JPS63283947A - Preparation of laminated sheet - Google Patents

Abstract

PURPOSE:To prepare a polyimide type laminated sheet having a stable quality, by laminating a plurality of base materials of continuous length impregnated with a polyimide resin, passing it through double belts formed with a pair of conveyer belts and pressing it while being heated to cure the polyimide resin. CONSTITUTION:A base material 1 of continuous length wound in a coil-like shape is unwound, and is impregnated with a polyimide resin 2 by immersing it in a polyimide resin 2 vanish and so on while being transferred continuously, and is sent continuously while being laminated. Moreover, metal foils 9 of continuous length are continuously laminated on one or both faces thereof while being unwound from a coil. Then, it is sent continuously in double belts 4 and molding where the polyimide resin is cured by pressing while being heated can be carried out. It is thereby possible to obtain a laminated body of continuous length where the base materials among themselves and the base materials and the metal foils are integrally laminated with the cured polyimide resin. A laminated plate A is obtained by cutting the laminated body 5 of continuous length thus prepared in a required dimension by means of a cutting apparatus 13.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field J] The present invention relates to a method for producing a polyimide resin-based laminate.

[Background Art 1] Polyimide resin laminates have excellent heat resistance, electrical properties, etc., and are therefore used as electrical laminates such as high-grade printed wiring boards. To manufacture polyimide resin laminates, prepregs are created by impregnating the base material with polyimide resin, drying it, and cutting it into the required dimensions. Layer metal foil such as #4 foil and sandwich it between metal plates, make 10 to 15 sets of this and sandwich them between hot platens, set in a 20 to 30 stage multi-stage press machine, and in this state. Conventionally, it has been common to carry out heating and pressure molding.

However, the molding temperature of polyimide resin is 170℃~200℃.
It is impossible to perform molding while uniformly applying heat to each of the 10 to 15 sets of resin-impregnated base materials sandwiched between the heating plates. There was a problem in that the performance of each of the 10 to 15 sets of laminates formed between the two was inevitably subject to large variations.

[Object of the Invention] The present invention has been made in view of the above points, and an object of the present invention is to provide a method for manufacturing a polyimide resin-based laminate that can be manufactured with stable quality. It is.

Disclosure 1 of the Invention The method for manufacturing a laminate according to the present invention involves impregnating a long strip-shaped base material with a polyimide resin, stacking a plurality of long base materials impregnated with the polyimide resin, and then stacking the long base materials impregnated with the polyimide resin. A long laminate is created by hardening the polyimide resin by passing it through a double belt formed by a pair of conveyor belts while applying heat and pressure, and then cutting it into the required size. The present invention will be described in detail below.

In the present invention, as the polyimide resin, in addition to general polyimide resins, polyimide resins modified with epoxy resins, unsaturated polyester resins, etc., polyimide resins mixed with epoxy resins, unsaturated polyester resins, etc. can also be used. Furthermore, it is also possible to use a polyimide resin made flame retardant by containing one or a combination of aliphatic bromine compounds, alicyclic bromine compounds, and aromatic bromine compounds. For example, the aromatic bromine compound is one whose general formula is represented by formula (1), the aliphatic bromine compound is one whose general formula is represented by formula (II), and the alicyclic bromine compound is one whose general formula is represented by formula (II). Those whose general formula is represented by the formula (■) can be used.

RCHzBr, RCHBr R', R-CBr-
R' (II) R'' Specific examples of these include brominated polyphenyl, tetrabromobutane, tetrabromoethane, 1.2.3)
Liprompropane, hexabromocyclododecane, tetrabromobenzene, tetrabromohetatalic anhydride, tetrabromobisphenol A.

Bromine-containing polyol, tris(2,3 dibromopropyl)
phosphate, tris(promchlorp-a-pyr) phosphate, chlorbentabromocyclohexane, dibrominated phenyl ether, pentabromphenyl, allyl ether, bromoalkenyl ether, and the like. In this case, the total bromine content is preferably set to 30 vIL amount % or less in the resin. That is, if the content exceeds 30% by weight, the strength of the laminate tends to decrease.

The base material can be a long strip of paper, plush cloth, plush paper, synthetic fiber cloth, natural fiber cloth, nonwoven fabric, mat, felt, net, cheesecloth, etc. If necessary, for example, laminate It is also possible to use a combination of multiple types, such as using a nonwoven fabric for the core material and a plush fabric for the front and back materials.

Then, the base material 1 is impregnated with the polyimide resin 2 by unwinding the long base material 1 wound into a coil and immersing it in the polyimide resin 2 while continuously flowing it. The amount of impregnated resin should be such that the proportion of polyimide resin 2 in base material 1 impregnated with polyimide resin is about 40 to 60% by weight. It is preferable to adjust the R. In this case, the impregnation is divided into two times, and the first impregnation is performed by using a low viscosity melamine resin varnish or low viscosity 7 el resin varnish that has good permeability to the base material 1, and adjusting the resin amount. It may be done so that the amount of resin is about 1 to 10% by weight, and then impregnated with polyimide resin varnish as a second impregnation so that the total amount of resin is 40 to 60% by weight. .

In this way, a plurality of elongated base materials 1 impregnated with polyimide resin are continuously fed while being overlapped, and further, elongated metal M9 is unwound from the coil on one or both sides of the elongated base materials 1 and continuously overlapped. The base materials 1 impregnated with polyimide resin may be layered without drying, but they may be layered after being passed through a drying furnace 10 such as a tunnel furnace and dried, as shown in the attached diagram. Either is fine.

Further, as the metal foil 9, a foil made of copper, aluminum, iron, nickel, zinc, etc. or an alloy thereof can be used, and if necessary, an adhesive may be provided on the side that overlaps the base material 1. It's okay.

Next, the plurality of elongated base materials 1 impregnated with polyimide resin and the metal M9 stacked together are continuously fed to the double belt 4, which is a pair of metal conveyor belts 3. , 3 facing each other vertically, and both conveyor belts 3, 3 are operated by air pressure, hydraulic pressure,
0.5-10 due to the action of the pressurizing device 11 using magnetic force etc.
The double belt 4 is designed to be brought into contact with a pressurized state of about 1.5 kg/cm". Also, the double belt 4 can be heated in a tunnel furnace at a temperature of about 170 to 200°C, which is necessary for curing polyimide resin. It is arranged in a heating furnace 12.Therefore, a plurality of elongated base materials 1 impregnated with polyimide resin and a metal M9 are stacked and passed through the double belt 4, thereby heating and pressurizing the material. Molding can be performed by curing the polyimide resin, and it is possible to obtain a long laminate in which the base materials or the base material and the metal foil are laminated and integrated with the hardened polyimide resin.Here,
If the length of the double belt 4 is too long, the equipment cost will increase and it will be difficult to maintain uniformity in pressurization, so heating and pressurization can be completed sufficiently within the specified double belt 4. It is preferable to provide a device that can perform preheating immediately before the double belt 4.The long laminate 5 thus created is cut into required dimensions by the cutting device fi13. The weight of the laminate A can be obtained by The laminate A can be further heated in an oven or an infrared heating furnace 77 as required.
You can also do 77 turkeys.

The invention will now be illustrated by examples.

K (K polyimide resin (Kelimide 601 manufactured by Rhone Poulenc)
) 85 parts by weight, 5 parts by weight of tetrabromoethane, 10 parts by weight of brominated diphenyl ether, 10 parts by weight of N-methylpyrrolidone
1 piece of polyimide resin varnish consisting of 0 parts by weight 0.
2-1. Pass a long piece of glass cloth with a width of 10105 mm as shown in the attached diagram, impregnate each glass cloth with polyimide resin so that the resin amount is 45% by weight, and then add the glass impregnated with this polyimide resin. Pass the cloth through a tunnel furnace to 140℃
After drying with heat, stack the four sheets and apply 984M adhesive with a thickness of 0.035 on both top and bottom surfaces.
The laminate is made by stacking the adhesive layer on top of each other and passing it through a double belt.Then, the polyimide resin is cured by applying heat and pressure at 5 kg/'am'' at 180°C for 30 minutes. The laminate thus obtained was
An electrical laminate was obtained by cutting a sized laminate into a size of 1000 x 1000e and placing it in an open air oven at 260° C. for 120 minutes with 77 degrees of Turkish air.

After impregnating a long length of glass cloth with polyimide resin in the same manner as in the Example, each polyimide resin-impregnated glass cloth was heated and dried, and then cut into a size of 101050 x 1050 to prepare a prepreg. 4 sheets of prepreg were stacked, and 0.035 mm thick @ foil was layered above and below it, and this was sandwiched between 1°0-thick stainless steel plates, and 15 sets were sandwiched between hot plates. , set this on a 30 Pi press gtl! and set the molding pressure to 40
kg/0m2. A laminate was produced by molding at 170°C for 120 minutes. After this laminate was taken out, it was subjected to an after-cure at 200° C. for 120 minutes to obtain an electrical laminate.

Of the laminates obtained as described above, 15 of the examples were taken out, and 15 of the comparative examples were taken out between a pair of heating plates, and each laminate was peeled off with #l whistle. The strength, water absorption rate, bending strength, and normal insulation resistance were each measured, and the maximum values and the table results confirmed that the range of variation in each property of the example was small and the quality of the laminate was stable. be done.

[Effects of the Invention] As described above, in the present invention, a long diagonal-shaped base material is impregnated with a polyimide resin, and then a plurality of long base materials impregnated with the polyimide resin are stacked, and then a pair of these long base materials are stacked. After creating a long laminate by passing it through a double belt formed by a conveyor belt and applying heat and pressure to harden the polyimide resin, the laminate is manufactured by cutting it to the required size. Therefore, the heating and pressure forming of the laminate can be done one set at a time by stacking long base materials impregnated with polyimide resin, instead of stacking a large number of prepregs. It is possible to produce laminates with stable quality by uniformly adding laminates, and furthermore, this heating and pressure forming can be carried out while continuously feeding the long base material with a double belt. It can be manufactured in a continuous process with high production efficiency.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of an embodiment of the present invention, in which 1 is a base material;
2 is a polyimide resin, 3 is a conveyor belt, 4 is a double belt, 9 is a metal foil, and A is an FA layer plate.

Claims (1)

[Claims] (1) After a long strip-shaped base material is impregnated with polyimide resin, a plurality of long base materials impregnated with this polyimide resin are stacked and heated by passing them through a double belt formed by a pair of conveyor belts. 1. A method for manufacturing a laminate, which comprises creating a long laminate by applying pressure to harden the polyimide resin, and then cutting the laminate into required dimensions.