JPS61215049A - Tent material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to tent materials. More specifically, the present invention relates to a tent material provided with a protective layer having excellent stain resistance, adhesion, and weather resistance.

[Conventional technology]

Conventionally, solutions, latex, organosol, etc. of vinyl chloride resin, urethane resin, natural rubber, synthetic rubber, etc.
Tent materials made of woven fabric coated with plastisol are widely used.

[Problem that the invention seeks to solve]

Conventional tent materials have a problem in that over time, the plasticizers and various additives blended into the tent migrate to the surface due to bloom or bleed, which tends to cause surface contamination and a decrease in flexibility. Furthermore, since it has poor weather resistance, there is a problem that its durability is extremely short.

An object of the present invention is to provide a tent material that has excellent stain resistance, flexibility, easy handling, and excellent weather resistance.

[Means for solving problems]

The present invention relates to a tent material provided with a protective layer containing as a main component a vinylidene fluoride copolymer having a functional group and/or a crosslinked product of a vinylidene fluoride copolymer having a functional group.

[Function and Examples]

The protective layer in the present invention is usually a vinylidene fluoride copolymer having a functional group (hereinafter referred to as a fluorine-containing copolymer).
It consists of a polymer composition whose main components are: and a crosslinking agent.

It is obtained by applying a fluororesin paint and cross-linking and curing it at room temperature.

The former commemorative fluorine copolymer has properties that conventional fluororesins do not have, namely, it hardens at room temperature to form a flexible film.
Moreover, the formed coating film has the corrosion resistance of fluoropolymer,
It retains its properties such as weather resistance and stain resistance. It also has good adhesion to various fiber materials, plastics, and rubber. Each component of such a fluorine-containing copolymer,
The composition etc. are explained in detail in Japanese Patent Application No. 175123/1983.

In the present invention, the fluorine-containing copolymer usually contains 50 to 99 mol% vinylidene fluoride, preferably 65 to 85 mol%, and 1 to 50 mol% vinyl monomer having a functional group, preferably 1 to 10 mol%. or 50 to 99 mol% of vinylidene fluoride, preferably 65 to 85 mol%, 1 to 50 mol% of vinyl monomers having functional groups, preferably 1 to 10 mol%, and less than 30 mol% of fluoroolefins other than vinylidene fluoride. Preferably it consists of 10 to 25 mol%.

The molecular weight measured by gel permeation chromatography (GPC, polystyrene standard) of fluorine-containing resins containing vinylidene fluoride as the main component and functional groups is usually in the range of 10,000 to 500,000. It is in.

”-The vinyl monomer having the functional group usually has the formula: % formula %
) (wherein, X is a hydroxyl group, a carboxyl group or a glycidyl group, k is 0 or 1, m is an integer of 0 to 10,
n is 0 to 4 [However, when X is hyroxyl group, 1 to
4] is an integer. ), a compound represented by the formula: %formula%) (wherein, ~4 integer,
X is as above. ) A compound or a compound represented by the formula: %Formula% (wherein, Y is as defined above).

The fluoroolefins other than vinylidene fluoride mentioned above are usually tetrafluoroethylene, chlorotrifluoroethylene, monofluoroethylene, trifluoroethylene, hexafluoropropene, lower fluoroalkyl vinyl ether, etc., and preferably tetrafluoroethylene or chlorotrifluoroethylene. be.

The method for producing the fluorine-containing copolymer used in the present invention includes, for example, combining each component in the presence of a solvent using a polymerization catalyst,
-20 to 150 °C, preferably 5 to 95 °C and 0 to 30 kg/ci G, preferably 10 kg/
Methods such as emulsion polymerization, suspension polymerization, or solution polymerization in an aqueous medium under pressure conditions of cJ G or less may be employed.

Further, the fluorine-containing copolymer of the present invention has good compatibility with an acrylic resin and can be used in combination with an acrylic resin.

The above-mentioned acrylic resin refers to a single or copolymer of acrylate or methacrylate containing an alkyl group having 1 to 8 carbon atoms. For example, single or copolymers of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, etc., copolymers of the above acrylates or methacrylate-I with hydroxyethyl methacrylate, methacrylic acid, glycidyl methacrylate, styrene, acrylonitrile, etc. Commercially available acrylic resins include Hitaroid 3004, Hitaroid 3018, Hitaroid 3046G (all manufactured by Hitachi Chemical), Acrizoink A 810-45, Acridic A314, Acridic 47-540.
(both manufactured by Dainippon Ink and Chemicals), etc., but are not limited to these.

The acrylic resin preferably contains 50% by weight or more of methyl methacrylate and has a molecular weight (GPC) of 5,000 to 300,000 from the viewpoint of compatibility with the fluorine-containing copolymer.

The mixing ratio of the fluorine-containing heavy rope and acrylic resin is usually 10 to 10 parts by weight of the acrylic resin to 100 parts by weight of the fluorine-containing heavy weight.
The amount is 1900 parts by weight, preferably 25 to 400 parts by weight. When blended within this range, the weather resistance, translucency, pigment dispersibility, etc. of the paint are good.

The protective layer in the present invention is usually prepared by applying a coating composition obtained by blending a fluorine-containing copolymer with a crosslinking agent, uniformly mixing and dissolving it in an appropriate solvent as described above, or directly applying it to the base fabric. It is formed by coating the surface layer through a layer of vinyl chloride resin, urethane resin, natural rubber, or synthetic rubber, and crosslinking and curing it at room temperature. Curing progresses rapidly at room temperature, and a flexible coating film can usually be replaced within 1 to 10 days, but if the temperature is raised to a level that does not adversely affect the base fabric and it dries,
The time required for curing can be shortened.

Examples of the base fabric include woven fabrics such as cotton, rayon, nylon, vinylon, Tetron, polypropylene, aramid, polyamide, glass, and carbon.

The crosslinking agent is a functional group (
hydroxyl group, carboxyl group or glycidyl group)
It is a compound having two or more groups capable of crosslinking the fluorine-containing copolymer by reacting with the fluorine-containing copolymer. When the functional group is a hydroxyl group, the crosslinking agent is usually an isocyanate, an acid anhydride, or the like. When the functional group is a carboxyl group, it is usually an isocyanate, an amine, an amino resin, a compound containing a glycidyl group, etc. When the functional group is a glycidyl group, it is usually an amine. Examples of isocyanates include, but are not limited to, hexamethylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, and block isocyanates thereof. Examples of amines include, but are not limited to, diethylenetriamine, triethylenetetramine, xylenediamine, metaphenylenediamine, benzyldimethylamine, bisaminopropyltetraoxaspiroundecane, and the like. Examples of acid anhydrides include, but are not limited to, phthalic anhydride, pyromellitic anhydride, and mellitic anhydride. Examples of amino resins include, but are not limited to, alkyl etherified methylolmelamine, alkyl etherified methylolurea, alkyl etherified benzoylguanamine, and the like. An example of a compound containing a glycidyl group is the formula: %Formula% (wherein, Z represents a glycidyl group, and R1 represents an alkylene group having 2 to 10 carbon atoms or a divalent aromatic group having 6 to 10 carbon atoms. ), aliphatic dieboxides or aromatic dieboxides represented by the formula; but not limited to.

The amount of the crosslinking agent is preferably adjusted to 0.5 to 2 equivalents based on all the functional groups in the fluorine-containing copolymer and the acrylic resin.

As the solvent, unlike conventional fluorine-containing copolymers, a wide variety of ordinary solvents can be used. Specific examples include esters such as ethyl acetate, butyl acetate, isobutyl acetate, and cellosolve acetate; acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl quinone; cyclic ethers such as tetrahydrofuran; amides such as N-dimethylformamide and N-dimethylacetamide; alcohols such as methyl alcohol, ethyl alcohol, and butyl alcohol; toluene, xylene, etc. One or more aromatic hydrocarbons may be used.

The concentration of the fluorine-containing copolymer varies depending on the coating method and coating manufacturing method, but is usually 5 to 70% by weight, preferably 20 to 60% by weight.

The fluorine-containing copolymer coating composition may optionally contain other polymers, curing accelerators, dyes, pigments, viscosity modifiers, leveling agents, gelling inhibitors, ultraviolet absorbers, light stabilizers, and coating compositions. Anti-foaming agents, dispersants, antifoaming agents, fillers, etc. may be added.

As fillers, powders such as calcium carbonate, clay, tank, silica, diatomaceous earth, mica, barium sulfate, fibers such as glass, carbon, asbestos, potassium titanate, and spheres or hollows such as glass, carbon, shirasu, etc. The body is used. In particular, fibrous, plate-like, spherical and hollow fillers are suitable for thickening the film.

Application to the base fabric can be carried out by a conventional method such as a spray method, a brush coating method, a dipping method, a roll coating method, or a knife coating method.

The tent material of the present invention can be widely applied to tents and covers such as general tents, flexible containers, oil fences, tanks, pneumatic fenders, automobile canopies, cooler outdoor unit covers, and automobile covers. .

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example I 70 mol% VdF, 20 mol% CTFE and M5FP
50 parts (parts by weight,
) was added to 50 parts of methyl isobutyl ketone and mixed uniformly, and furthermore, as a crosslinking agent, Coronet 1-EH (a polyisocyanate crosslinking agent manufactured by Nippon Polyurethane Industries) was added to the 014 valent 1 of the fluorine-containing copolymer. Against Coronet I
An amount equivalent to 1.1 in NC0 value of EH and 0.05 g of dibutyltin dilaurate as a curing accelerator were added and mixed uniformly to prepare a coating composition.

On the other hand, a base fabric was prepared by providing a polyester woven fabric with a vinyl chloride resin layer and degreasing the surface with ethyl alcohol.

The coating composition was applied to the base fabric by a dipping method, and dried and cured at 25° C. for 7 days to obtain a test piece.

