JPH0649357B2 - Tent material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a tent material. More specifically, the present invention relates to a tent material provided with a protective layer having excellent antifouling property, adhesiveness, and weather resistance.

[Conventional Technology] Conventionally, solutions of vinyl chloride resin, urethane resin or natural rubber, synthetic rubber, etc., rotex, organosol,
A tent material in which plastisol or the like is applied to a woven fabric is widely used.

[Problems to be solved by the invention]

In the conventional tent material, there is a problem that the plasticizer and various additives that are blended with each other over a period of time migrate to the surface by blooming or bleeding, and the surface is apt to be contaminated or the flexibility is deteriorated. Further, since it has poor weather resistance, it has a problem that the durability is extremely short.

It is an object of the present invention to provide a tent material having excellent antifouling property, flexibility, easy handling, and excellent weather resistance.

[Means for solving problems]

The present invention uses vinylidene fluoride (50 to 99 mol%) and a vinyl monomer (1 to 50 mol%) having a hydroxyl group, a carboxyl group or a glycidyl group as a functional group, or in addition to these, other than vinylidene fluoride. And a protective layer containing a functionalized vinylidene fluoride copolymer cross-linked product as a main component.

[Operation and Example]

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).
And a cross-linking agent.

It can be obtained by applying a fluororesin paint and crosslinking and curing at room temperature.

The above-mentioned fluorocopolymer has characteristics that conventional fluororesins do not have, that is, it is cured at room temperature to form a film having plasticity, and the formed coating film has the corrosion resistance, weather resistance, and antifouling property of the fluoropolymer. It retains characteristics such as sex. Also, it has good adhesion to various fiber materials, plastics, and rubber. Each component, composition and the like of such a fluorinated copolymer are described in detail in Japanese Patent Application No. 58-175123.

In the present invention, the fluorine-containing copolymer is usually vinylidene fluoride 50 to 99 mol%, preferably 65 to 85 mol% and a vinyl monomer having a functional group 1 to 50 mol%, preferably 1 to 10 mol%, or Vinylidene fluoride 50-99 mol% preferably 65
~ 85 mol%, vinyl monomer having a functional group 1-50 mol%
It preferably comprises 1 to 10 mol% and less than 30 mol% of fluoroolefins other than vinylidene fluoride, preferably 10 to 25 mol%.

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

The vinyl monomer having a functional group is usually represented by the formula: CF ₂ ═CFO _K (CH ₂ ) _m (CH ₂ ) _n X (wherein X is a hydroxyl group, a carboxyl group or a glycidyl group, and k is 0 or 1). , M is an integer of 0 to 10, n
Represents an integer of 0 to 4 (provided that X is a hydroxyl group, 1 to 4). ), A compound represented by the formula: CH ₂ ═CHO (CH ₂ ) _n X (wherein X and n are the same as those described above), a compound represented by the formula: CH ₂ ═CYCOO (CH ₂ ) _P X (the formula Wherein Y is hydrogen or a methyl group, p is an integer from 1 to 4,
X is the same as above. ) Or a compound represented by the formula: CH ₂ = CYCOOH (wherein Y is the same as the above).

The fluororefin other than vinylidene fluoride is usually tetrafluoroethylene, chlorotrifluoroethylene, monofluoroethylene, trifluoroethylene, hexafluoropropene, lower fluoroalkyl vinyl ether, etc., preferably tetrafluoroethylene or chlorotrifluoroethylene. Is.

As a method for producing the fluorine-containing copolymer used in the present invention, for example, 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
A method such as emulsion polymerization, suspension polymerization or solution polymerization in an aqueous medium under a pressure condition of kg / cm ² G, preferably 10 kg / cm ² G or less can be adopted.

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

The acrylic resin means a homopolymer or copolymer of acrylate or methacrylate containing an alkyl group having 1 to 8 carbon atoms. For example, a homopolymer or copolymer of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, a copolymer of acrylate or methacrylate with hydroxyethyl methacrylate, methacrylic acid, glycidyl methacrylate, styrene, acrylonitrile, or the like, a commercially available acrylic resin. Hitaroid 3004, Hitaloid 30
18, Hitaloid 3046C (all manufactured by Hitachi Chemical Co., Ltd.), Acridic A810-45, Acridic A814, Acridic 47-540 (all manufactured by Dainippon Ink and Chemicals) and the like, but not limited thereto.

The acrylic resin having a molecular weight (GPC) of 5,000 to 300,000 containing 50% by weight or more of methyl methacrylate is preferable from the viewpoint of compatibility with the fluorocopolymer.

