glass fiber base material impregnated with the allyl ester resin solution and dried in this way can be stacked together to form a laminate, or can be stacked to form a laminate and substantially spread over the entire pressure zone. The material is heated and pressed by a double belt press with uniform pressure, and is cured in a short time to form a laminate.

The double belt press according to the present invention, which has a substantially uniform pressure over the entire pressure zone, is a double belt press in which, for example, endless belts made of stainless steel with a thickness of about 1 are installed above and below, and between the upper and lower belts. The base material impregnated with a resin liquid can be sandwiched between the base materials and heated and pressurized, and the structure is such that the pressure of the pressure band is substantially uniform.

To give a specific example, (1) A plurality of rows of roll pairs are arranged to sandwich the upper and lower belts and apply pressure to the belts, and the roll diameter is 501111a or less and the ratio of the roll pitch to the roll diameter is This method reduces the pressure drop between adjacent rolls by keeping it below 1.2.
The position of the rolls can be fixed, or they can be placed above and below the endless belt.

The belt may be disposed between a pressure plate and the endless belt, and may revolve around the pressure plate. The diameter of the roll increases,
If the distance between the rolls is too large, large waves will occur in the pressure applied to the substrate, which is undesirable. (2) A method in which the upper and lower endless belts are sandwiched, a pressure plate is arranged to apply pressure to the belt, and a pressure medium is press-fitted and circulated between the pressure plate and the endless belt for the purpose of lubrication, or (
3) The upper and lower endless belts are sandwiched to form a container for storing the press-fitting medium, and the opening of this container is in contact with the endless belt, and the pressure medium directly presses the endless belt. This formula is particularly suitable because the pressure difference across the entire pressure zone is small.

What is shown in FIG. 1 is an example of this pressure medium storage type double belt press. This Tuffle Belt Brace 1 is roughly composed of a drum 2.2a, endless belts 3, 3, a pressurizing chamber 4, and a pressure medium 5 made of a high temperature fluid. and a heater 8 are connected by a piping vibrator 9. The drums 2, 2 and 2a, 2a consist of a pair of upper and lower drums that rotate in opposite directions to each other along the traveling direction of the impregnated base material 1O, and are arranged in front and behind on one side of the resin-impregnated base material 1O. Endless belts 3, 3 are tensioned between the drums 2, 2a, which rotate in the same direction. Behind this endless belt 3゜3, heat and pressure ( A pressurizing chamber 4 is provided which is filled with a pressure medium 5 for holding.This pressurizing chamber 4 is a container of any shape, and its -
The construction surface is constituted by the endless belt 3, and a pressure medium 5 is press-fitted into the pressurizing chamber 4 for applying heat and pressure from the endless belt 3 to the resin-impregnated base material 10. . Further, in the pressurizing chamber 4, a pressure medium supply device 6 is arranged, which is configured by a pump 7 for supplying a pressure medium 5 and a heater 8 such as an electric heater for heating the pressure medium, which are connected by a piping pipe 9. ing. Naohi.

- 8 may be incorporated into this pressurizing chamber 4.

The pressure medium 5 is circulated between the pressure medium supply device 6 and the pressurizing chamber 4 by a pump 7, and the pressure medium 5 can be replenished, pressurized, and heated from outside the pressurizing chamber 4. There is. The inside of the pressurizing chamber 4 can be heated indirectly by heating the pressure medium 5 with the heater 8 . Furthermore, the same amount of pressure medium 5 that flows out of the pressurizing chamber 4 as the endless belt 3.3 runs is pumped into the pressurizing chamber 4 by the pump 7.
The pressure inside the pressurizing chamber 4 is kept constant.

Then, the resin-impregnated base material 10 sandwiched between the endless belts 3 and 3 is heated and pressurized by the pressure medium 5 press-fitted into the pressurizing chamber 4, and the impregnated resin liquid is remelted. It spreads uniformly, fills the voids, and is cured and integrated. The pressure medium 5 may be any fluid as long as it exhibits fluidity under the operating conditions of the double belt press 1. For example, air or nitrogen may be used as a gas; Examples of waxes and low melting point polymers include polyethylene wax and paraffin, and examples of low melting point metals include solder wood metal and the like.

Regardless of the type of double belt press, the existence of a large pressure distribution, especially the presence of large pulsating pressure in the direction of movement, causes the impregnated resin to remelt and integrate with the base material. This not only makes it difficult to selectively discharge air bubbles in the impregnated base material, but also tends to cause uneven thickness and distortion of the laminate, which should be avoided. For example, pressure distribution of ±50%
and preferably ±5 kg/cm' or less.

