JPH0462792B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a fibrous coating film having a suede-like or felt-like texture and pattern by spray coating on a base material such as a film, sheet, molded product, etc., such as plastic. BACKGROUND ART Conventionally, it has been known to impregnate a nonwoven fabric, a raised fabric, or the like with a resin such as polyurethane to form a pattern having a suede-like or felt-like texture. However, this method is very complicated,
Requires advanced technology. On the other hand, it has been difficult to impregnate plastic films, sheets, and molded products with resin, and it has been difficult to form patterns with suede-like or felt-like textures using the above-mentioned methods. As one method to solve these problems, it has been considered to create a suede-like or felt-like texture and pattern by electrostatically flocking onto the base material of plastic films, sheets, and molded products, but it has been considered that Therefore, it is difficult to perform partial surface finishing on objects with three-dimensional base materials or molded objects, and there are also problems in terms of cost. In order to solve these problems, the inventors of the present invention conducted extensive studies and found that it is economical and relatively easy to form a suede-like or felt-like pattern, and completed the present invention. That is, the present invention uses 100 parts by weight of a polyurethane elastomer and an organic isocyanate prepolymer.
50 parts by weight or less of polyurethane resin, 10 parts by weight or more and 200 parts by weight or less of pile of 3 denier or less and/or plastic or cellulose powder of 100μ or less as a filler are blended, and if necessary, a solvent This is a method for forming a suede-like or felt-like pattern, which is characterized by forming a fibrous coating film by spray painting a paint containing , other fillers, additives, etc. For example, the polyurethane elastomer used in the present invention has a number average molecular weight of 300 to
3000 or so polyester polyols and/or polyester-polyether polyols and/or polyhydric alcohols such as ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, trimethylolpropane, etc., and an organic isocyanate such as toluene diisocyanate, diphenylmethane. Diisocyanate, xylylene diisocyanate, naphthylene diisocyanate,
A prepolymer obtained by reacting hexamethylene diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane diisocyanate, etc. under conditions where the equivalent ratio of isocyanate groups to hydroxyl groups is 1 or more,
Further examples include elastomers obtained by reacting a chain extender under conditions where the amount is more than or equal to the equivalent of the isocyanate group. Examples of chain extenders used in this case include the above polyhydric alcohols, aliphatic diamines such as ethylenediamine and hexamethylene diamine, aromatic diamines such as toluene diamine, metaphenylene diamine, and xylylene diamine, isophorone diamine, and dicyclohexylmethane diamine. Examples include alicyclic diamines such as. The number average molecular weight of the polyurethane elastomer used in the present invention is not particularly limited, but from the viewpoint of finished appearance etc.
(Polystyrene equivalent value determined by gel permeation chromatography) is preferably used. In the present invention, the organic isocyanate prepolymer has a number average molecular weight of 300 to 3000, for example.
polyester polyols and/or polyether polyols and/or polyester-polyether polyols and/or low molecular weight polyhydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,3
-butanediol, 1,5-pentanediol,
1,6-hexanediol, glycerin, trimethylolpropane, neopentyl glycol, etc. and organic isocyanates such as toluene diisocyanate, diphenylmethane diisocyanate,
xylylene diisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate,
Prepolymers obtained by reacting isophorone diisocyanate, lysine isocyanate, cyclohexylmethane diisocyanate, etc. under conditions where the equivalent ratio of hydroxyl groups to isocyanate groups is 1 or more, preferably 1.3 to 2.5 are used. Among these prepolymers, a widely known prepolymer is a polyisocyanate compound having three or more isocyanate groups per molecule obtained by reacting 3 moles of the above diisocyanate with 1 mole of water or trimethylolpropane. For example, polyisocyanate (Olestar NP-1000, manufactured by Mitsui Toatsu Chemical Co., Ltd., trade name) consisting of hexamethylene diisocyanate/water = 3/1 (mole ratio), hexamethylene diisocyanate/trimethylolpropane = 3/1 ( molar ratio)
Polyisocyanate (Orester NP-
2000, manufactured by Mitsui Toatsu Chemical Co., Ltd. (trade name), polyisocyanate consisting of isophorone diisocyanate/water = 3/1 (mole ratio) (T-01890, manufactured by West German Hulls, trade name), toluene diisocyanate/
Polyisocyanate (desmodyur L-
75, manufactured by Bayer AG, product name), etc. In the present invention, the blending ratio of the polyurethane elastomer and the organic isocyanate prepolymer is in the range of 50 parts by weight or less based on 100 parts by weight of the polyurethane elastomer. More preferably,
The amount is in the range of 5 parts by weight or more and 30 parts by weight or less. If the amount of the organic isocyanate prepolymer is less than 3 parts by weight, the finished ivy pattern will have poor chemical resistance, solvent resistance, abrasion resistance, and adhesion to the material. Moreover, when the amount is more than 50 parts by weight, the appearance and texture of the finished ivy pattern becomes hard, which is not good. The pile to be used as a filler in the present invention is normally made of rayon, nylon, polyester, polyacrylic resin, etc. and has a pile shape with a diameter of 3 deniers or less and a length of 2 mm or less, but commercially available piles may be used. As an example,
1.5d×0.3mm, 1.5d×0.6mm, 2.0×1mm, 2.0d×1.3
mm, 3.0d×0.8mm, 3.0d×1.5mm, 1.0d×0.4mm,
There are various types such as 1.0d x 0.8mm, 0.75d x 0.3mm, 0.75d x 0.6mm, etc., and these piles can be used alone or in a mixture of various sizes. When a particularly good painted appearance is required, it is better to use a mixture of piles of various sizes. In addition, the plastic powder used in the present invention includes:
Examples of the nylon, polyester, acrylic, melamine resin, polyurethane resin, phenolic resin, urea resin, and cellulose powder include powders made of pulp cellulose and the like and having a particle size of 100 μm or less, preferably 80 μm or less. Although these powders can be used alone or in a mixture of various sizes, it is preferable to use pile and powder in combination from the viewpoint of spray workability and coating appearance. The blending ratio of these piles and/or plastic powders is from 10 parts by weight to 200 parts by weight, preferably from 10 parts by weight to 100 parts by weight of the polyurethane resin.
The range is 50 parts by weight or more and 150 parts by weight or less. Therefore, if this proportion is less than 10 parts by weight or more than 200 parts by weight, a good pattern cannot be obtained. In the present invention, in addition to the above, during coating, solvents necessary for adjusting coating viscosity, such as ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters such as ethyl acetate and butyl acetate, toluene, xylol, etc. Additives such as aromatic solvents, fillers such as charcoal, silica, titanium oxide, talc, pigments, coloring dyes, flame retardants, surface conditioners, dispersants, etc.
They can also be used in combination as long as they do not impede the effects of the present invention. The paint thus obtained can be spray coated by a conventional coating method, such as air spray, airless spray, or electrostatic coating. The suede-like or felt-like pattern of the present invention can be obtained by applying the coating once or several times so that the coating thickness is usually about 0.3 mm to 2 mm. In the present invention, the material to be coated is not particularly limited, but it can be coated on plastic molded products such as PVC, polystyrene, ABS resin, polyethylene, polypropylene, PET resin, etc., and after surface treatment and undercoating as necessary. , is commonly painted. The pattern obtained in this way can be finished by setting the paint film at room temperature until it hardens, or by setting it for 0.5 minutes to 1 hour after painting and then baking it in an atmosphere of 40°C to 120°C. You can also finish it by The thus obtained coated product having a suede-like or felt-like pattern has an excellent visual appearance and texture and is used for various purposes such as architectural interior materials and automobile interior materials. The present invention will be explained below with reference to Examples and Comparative Examples, and unless otherwise specified, parts in the examples represent parts by weight and % parts by weight. Production Example 1 200 parts of a polyester polyol (condensation product of 1,4-butanediol and adipic acid) with a molecular weight of 2000 and a molecular weight of 1000 were placed in a four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction device. 100 parts of polyester polyol (condensation product of 1,4-butanediol and adipic acid), 89 parts of isophorone diisocyanate and 260 parts of toluene were charged.
The reaction was carried out at 100° C. for 4 hours while introducing nitrogen gas.
The obtained prepolymer had an NCO of 4.2% (calculated as solid content). After cooling this prepolymer,
It was diluted with ethyl acetate so that the nonvolatile content was 30%. 30 parts of isophorone diamine was added to this to obtain a polyurethane elastomer having a viscosity of 200 poise.
Furthermore, 10 parts of isopropyl alcohol was added to treat remaining NCO. The obtained polyurethane elastomer is referred to as (A). Production Example 2 In a four-necked flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen gas introduction device, 220 parts of polyether polyol (polypropylene glycol) with a molecular weight of 1000, 46 parts of trimethylolpropane, 325 parts of isophorone diisocyanate, 200 parts of xylol and 200 parts of cellosolve acetate were charged and reacted at 80° C. for 5 hours while introducing nitrogen gas. The obtained prepolymer had an NCO of 6.1% and a non-volatile content of
It was 60.2%. The obtained prepolymer is designated as (B). Example 1 Polyurethane elastomer 333 obtained in Production Example 1
In addition, Olestar NP-2000 is used as a prepolymer.
(manufactured by Mitsui Toatsu Chemical, trade name, non-volatile content 75%)
13.3 parts, 30 parts of nylon pile 1.5d x 0.3mm, 10d
20 parts of x0.4mm, 20 parts of 0.75d x 0.3mm and particle size 50μ
30 parts of nylon powder was added and diluted with 220 parts of a mixed solvent of acetone/ethyl acetate/toluene 40/30/30. The blending ratio of the paint is polyurethane elastomer: prepolymer: filler = 100:10:100 in terms of solid content. Apply the obtained paint to the coating pressure
The coating was applied onto the ABS molded sheet using air spray at 4.0 Kg/cm ² so that the coating film thickness was 400 μ to 600 μ. After painting, leave it at room temperature for 30 minutes, then
It was cured for 30 minutes in an atmosphere of 80°C. The evaluation results of the obtained painted objects are shown in Table-2. Examples 2 to 5 and Comparative Examples 1 to 6 Paints were manufactured in the same manner as in Example 1, using the formulations shown in Table 1. Next, it was painted and cured in the same manner as in Example 1. The evaluation results are shown in Table-2.

[Table] * The same solvent composition as in Example 1 was used as the diluting solvent.

[Table] Judgment: ◎, ○ Indicates that the product is good without any problems.
×, ×× Indicates that it cannot be used.

Claims (1)

[Claims] 1 100 parts by weight of a polyurethane resin consisting of 100 parts by weight of a polyurethane elastomer and 50 parts by weight or less of an organic isocyanate prepolymer, and 10 parts by weight or more of 200 parts by weight or more of pile of 3 denier or less and/or plastic or cellulose powder of 100 μ or less as a filler. 1. A method for forming a suede-like or felt-like pattern, characterized by forming a fibrous coating film by spray painting a paint comprising the following: