JPH02249645A - Manufacture of composite film - Google Patents

Abstract

PURPOSE:To obtain the composite film which is excellent in weathering resistance and peel strength and contains base cloth by a method in which the base cloth is impregnated with the organic solvent solution of specified resin, and further said base cloth is coated with the aqueous dispersion of the copolymer of urethane-vinyl chloride resin and is pressure bonded under heating. CONSTITUTION:A base cloth is impregnated with the organic solvent solution of at least one kind-resin selected from the copolymer of urethane-vinyl chloride, polyalkyl methacrylate and polyamide, and after the surface of the obtained resin-impregnated base cloth has been coated with the aqueous dispersion of the copolymer of urethane-vinyl chloride, it is dried and pressure-bonded under heating. Further, a fluorine plastic film is pressure-bonded under heating onto the surface of a dispersion-holding base cloth or the composite film containg the base film through the adhesive layer composed of polyalkyl methacrylate. The composite film containing the base cloth may be produced by simple process without using much organic solvent. Since the bond strength of the fluorine plastic film is high, and the aging of said film is little, it is used for the water resistant sheet such as a tent or a sheet for a truck, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Object of the invention [Field of industrial application] The present invention generally relates to a composite membrane used for waterproof fabrics such as tents, tents, cushions, etc., and for various other uses.

[Conventional technology]

As a waterproof fabric with good weather resistance, a composite membrane (unexamined patent application) is made by laminating a base fabric coated with a soft polyvinyl chloride resin compound, a polymethacrylic resin as an intermediate layer, and a fluorine resin film as the outermost layer. Publication No. 59-140053) or a composite membrane of the same type as the above composite membrane, which uses a urethane-vinyl chloride copolymer instead of the above-mentioned soft polyvinyl chloride resin compound (Japanese Patent Laid-Open No. 61 297139) etc. have already been proposed.

Regarding the air membrane, a composite membrane in which a glass fiber woven cloth is coated with a tetrafluoroethylene resin has been proposed.

Since the coating film described in JP-A-59-140053 uses polyvinyl chloride containing a plasticizer, the peel strength of the film tends to decrease over time due to interfacial migration of the plasticizer. On the other hand, although the composite membrane described in JP-A No. 61-297159 has excellent peel strength and durability, the manufacturing process is complicated and requires the use of a large amount of organic solvent. The problem was that it didn't. That is, in order to impregnate the base fabric with the urethane-vinyl chloride copolymer, an organic solvent solution of the copolymer is used, but in the method using Yu43 & bath agent mochi liquid,
In order to coat the base fabric with the required amount of copolymer, the operations of impregnating and drying must be repeated many times, which is not economical as it consumes a large amount of organic solvent, and also poses a fire hazard. There was a hygiene problem.

An object of the present invention is to solve the above-mentioned problems and to provide a method for producing a coating film containing a base fabric, which has excellent weather resistance and peel strength, and which involves simple work steps.

(B) Structure of the Invention [Means for Solving the Problems] As a result of intensive studies to solve the above problems, the present inventors have found that: By obtaining a base fabric coated with resin, then coating the base fabric with a water-based diced version of urethane-vinyl chloride copolymer, and bonding with heat, we can create a base fabric with good performance that can be used in a variety of fields. We found that it is possible to manufacture a composite membrane, and that by thermocompression bonding a fluororesin film to the surface of this composite membrane via an adhesive layer made of polyalkyl methacrylate, a highly weather-resistant composite membrane with strong peel strength can be easily manufactured. This discovery led to the completion of the present invention.

That is, the present invention impregnates a base fabric with an organic solvent solution of one or more resins selected from urethane-vinyl chloride copolymers, polyalkyl methacrylates, and polyamides, and then evaporates the organic solvent. After applying an aqueous dispersion of urethane-vinyl chloride copolymer to the surface of the resulting resin-impregnated base fabric, the moisture is removed by drying to obtain a dispersion-supported base fabric, and the base fabric is then thermocompression bonded. A method for producing a composite membrane containing a base fabric characterized in that the method further comprises applying a fluororesin film onto the surface of the dispersion-supporting base fabric or composite membrane containing a base fabric via an adhesive layer made of polyalkyl methacrylate. This is a method for producing a highly weather resistant composite membrane, which is characterized by thermocompression bonding.

Hereinafter, the present invention will be explained in more detail.

[Base fabric]

The base fabric used in the present invention is, for example, polyester,
Synthetic fibers such as aromatic polyamide, glass fibers, and carbon fibers are used.

The thickness of the base fabric layer is preferably 0.2 to 0.6M.

If the thickness is not 0.2g, the tensile strength of the composite membrane tends to be weak, and if the thickness exceeds 0.61111, the cost increases, and although the strength increases with thickness, it is likely to be too large for the purpose of the present invention. .

[Resin for impregnation]

In the present invention, the impregnating resin to be impregnated into the base fabric as an organic solvent solution is obtained by preparing vinyl chloride in an aqueous medium in the presence of a urethane-vinyl chloride copolymer, such as a thermoplastic polyurethane soluble in vinyl chloride monomer. Urethane-vinyl chloride copolymer obtained by polymerizing a monomer alone or a vinyl chloride monomer mainly composed of the monomer (Japanese Patent Application Laid-Open No. 58-40
No. 312) etc.; polyalkyl methacrylate; polymethyl methacrylate, polyethyl methacrylate, and copolymers of methyl methacrylate or ethyl methacrylate and other alkyl methacrylates or alkyl acrylates in which the alkyl group has 1 to 4 carbon atoms;
and polyamides such as polyamides or copolyamides consisting of piperazine and aliphatic dicarboxylic acids.
260671).

The polyurethane content in the urethane-vinyl chloride copolymer resin is preferably 40 to 60% by weight.

If the polyurethane content is less than 40 weights, the resin will be hard and the tear strength will tend to be weak, and if it exceeds 60 weights, the resin will become soft and the durability will tend to deteriorate.

Specific examples of urethane-vinyl chloride copolymer resins include:
For example, Aron NP-5000, Aron NP-6000,
Aron NP-7000 <Toagosei Kagaku Kogyo ■ Crotch product name) is mentioned.

When a copolymer of methyl methacrylate or ethyl methacrylate is used as the polyalkyl methacrylate, a copolymer containing 50 or more methyl methacrylate monomer units or ethyl methacrylate monomer units is preferred.

Specifically, Acrivet MA, Hypet HBR1 Diannaru BR-90, Diannaru BR-93, Diannaru BR-107 (all names of parts manufactured by Mitsubishi Rayon ■), etc. are mentioned.

When polyamide or copolyamide is used, it is preferable to use 0.05 to 10 parts by weight of epoxy silane such as γ-glycidoxyglobytrimethoxysilane per 100 parts by weight of polyamide or copolyamide. There are products such as FS-175SV manufactured by Synthetic Chemical Industry ■.

As organic solvents for dissolving the impregnating resin, toluene, methyl ethyl ketone, tetrahydrofuran, etc. are suitable for urethane-vinyl chloride copolymers and polyalkyl methacrylates, lower alcohols such as methanol, ethanol, and globanol, and water, Mixed solvents such as chloroform, trichloroethylene and dichloromethane are suitable for polyamides or copolyamides.

The resin solution concentration may be about 10 to 60% by weight, and the base fabric is immersed in the resin solution at such a concentration for a short time to coat the base fabric with a resin amount of preferably 81/ze or more, and then 100% by weight or more. By placing it in an oven at ~120°C or evaporating the organic solvent on a hot plate,
A resin-impregnated base fabric can be obtained.

Is the amount of impregnation resin impregnated into the base fabric 8? /d is less than
In the heat-press bonding process, which is performed after applying an aqueous dispersion (described later) to the resin-impregnated base fabric and evaporating the water,
The urethane-vinyl chloride copolymer derived from the dispersion tends to be insufficiently penetrated into the base fabric, and the strength of the resulting composite membrane is low.

[Aqueous dispersion of urethane-vinyl chloride copolymer]

The urethane-vinyl chloride copolymer in the aqueous disvergy run used in the present invention is the same type of copolymer as the urethane-vinyl chloride copolymer used as the impregnating resin described above, and The dispersion can be obtained, for example, by adding preferably a polyacrylic acid thickener to a suspension of a urethane-vinyl chloride copolymer obtained by a suspension polymerization method.

The particle size of the copolymer particles in aqueous dispersion is
The smaller the diameter is, the more preferable it is, and specifically, 10 to 100 μm is appropriate. If the particle size is large, phase separation may occur or coating properties may be poor.

In addition, the preferred solid content concentration of the aqueous dispersion is:
40-70 weight range.

Examples of the above-mentioned polyacrylic acid-based thickener include Aron A-20P manufactured by Toso Gosei Kagaku Kogyo (■), and the preferred amount used is a urethane-vinyl chloride copolymer with a solid content degree of about 40 to 7 ooms. Suspension of union'g! It is 0.5 to 1.5 parts by weight per 1.100 parts by weight, and more preferably 0.8 to 1.2 parts by weight.

In the present invention, after applying an aqueous dispersion to the resin-impregnated base fabric, there is a step of drying and removing moisture to obtain a dispersion-supported base fabric, and further heat-pressing the base fabric. In order to suppress thermal decomposition of the system, it is preferable to add a thermal stabilizer such as epoxidized soybean oil and a Ba--Zn thermal stabilizer to the aqueous dice version.

Additionally, flame retardants such as antimony pentoxide, zinc borate and glass peas may be added to obtain a flame retardant composite membrane.

The preferred amount of the aqueous dispersion supported on the resin-impregnated base fabric is 300 to 600 l/m' in terms of solid content. If it is less than 300 y/m, the adhesive strength between the obtained base fabric-containing sheet and the fluorine-containing resin film described later will be poor, and even if it exceeds 600 y7.1, there will be no improvement in the adhesive strength, resulting in high cost. Become.

Moisture removal after applying the aqueous dispersion to the resin-impregnated base fabric can be performed by a conventional method, and thermocompression bonding can be performed using a hot press, a heated roll, etc. For example, according to the hot press, 3 at a pressure of 5 kg/m at 170°C
Heat compression bonding can be achieved by applying heat for a certain amount of time.

By thermocompression bonding, the urethane-vinyl chloride copolymer penetrates into the base fabric, and the copolymer adheres closely to the base fabric fibers, resulting in a membrane with excellent strength and no voids such as air bubbles. .

The fabric-containing composite membrane containing the phletane-vinyl chloride copolymer as a resin component obtained by the above method can be used by itself in various applications for which soft vinyl chloride resin sheets were conventionally used, and furthermore, A synthetic resin film layer such as polymethyl methacrylate may be formed on the surface and used.

[Fluororesin]

In the present invention, examples of the fluororesin used to obtain a highly weather resistant composite membrane include polyvinyl fluoride, polyvinylidene fluoride, ethylene-47fluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychloroethylene trifluoroethylene, tetrafluoroethylene-perfluorovinyl ether copolymer, ethylene-
Examples include chlorotrifluoroethylene copolymer.

The fluororesin is used in a film, and the thickness of the fluororesin film is preferably 5 to 80μ.

If it is less than 5μ, it will be difficult to mold and the weather resistance will likely be insufficient, and if it exceeds 80μ, the cost will increase and the durability will not improve.

The above-mentioned fluororesin film is attached to the base fabric-containing composite film containing the above-mentioned urethane-vinyl chloride copolymer as a resin component via an adhesive layer made of polyalkyl methacrylate, or to the composite film before going through a thermocompression bonding process. By thermocompression bonding to the copolymer dispersion-supporting base fabric,
Highly weather resistant composite membranes can be manufactured.

As the polyalkyl methacrylate forming the adhesive layer, the same kind as the polyalkyl methacrylate used as the impregnating resin can be used.

The thickness of the adhesive layer is preferably 5 to 50 microns. If the thickness is less than 5μ, the adhesion is insufficient, and if it exceeds 50μ, the composite film tends to become too hard.

Additional embodiments of the method for producing a highly weather resistant composite membrane include the methods shown below.

(a) A polyalkyl methacrylate solution is applied onto a fluororesin that has been made into a film by T-die extrusion in advance, and after the solvent is evaporated, it is bonded by thermocompression to a composite membrane containing a base fabric or a dispersion-supporting base fabric using a laminator.

(b) A polyalkyl methacrylate solution is preliminarily applied to the surface of the composite membrane containing the base fabric, and after the solvent is evaporated, extrusion lamination is carried out to laminate the fluororesin when it is made into a film by T-die extrusion.

(C) A two-layer film is formed using a 7-strand resin and a polyalkyl methacrylate by coextrusion, a two-layer inflation method, etc., and the film and a composite membrane containing a base fabric or a dispersion-supported base fabric are bonded by thermocompression using a laminator. let

Fluorine resin film (polyalkyl methacrylate)
For thermocompression bonding to a base fabric-containing composite membrane or a dispersion-supported base fabric via fd, at 170-180°C
Conditions such as applying kllF/crI pressure for 3 minutes may be used.

[Examples and comparative examples]

EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples. Note that parts represent parts by weight.

Furthermore, it goes without saying that the present invention is not limited to the following embodiments.

Example 1 Glass fiber 1001 cloth (thread thickness 6μ, number of vertical and horizontal threads 25/in, weight 3i550P/m, cloth thickness 0.5
1111) polyamide resin solution FS-175SV
(manufactured by Toko Gosei Kagaku Kogyo ■) was coated with a solid content of 24 t/m'.

Thermoplastic polyurethane T- manufactured by Dainippon Ink & Chemicals
60 parts of vinyl chloride monomer in the presence of 5275540 parts
4% of a polyacrylic acid thickener Aron A-20P was added to 80 parts of a suspension of a urethane-vinyl chloride copolymer with a solid content concentration of 50% by weight @ 80 parts of a suspension polymerized in an aqueous medium. 20 parts of aqueous solution, heat stabilizer mark AC-190 (Ba-7
, n-based thermal stabilizer (manufactured by Coredeca Argus Chemical Co., Ltd.) at 1.2
parts and flame retardants (11! antimony chloride 6 parts, zinc borate 6 parts
A disvergilan solution obtained by adding and mixing parts) is applied to the glass fibers and coated with resin in an amount of 500 P/g. This was pressed at a temperature of 170° C., a pressing pressure of 5 kg/d, and a time of 5 minutes to obtain a composite membrane containing a base fabric.

On the other hand, after obtaining a polyvinylidene fluoride film (30μ) by T-die extrusion method, a toluene bath solution of polymethacrylate resin (Dyanal BR-93) was coated with a roll coater.
A two-layer film coated to a thickness of 20 μm (after drying) and the composite membrane containing the base fabric were bonded together at a temperature of 1.
80℃, press pressure 5kli+/c! ! , thermocompression bonding was carried out for 5 minutes to obtain a highly weather resistant composite membrane whose outermost layer was composed of a fluororesin.

Example 2 In Example 1, instead of the polyamide resin FS-175SV, polymethacrylate resin (Dianal BR-
A highly weather resistant composite membrane was obtained in the same manner except that 93') was used and the coating amount was 47 f/lrl.

Example 3 The same procedure as in Example 1 was carried out except that a urethane-vinyl chloride copolymer (Aron NP-6000, manufactured by Toagosei Kagaku Kogyo ■) was used as the impregnating resin, and the coating amount was changed to 92y-/rrl. A highly weather resistant composite membrane was obtained by this method.

Comparative Example 1 A highly weather resistant composite membrane was obtained in the same manner as in Example 1 except that the impregnating resin was not used.

Comparative Example 2 A resin-impregnated base fabric coated with a urethane-vinyl chloride copolymer at 92P/rtt in the same manner as in Example 3 was coated with the same copolymer instead of an aqueous dispersion of the urethane-vinyl chloride copolymer. A resin film made of a polymer with a thickness of 400 μm was thermocompression bonded at 170° C. by applying a pressure of 10 to 9/cII for 3 minutes to obtain a coating film of urethane-vinyl chloride copolymer of 500 P. A coating film containing base fabric of /i was obtained.

Thereafter, a highly weather resistant composite membrane was manufactured in the same manner as in Example 1.

The tensile strength (JISL 1096A
) and the peel strength between the fluororesin film and the urethane-vinyl chloride copolymer coating film (based on the method specified in JI
(according to the method specified in SK 6328).

The results are shown in Table-1.

0→ Effects of the Invention According to the present invention, a composite membrane with a base fabric coated with a urethane-vinyl chloride copolymer can be produced by a simple method without using a large amount of organic solvent, and the composite membrane can be manufactured by a simple method without using a large amount of organic solvent. It can be used by itself for various purposes.

Furthermore, another type of resin film can be firmly bonded onto the composite membrane. In particular, a highly weather-resistant composite membrane can be easily obtained by bonding a fluororesin film as the outermost layer, and the composite membrane has excellent bonding strength with the fluororesin film, and its change over time is small. It is useful as a tarpaulin for tents, truck seats, etc.

Claims (1)

[Claims] 1. The base fabric is 1 selected from urethane-vinyl chloride copolymer, polyalkyl methacrylate, and polyamide.
After impregnating more than one type of resin with an organic solvent, the organic solvent is evaporated, and an aqueous dispersion of urethane-vinyl chloride copolymer is applied to the surface of the resulting resin-impregnated base fabric, and then the moisture is removed by drying. 1. A method for producing a composite membrane containing a base fabric, which comprises obtaining a dispersion-supporting base fabric and then thermocompression bonding the base fabric. 2. High weather resistance, characterized in that a fluororesin film is thermocompressed onto the surface of the dispersion-supporting base fabric or base fabric-containing composite membrane according to claim 1 via an adhesive layer made of polyalkyl methacrylate. Method for producing a composite membrane.