In addition, reference number 11 in FIG. 1 is a delivery roll for delivering the glass fiber base material, 12 is a resin impregnation tank for impregnating an allyl ester resin solution, and 13 is a drying oven.

The applied pressure also varies depending on the melt viscosity and curing rate of the resin in the impregnated base material used and the type of base material, but is selected as appropriate to control the base material impregnation in the resulting laminate. . Usually 1kg/c ■ 1G to 100 kg/
cm”G, preferably 1゜0 kg/am
"G to 50 kg/am" G. pressure is 1
kg/am” G, not only is it difficult to increase the base material content, but the air evacuation effect is small, and the laminate is likely to have bubbles mixed in. On the other hand, if the pressure is 100 kg/C
If it exceeds 1 l''G, not only is it unnecessary to remove bubbles, but also the base material content in the resulting laminate becomes too large, which tends to cause deterioration in strength such as delamination.

The temperature used for pressure heating varies depending on the type of allyl ester resin liquid used, the type of curing catalyst, etc., but the temperature is usually in the range of 50'C to 200°C, preferably 100°C. The temperature is 200°C. 50℃
If the temperature is lower than 200°C, the time required for curing is too long and it is uneconomical. If the temperature exceeds 200°C, internal distortion occurs due to the rapid progress of curing, and when a crosslinkable vinyl monomer is used, delamination may occur due to evaporation of the monomer. more likely to occur.

On the other hand, the time required for curing the impregnated base material varies depending on the type of allyl ester resin used, the type of curing catalyst, the heating temperature, the thickness of the resulting laminate, etc., but is usually in the range of 10 minutes to 2 hours. However, it is not necessary to apply pressure and heat using a double belt press for the entire time of milling, and the time of pressure and heating should be kept to the minimum necessary to reach a degree of hardening that allows the laminate to be transported, cut, etc. It is economical to carry out heating after continuous conveyance without applying pressure or heating after cutting into a predetermined length in batches. Since the dry resin-impregnated base material using the allyl ester resin of the present invention has a faster curing speed than that using an epoxy resin, delamination may occur after the pressure is released due to the restoring force of the base material. It is also possible to set the time to about 1 minute.

Although the amount of the glass fiber base material in the laminate in the present invention varies depending on the type of glass fiber base material and allyl ester resin used, it is usually preferably in the range of 30 to 70% by weight. If it is less than 30% by weight, the dimensional stability of the laminate deteriorates, and if it is more than 701% by weight, machinability deteriorates, which is not preferable.

Also, to produce metal foil laminates, resin.

This is carried out by overlaying metal foil on one or both sides of a laminate made of liquid-impregnated base materials at the same time as or a little later than the overlapping of the base materials, and then feeding this to a double belt press.

As the metal foil used here, an electrolytic copper foil intended for use in printed circuit boards is suitable from the viewpoint of corrosion resistance, etching property, and adhesiveness, but aluminum foil or the like may also be used. Further, as such metal foil, one having a thickness of 10 to 100 .mu.- is usually used, and it is more preferable that the adhesive surface is roughened to improve adhesiveness.

An adhesive may be used to improve the adhesion between the metal foil and the resin-impregnated base material. The adhesive is preferably a liquid or semi-fluid adhesive that does not generate unnecessary reaction by-products during the curing process, that is, an adhesive that preferably has a viscosity of 50 oO Boise or less. From this point of view, for example, epoxy-acrylate adhesives, epoxy resin adhesives,
Polyisocyanate adhesives or various modified adhesives thereof are suitable. As the epoxy adhesive, a mixture of a bisphenol A type epoxy resin and a curing agent such as a polyamide resin or amines is suitable. By introducing such an adhesive, it is possible to produce a metal foil-clad laminate that has excellent adhesive strength of metal foil, and also has excellent solder heat resistance and electrical insulation properties.

When the adhesive is used in a state where it is applied to metal foil, it may be precured to a semi-cured state by heat treatment at 60 to 150° C. for 2 to 7 minutes after application. Furthermore, the adhesive can be applied simultaneously during lamination. The thickness of the adhesive coating may be about 10-100 u+a, and a thickness of 20 to 50 μm is particularly suitable.

Although the thickness of the laminate obtained in the present invention varies depending on the type of substrate, the composition of the thermosetting resin liquid, the use of the laminate, etc., it is usually preferably 0.5 to 3.0 mm.

EXAMPLES Hereinafter, the method for manufacturing a laminate of the present invention will be specifically explained using examples, but the following examples do not limit the present invention.

[600 g of diallyl terephthalate and 78.4 g of ethylene glycol were placed in an IC Mitsuro flask equipped with a co-distillation device for production of allyl ester resin (A).
, dibutyltin oxide 0, Ig were charged and heated to 180° C. under a nitrogen stream, and allyl alcohol produced was distilled off. When about 140 g of allyl alcohol b<140 g was distilled out, the pressure inside the flask was reduced to 50 mlHg.
The distillation rate was increased.

After the theoretical amount of allyl alcohol was distilled off, the reaction solution was heated to 1 mmHg while maintaining it at 200°C using a thin film evaporator.
In the step, unreacted diallyl terephthalate was distilled off. The reaction solution was poured into a vat, cooled, and pulverized to obtain powdered allyl ester resin (1).

Furthermore, allyl ester resins (II) to (V) were obtained using the same method as that for obtaining the allyl ester resin (I), except that the materials shown in Table 1 were used.

Table 1 shows the materials used and their blending amounts.

(Examples 1 to 6) Long glass fiber cloth (WEA18W manufactured by Nittobo Co., Ltd.)
105-F-115, basis weight 215 g/s'),
After being continuously impregnated with the allyl ester resin solution shown in Table 2, it was continuously dried for 5 minutes at 120° C. in a hot air circulation type drying oven to obtain a dry resin-impregnated base material. The resin content of this impregnated base material is shown in Table 2.

Next, using 8 sheets of impregnated substrates, a 35μ thick electrolytic copper foil with epoxy resin adhesive was laminated as the outermost layer, and a double belt press containing a pressure medium as shown in Fig. 1 was used to continuously stack the sheets. Heat and pressure mold at 150°C for 3 minutes, then further heat to 160°.
After curing at C for 20 minutes, a double-sided metal foil-clad laminate was obtained.

The thickness of the obtained laminate was 1.5 to 1.7+nm.

The properties of this laminate are shown in Table 3.

(Comparative Example 1) The same procedure as in Example 1 was carried out, except that the resin solution was an epoxy resin solution consisting of Ebicor 827/Epicote 154/dicyandiamide/methyl ethyl ketone/methyl cellosolvenyl 4515/2/28/20 (weight ratio). A double-sided metal foil-covered laminate was obtained. The properties of this product are shown in Table 3.

(Comparative Example 2) A double-sided metal foil-clad laminate was obtained in the same manner as in Comparative Example 1, except that the pressure and heating time using the double belt press was 20 minutes. The properties of this product are shown in Table 3.

As is clear from Table 3, the laminates of Examples exhibit no delamination or bubbles even after continuous pressure and heat molding for a short period of time, and exhibit excellent heat and moisture resistance.

The methods for measuring solder heat resistance, volume resistivity, and water absorption in Table 3 were carried out in accordance with -JIS C6481. Further, the glass transition temperature of the laminate was measured using a thermal stress strain measuring device.

"Effects of the Invention" As explained above, according to the method for continuously manufacturing a laminate of the present invention, a highly heat-resistant laminate made of allyl ester resin and glass fiber can be economically manufactured with high productivity. I can do it.

[Brief explanation of the drawing]

FIG. 1 is a schematic configuration diagram showing an example of a double belt press used in the present invention.

Claims (4)

[Claims] (1) Continuously dry one or more long glass fiber substrates impregnated with an allyl ester resin solution, and then stack the plurality of resin-impregnated substrates in a layered state to substantially cover the entire pressure zone. 1. A method for continuously manufacturing a laminate, which comprises curing the laminate by continuously applying pressure and heating using a double belt press configured with an endless belt that applies uniform pressure. (2) The continuous production method of a laminate according to claim 1, wherein the laminate is a metal foil-clad laminate formed by laminating a plurality of sheets of metal foil and a resin-impregnated base material simultaneously or in separate steps. (3) A double belt press consisting of an endless belt that has a substantially uniform pressure over the entire pressure zone, has a pressurizing chamber with the endless belt as one of its constituent surfaces, and uses a fluid as a pressure medium. The method for continuously manufacturing a laminate according to claim 1, which is a double belt press. (4) The method for continuously manufacturing a laminate according to claim 1, wherein the pressurizing pressure is in the range of 1 to 100 kg/cm^2.