JPS5838301B2 - Seizouhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing thin resin composites.

In recent years, with regard to the use of thin leaf materials, especially thin leaf synthetic resin materials, due to the diversification of their uses and functions, thin leaf materials made of a single variety have little utility value, and thin leaf materials made of composites of multiple types of materials are being widely used. The demand for these products is also increasing.

As a composite thin resin material, products in which multiple types of synthetic resin films are bonded together, which is usually called a laminate product, are generally commercialized, but the manufacturing method thereof is as follows: Method of bonding each other (2) A film forming method in which different kinds of joint resin solutions are applied onto a synthetic resin film and dried.

(3) Extrusion lamination is carried out in which a resin melt is directly laminated onto a resin film while being extruded from an extruder.

However, in the method (1) above, the properties of the adhesive significantly affect and limit the properties of the laminate product, and in the method (2), the mutual adhesion is limited when coating and drying. In addition, the method (3) has drawbacks such as the fact that the meltable materials are limited to resins with relatively low softening points.

Another method for producing a thin composite material consisting of two different layers by a wet molding method is to apply a synthetic resin solution to a nonwoven fabric or a cloth-like material, and then transform the coated layer into a resin layer by wet molding, such as in a method for manufacturing synthetic leather. A method of converting is known, but in this method, the adhesion of both layers is mostly due to the coating solution being mixed between the fibers of the nonwoven fabric or cloth layer, and the synthetic resin to be coated is an organic solvent. Because it uses materials that can be dissolved in water, it has been impossible to scale laminate products, which have excellent heat resistance.

The present invention has been made as a result of intensive research to improve these drawbacks, and as a result, a manufacturing method for producing laminated products with excellent heat resistance has been discovered, leading to the present invention.

That is, a sulfuric acid-soluble and non-degradable resin thin sheet material is used as a carrier, and a sulfuric acid solution of a sulfuric acid-soluble and non-degradable synthetic resin is cast on one or both sides of the carrier, and then this is poured into water. A thin resin composite material having a synthetic resin film integrally bonded to the surface of the carrier is obtained by immersing the carrier in a coagulation bath mainly containing a liquid miscible with both the carrier and sulfuric acid and coagulating and drying it.

To explain the present invention in more detail, thin resin materials that are soluble in sulfuric acid and substantially non-decomposable, such as polyacrylonitrile,
Polyamide, polyamideimide, polybenzimidazole, polybenzimidazopyrroline, polybenzthiazole, polybenzoxazole, polyoxadiazole,
Polythiadiazole, polyhydrazide, polyhydantoin, polyhalabanic acid, polyphenyl ether, or a copolymer thereof, or a mixed resin mainly composed of these resins, or a combination of these resins with carbon black, glass powder, glass fiber, A film, nonwoven fabric, paper, cloth, impregnated cloth, etc. containing fillers or fibers such as carbon fiber, metal fiber, aluminum oxide, titanium oxide, etc. is used as a carrier, and the surface of the carrier is made soluble in sulfuric acid. After coating a sulfuric acid solution of a substantially non-degradable synthetic resin, such as a synthetic resin selected from the above resin group, or extruding it through a slit and casting, a coagulating liquid that is miscible with both water and sulfuric acid as it is, such as water. , an aqueous solution of sulfuric acid, nitric acid, phosphoric acid, organic acid, etc., or a single or mixed liquid of two or more of organic solvents such as alcohol, acetone, etc., or an inorganic salt such as sodium sulfate, zinc sulfate, ammonium sulfate, etc. It is immersed in a small amount of liquid, solidified, and then dried.

Note that, if necessary, heat treatment may be performed at an appropriate temperature after drying.

Note that by adding an inorganic salt to the coagulation liquid, the transparency and heat resistance of the thin resin composite material obtained can be significantly improved.

Further, the temperature of the coagulating liquid does not need to be particularly limited, but the decomposition of the synthetic resin by sulfuric acid becomes significant at high temperatures, so it is preferably 50° C. or lower.

In the present invention, since the solvent of the resin solution to be applied is sulfuric acid and the coated layer is soluble in sulfuric acid, the coated surface not only has excellent wettability and affinity, but also has no heat generation in the coagulation liquid. Since a moderate amount of resin is diffused at the interface between the thin leaf material carrier and the synthetic resin film between the eyebrows, there is no need to perform any special treatment on the surface to be coated to improve adhesion, such as surface treatment.

Since a clean active surface is obtained with sulfuric acid, the carrier and the resin film can be strongly bonded, and the desired thin-sheet composite resin material can be easily obtained.

Therefore, conventionally it has not been possible to make a laminate product by bonding a thin leaf material carrier with excellent heat resistance and a synthetic resin insoluble in organic solvents, such as a so-called heat-resistant resin made of wholly aromatic compounds, by a coating method. However, in the present invention, this can be easily achieved with the L-type resin composite material, and the resulting thin resin composite material has much better heat resistance than conventional products, so it can be used as an electrical insulating material or a thermal insulating material. It is used in a wide range of industrial materials such as packaging materials and protective materials.

Next, the present invention will be explained in detail by way of examples.

Example 1 Paper obtained from polymetaphenylene isophthalamide fibers (trade name: Nomex 4, manufactured by du Pont;
10 thickness 50μ) with a resin concentration of 6% on one side.
A sulfuric acid solution (solution viscosity: 1200 poise at 30°C) of 5-p/m phenylene 1,3,4-oxadiazole) copolymer (p/m ratio 85/15) was cast, After coagulating by immersion in an aqueous solution at 18° C. containing 45% sodium sulfate and 45% sulfuric acid, the sample was washed with water, immersed in a 0.2% caustic soda solution, washed with water, and dried.

The thus obtained polyamide polyoxadiazole composite was further heat treated at 280°C for 5 minutes to obtain No.
A thin resin composite material consisting of a 50μ mex layer and a 25μ polyoxadiazole layer was obtained.

Example 2 Poly(2,5-P-
A mixture of 80 parts of phenylene-1,3,4-oxadiazole (intrinsic viscosity 3.1) and 20 parts of poly(ethylene terephthalamide) (intrinsic viscosity 1.9) dissolved in concentrated sulfuric acid. The solution was extruded through a hopper with a slit of 057rLrIL and cast.
It was immersed in a 48% sulfuric acid aqueous solution at 20° C. to solidify, washed with water, then immersed in a 1% monoethanolamine aqueous solution at 20° C., immediately washed with water, and dried.

The thus obtained polyimide polyoxadiazole composite was further heat treated at 350°C for 2 minutes to obtain a thin resin composite material consisting of a 25μ polyimide layer and a 30μ polyoxadiazole/polyamide layer.

Example 3 Poly(P-phenylene 1,3,4-oxadiazole)
P-phenylene 1.3 on one side of the film (thickness 25μ)
・A sulfuric acid solution of 4-oxadiazole-N-methyl terephthalate-hydrazide copolymer (copolymerization ratio 71/29) (intrinsic viscosity 28) was extruded and cast through a hopper with a gap of 500 μm in width. was immersed in an aqueous solution of 48% sulfuric acid and 5% nitric acid at 20°C to solidify, then washed with water, then immersed in a 0.1% aqueous solution of caustic soda, immediately washed with water, and dried. .

The thus obtained polyoxadiazole-P phenylene oxadiazole composite was further heat-treated at 260°C for 3 minutes to obtain a thin resin composite material consisting of a 25μ polyoxadiazole layer and a 25μ polyterephthalic acid hydrazide layer. .

Table 1 shows the results of measuring the strength and other properties of the thin resin composite materials obtained in Examples 1 to 3 above.

Example 4 Poly(bibenzimidazopyrolone) (
A sulfuric acid solution with an intrinsic viscosity of 16) was cast, immersed in an aqueous solution containing 5% magnesium sulfate and 42% sulfuric acid at 22°C to coagulate, washed with water, and then poured into a 0.5% monoethanolamine aqueous solution. After soaking, it was washed with water and dried.

The thus obtained polyamide-polypenzimigzopyrrolone composite was further heat-treated at 260° C. for 3 minutes to obtain a thin resin composite material consisting of a polyamide cloth layer of 0.75 mm and a polybenzimidazopyrrolone layer of 15 μm.

Table 2 shows the results of measuring the tear strength and other properties of the thin resin composite material obtained in this example.

Table 2 Tear strength (Mullen type) 10k9-crA180℃×
1000 hours 98% of the strength before heating Change in tear strength after heating No delamination even after heating) Tensile strength 15 kg/crrL Elongation 8% Peel test 0. 9 k9 7 cm As detailed above, according to the method of the present invention, it is possible to obtain a thin composite resin material using a coating method that is completely different from conventional methods, and the resulting product is extremely superior in heat resistance and other properties. It has industrial utility value, such as being suitable as an electrical insulating material and other uses.

Claims (1)

[Claims] 1. After using a thin leaf material of a resin that is soluble in sulfuric acid and non-degradable as a carrier, and casting a sulfuric acid solution of a synthetic resin that is soluble in sulfuric acid and non-degradable on one or both sides of the lees, A method for producing a thin resin composite material, which comprises immersing the thin resin composite material in a coagulation bath containing a liquid miscible with both water and sulfuric acid as a main component, and coagulating and drying it.