The mixing ratio of the above-mentioned fluorocopolymer and acrylic resin is usually 10 to 19 acrylic resin per 100 parts by weight of the fluorocopolymer.
The amount is 00 parts by weight, preferably 25 to 400 parts by weight. When blended within this range, the paint has good weather resistance, translucency, pigment dispersibility and the like.

The protective layer in the present invention is usually prepared by blending a crosslinking agent in a fluorocopolymer as described above, and uniformly coating the coating composition obtained by uniformly mixing and dissolving it in a solvent, or by directly applying it to a base cloth or chlorination. Vinyl resin, urethane resin, or natural rubber,
It is formed by coating the surface layer through a synthetic rubber layer and crosslinking and curing at room temperature. Curing proceeds rapidly at room temperature,
Usually, a flexible coating film is obtained in 1 to 10 days, but if the temperature is raised to a level that does not adversely affect the base fabric and it is dried,
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 cross-linking agent is a compound having two or more groups capable of reacting with a functional group (hydroxyl group, carboxyl group or glycidyl group) usually contained in a fluorocopolymer to crosslink the fluorocopolymer. In the case of a functional group or a hydroxyl group, the crosslinking agent is usually isocyanates, acid anhydrides and 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, or the like. When the functional group is a glycidyl group, it is usually an amine. Examples of the isocyanates include, but are not limited to, hexamethylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate and the like, and blocked 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 dianhydride, and mellitic dianhydride. Examples of amino resins are alkyl etherified methylol melamine,
Examples thereof include, but are not limited to, alkyl etherified methylol urea and alkyl etherified benzoylguanamine. Examples of compounds containing a glycidyl group formula: Z-R 1 ^-Z (wherein, Z is a glycidyl group, R ¹ is a divalent aromatic C6-10 alkylene group or a C 2 to 10 carbon atoms An aliphatic diepoxide or an aromatic diepoxide represented by the formula: (In the formula, R ² is a trivalent aromatic group and Z is the same as above.) And the like, but the aromatic triepoxide is not limited to these.

The amount of the cross-linking agent to be blended is preferably adjusted so as to be 0.5 to 2 equivalents based on all functional groups in the fluorocopolymer and the acrylic resin.

Different from conventional fluorine-containing copolymers, ordinary solvents can be widely used as the solvent. Specific examples include esters such as ethyl acetate, butyl acetate, isobutyl acetate, cellosolve acetate; acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone; cyclic ethers such as tetrahydrofuran; amides such as N-dimethylformamide and N-dimethylacetamide; alcohols such as methyl alcohol, ethyl alcohol, butyl alcohol; aromatic carbonization such as toluene and xylene Examples thereof include one kind or two or more kinds such as hydrogens.

The concentration of the fluorinated copolymer varies depending on the coating method, the coating production method, etc., but is usually 5 to 70% by weight, preferably
20-60% by weight is adopted.

Other polymers, curing accelerators, dyes, pigments, viscosity modifiers, leveling agents, anti-gelling agents, UV absorbers, anti-stabilizers, and skins, if necessary, in the fluorine-containing copolymer coating composition. A burr prevention agent, a dispersant, an antifoaming agent, a filler, etc. may be added.

As the filler, powders of calcium carbonate, clay, tank, silica, diatomite, mica, barium sulfate, etc., fibers of glass, carbon, asbestos, potassium titanate, etc. and spheres or hollow bodies of glass, carbon, shirasu etc. Are used. In particular, fibrous, plate-like, spherical and hollow fillers are suitable for thickening the film.

The application to the base fabric can be carried out by a usual method such as a spray method, a brush coating method, a dipping method, a roll coating method, a knife coating method.

INDUSTRIAL APPLICABILITY The tent material of the present invention can be widely applied to tents and covers such as general tents, flexible container, oil fence, tank, pneumatic fender, automobile hood, cooler outdoor unit cover, and automobile cover. it can.

The present invention is described below with reference to examples, but the present invention is not limited to these examples.

Example 1 50 parts by weight of a fluorocopolymer consisting of 70 mol% of VdF, 20 mol% of CTFE and 10 mol% of M5FP (weight part, the same applies hereinafter)
Was added to 50 parts of methyl isobutyl ketone and mixed uniformly,
Further, Coronate EH (a polyisocyanate-based cross-linking agent manufactured by Nippon Polyurethane Industry Co., Ltd.) is used as a cross-linking agent.
A coating composition was prepared by adding an amount equivalent to 1.1 and 0.05 g of dibutyltin dilaurate as a curing accelerator and mixing them uniformly.

On the other hand, a polyester woven fabric was provided with a vinyl chloride resin layer, and the surface thereof was degreased with ethyl alcohol to prepare a base fabric.

The coating composition was applied to the base cloth by the 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 to the surface of a base fabric having a chloroprene rubber layer on a polyester woven fabric in the same manner as in Example 1 and dried and cured at 25 ° C for 7 days to give a test piece. I got it.

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

Example 4 Fluorine-containing copolymer consisting of 70 mol% VdF, 20 mol% CTFE and 10 mol% M5FP and 80 mol% MMA, E
An acrylic resin consisting of 10 mol% MA and 10 mol% HEMA was mixed with methyl isobutyl ketone in a ratio of 70/30 (weight ratio) to prepare a varnish of 50% by weight, and further, Coronate EH was used as a cross-linking agent for fluorine-containing copolymerization. Coronate EH for OH value of 1 for combined and acrylic resin
The coating composition was prepared by adding 1 × 10 ⁻³ g of 1-g solid content and 1 × 10 ⁻³ g of the curing accelerator dibutyltin dilaurate to an NCO value of 1.1.

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 base fabric in which a vinyl chloride resin layer was provided on a polyester woven fabric was used as a test piece.

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

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

[Adhesion]

100 squares of 1 mm square were cut on the coating film with a knife, and a cellophane adhesive tape peeling test was repeated 10 times. The existing numbers are shown in Table 1.

[Weather resistance] Using a Sunshine Weather Meter manufactured by Suga Test Instruments Co., Ltd., continuous irradiation, rain cycle 18 minutes / 120 minutes, humidity 60
%, Black panel temperature 63 ° C for 2000 hours to perform accelerated weathering test and observe the appearance.

The results are shown in Table 2.

[Anti-fouling property] 1 cm ² of the surface of the test piece is cherry pen touch (red) ((Co)
After smearing with Sakura Crepas) and leaving it for 24 hours, wipe it off with a tissue paper impregnated with ethyl alcohol / methyl ethyl ketone (9/1 weight ratio) to determine the antifouling property. The results are shown in Table 2. In Table 2, ◯ means that it can be completely removed, and x means that red color remains and cannot be removed.

Examples 7 to 23 A fluorine-containing copolymer or a fluorine-containing copolymer having a composition shown in Table 3 and an acrylic resin (ratio shown in Table 3) were dissolved in methyl isobutyl ketone, and the solid content concentration was 30% by weight. Adjusted to be%. Coronate EH has an NCO value of 1.1 equivalent to 1 OH value of the solid content of the solution and 1% of dibutyltin dilaurate to 1 g of the solid content.
After the addition of × 10 ^-3 g and thorough mixing, the same base cloth as in Example 1 was brush coated and cured at room temperature for 7 days. The obtained coating films were all glossy and flexible with 17 to 24 μm. Each test piece was tested for adhesion, weather resistance, and antifouling property.

The results are shown in Table 3.

In addition, each symbol which shows a monomer shows the following compound.

VdF: vinylidene fluoride CTFE: chlorotrifluoroethylene Le ethylene TFE: tetrafluoroethylene _{M5FP: CF 2 = CFCF 2 CH} 2 OH 3FHA: CF 2 = CFCF 2 CH 2 OH HBVE: hydroxybutyl vinyl ether GVE: glycidyl vinyl 7FHA: _CF 2 = CFCF ₂ CF ₂ CH ₂ CH ₂ OH MMA: Methyl Methacrylate EMA: Ethyl Methacrylate HEHA: Hydroxyethyl Methacrylate BMA: Butyl Methacrylate MA: Methacrylic Acid GMA: Glycidyl Methacrylate 5FBA: CF ₂ = CFCF ₂ COOH [Effects of the Invention] As described above, a coating film made of a polymer composition containing a vinylidene fluoride copolymer having a functional group as a main component is unlikely to be scratched, and the copolymer has antifouling properties and weather resistance. Since a coating film having excellent properties can be formed regardless of the type of tent base fabric, the tent material of the present invention in which the coating film is provided as a protective layer has excellent adhesion, antifouling property, and It has weather resistance and excellent durability.

Claims (1)

[Claims] 1. Vinylidene fluoride (50 to 99 mol%) and a vinyl monomer (1 to 50 mol%) having a hydroxyl group, a carboxyl group or a glycidyl group as a functional group, or in addition thereto, vinylidene fluoride. A tent material, which is provided with a protective layer containing a cross-linked product of a vinylidene fluoride copolymer having a functional group as a main component, the tent material being composed of a fluoroolefin (other than 30 mol%) other than.