Example 2 The coating composition prepared in Example 1 was applied in the same manner as in Example 1 to the surface of a base fabric comprising a polyester woven fabric with a chloroprene rubber layer, dried and cured at 25°C for 7 days, and a test piece was prepared. I got it.

Example 3 The coating composition prepared in Example 1 was applied directly to a polyester woven fabric in the same manner as in Example 1, dried at 25°C for 15 minutes, and then further dried and cured at 80°C for 60 minutes to form a test piece. I got it.

Example 4 70 mol% VdF, 20 mol% CTFE and M5FP
Fluorine-containing copolymer consisting of IO mol% and MMA80
An acrylic resin consisting of 10 mol% of HM A and 10 mol% of HEMAIO was mixed with methyl isobutyl ketone in a ratio of 70/30 (weight ratio), a face of a 50-weight machine was prepared, and Coronate EH was added as a crosslinking agent. OHH of fluorine-containing copolymers and acrylic resins
For I3, 1 g solid content of Coronate EHONCO value 1.1 equivalent and curing accelerator dibutyltin dilaurate
1X10-g was added to the solution and mixed uniformly to prepare a coating composition.

The above coating composition was applied to the same base fabric as in Example 1 and cured in the same manner as in Example 1 to obtain a test piece.

Example 5 The coating composition of Example 4 was applied to the same base fabric as in Example 2 and cured in the same manner as in Example 2 to obtain a test piece.

Example 6 The coating composition of Example 4 was applied to the same base fabric as in Example 3 and cured in the same manner as in Example 3 to obtain a test piece.

Comparative Example 1 A test piece was a base fabric in which a polyester woven fabric was provided with a vinyl chloride resin layer.

Comparative Example 2 A test piece was a base fabric in which a chloroprene rubber layer was provided on a polyester woven fabric.

The following tests were conducted on the test pieces obtained in Examples 1 to 6 and Comparative Examples 1 to 2, respectively.

[Adhesion]

100 squares of 111 squares were cut into the coating film using a knife, and the cellophane adhesive tape peeling test was repeated 10 times.

The remaining numbers are shown in Table 1.

Table 1 [Weather resistance] Using a sunshine weather meter manufactured by Suga Test Instruments, continuous irradiation, rainfall cycle of 18 minutes/120 minutes, humidity 6
0%, black panel temperature 63℃ for 2000 hours accelerated weather resistance test and appearance observed.

The results are shown in Table 2.

[Stain resistance]

After filling 1- on the surface of the test piece with Sakura Pentasochi (red) (@Sakura Crepas) and leaving it for 24 hours, ethyl alcohol/methyl ethyl ketone (9/1 weight ratio) was applied.
Wipe it with tissue paper impregnated with and determine the stain resistance. The results are shown in Table 2. In Table 2, ○ means that it can be completely removed, and × means that the red color remains and cannot be removed.

Examples 7 to 23 A fluorine-containing copolymer or a fluorine-containing copolymer and an acrylic resin (the proportions are shown in Table 3) having the compositions shown in Table 3 were dissolved in methyl isobutyl ketone, and the solid content concentration was ,3
The content was adjusted to 0% by weight. O of the solid content of the solution
An amount equivalent to Coronate EHONCO value 1.1 relative to HHI3 and dibutyltin dilaurate were added in an amount of 1X10-'g per 1g of solid content, mixed thoroughly, and then brushed onto the same base fabric as in Example 1 and coated at room temperature for 7 days. Allowed to harden for days. The resulting coating films were all glossy and flexible coatings of 17 to 24 μm. Each test piece was tested for adhesion, weather resistance, and stain resistance.

The results are shown in Table 3. In addition, each abbreviation showing a monomer shows the following compound.

■dF: Vinylidene fluoride CTFE: Chlorotrifluoroethylene TFE: Tetrafluoroethylene M5 FP: CFz=CFCFzCHzOH3FH
A: CF2=CFCHzCH20T (HBVE:
Hydroxybutyl vinyl ether GVE nigericidyl vinyl ether 7 FHA: CFz=CFCF2CFzC, HiC
HzOHMMA: Methyl methacrylate EMA: Ethyl methacrylate HEHA: Hydroxyethyl methacrylate BMA Nibutyl methacrylate MA: Methacrylic acid GMA j Glycidyl methacrylate 5 F B A: CF z = CF CF t
COOH [Effect of the invention] As described above, the coating film made of the polymer composition whose main component is vinylidene fluoride copolymer having the above-mentioned functional group is hard to be scratched, and the copolymer has antifouling properties, Since a coating film with excellent weather resistance can be formed regardless of the type of base fabric for tents, the tent material of the present invention provided with the coating film as a protective layer has extremely excellent adhesion and stain resistance. It has weather resistance and excellent durability.

Claims (1)

[Claims] 1. Vinylidene fluoride copolymer having a functional group and/or
Or a tent material provided with a protective layer mainly composed of a crosslinked vinylidene fluoride copolymer having a functional group.