JP2510099B2 - Gloss adjusting resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition suitably used for adjusting the gloss of a vinyl chloride resin layer,
For example, the present invention relates to a resin composition suitable for forming a so-called surface layer (such as a transparent layer provided on a printed layer on which a pattern or the like is printed) in a synthetic resin decorative sheet or the like.

[0002]

2. Description of the Related Art Conventionally, construction (ceiling materials, wall materials, floor materials, etc.),
Decorative sheets made of synthetic resin are widely used as surface materials for furniture, vehicles, electric appliances, footwear, bags and the like.

As such a decorative sheet, generally,
As shown in FIG. 1, a backing material 1 such as woven cloth, knitted cloth or paper
An intermediate layer 2 such as a foamed or non-foamed vinyl chloride resin
And a predetermined pattern is printed on the intermediate layer 2 with a printing ink such as a foamed or non-foamed vinyl chloride resin by various printing means such as a rotary screen method and a gravure method. It is known that the so-called printing layer 3 is formed and the transparent surface layer 4 is further formed.

By the way, the transparent layer 4 is formed by adding a stabilizer and, if necessary, a coloring agent to a so-called plastisol in which a polyvinyl chloride resin for paste is mixed with a plasticizer. The printing layer 3 is formed by applying it by an appropriate means such as a coating method, a doctor knife coating method, a rotary screen method or a gravure method.

[0005]

However, the above-mentioned plastisol uses a vinyl chloride resin for paste having an extremely fine particle size obtained by so-called emulsion polymerization or the like, which is applied to the backing material 1. When gelled by heating after coating, the surface of the coating film was highly smoothed due to these extremely fine resin particles, and the surface was unsuitable as an interior material because the surface became mirror-like and glossy. .

For this reason, the luster was adjusted by mixing the coarse-grained vinyl chloride resin with the paste vinyl chloride resin, but a product with a matte effect having a rough appearance like ceramics and pottery. Was something I couldn't get.

In view of the above points, it is an object of the present invention to provide a resin composition used for forming a surface layer of various materials, not limited to the transparent layer in the above decorative sheet. .

[0008]

The present inventors have found that the vinyl chloride resin for paste has an extremely fine particle size as described above, whereas the coarse particle vinyl chloride resin has a relatively small particle size. It is a polymer with a large amount, and when this vinyl chloride resin for paste is mixed with coarse particle vinyl chloride resin, a product with a matting effect can be obtained, but it is rough like ceramics and pottery. It was not possible to obtain a rough matte product having the above-mentioned appearance. As a result of repeated studies to achieve the above object, the present inventor uses three kinds of vinyl chloride-based resin for paste, coarse-grained vinyl chloride-based resin and vinyl chloride-based suspension polymer in combination within a specific range ratio. As a result, they have found that a rough matte product having a rough appearance such as ceramics and pottery can be obtained, and completed the present invention.

That is, a total of 100 to 100 parts by weight of 30 to 80 parts by weight of vinyl chloride resin for paste, 60 to 10 parts by weight of coarse particle vinyl chloride resin, and 50 to 10 parts by weight of vinyl chloride suspension polymer. The gist is a resin composition for adjusting gloss, which is characterized in that

The vinyl chloride resin for paste in the composition of the present invention is extremely fine polymer particles, and the particles generally have a particle size of about 0.02 to 20 μm.
The vinyl chloride resin for paste is usually called a paste resin and can be formed into a plastisol by blending a plasticizer, and vinyl chloride alone, or vinyl chloride and ethylene, propylene, vinyl acetate, maleic acid ester, Generally, methyl methacrylate, methacrylic acid ester, acrylic acid ester, higher vinyl ether, etc.
An emulsion polymerization method in which radical polymerization is performed using a water-soluble polymerization initiator, an oil-based polymerization initiator is used, and a homogenizer or the like is used to mechanically uniformly disperse these monomers in water. The polymer obtained by the microsuspension polymerization method of polymerizing is mentioned. These may be used alone or in combination of two or more.

The coarse particle vinyl chloride resin (blending resin) in the composition of the present invention is a fine polymer particle, which is coarser than the particles of the vinyl chloride resin for paste and has a particle size of about 10 to 60 μm. It is common. Coarse particle vinyl chloride resin is usually obtained by a microsuspension polymerization method, examples of the synthetic resin constituting the coarse particle vinyl chloride resin include those similar to the above vinyl chloride resin for paste, The coarse particle vinyl chloride-based resin can be used alone or in combination of two or more.

The vinyl chloride-based suspension polymer is, as is well known, a vinyl chloride or another monomer copolymerized with vinyl chloride, and a polymer (that is, a vinyl chloride-based polymer) with these monomers. Polymer) is a vinyl chloride polymer obtained by a suspension polymerization method in which a polymer is dispersed by mechanical stirring in a liquid phase (generally water) in which both are hardly dissolved. The particle size is about 50 to 200 μm, which is as large as several tens to several hundred times the particle size of the above vinyl chloride resin for paste. Examples of the synthetic resin forming the vinyl chloride-based suspension polymer include the same as the above-mentioned vinyl chloride-based resin for pastes. These vinyl chloride-based suspension polymers are used alone or in combination of two or more. be able to.

The mixture of the vinyl chloride resin for paste, the coarse particle vinyl chloride resin, and the vinyl chloride suspension polymer is mixed with a plasticizer, a solvent and the like, and can be made into a paste. Examples of the plasticizer include di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (DINP), butylbenzyl phthalate (BBP), diisodecyl phthalate (DIDP), diundecyl phthalate ( General phthalate ester plasticizers represented by DUP) and the like, general fatty acid ester plasticizers represented by adipic acid dioctyl ester (DOA), sebacic acid dioctyl ester (DOS), azelaic acid dioctyl ester (DOZ) , Trimellitic acid trioctyl ester (TOTM) typified by trimellitic acid ester plasticizers, tricresyl phosphate (TCP) typified by phosphoric acid ester plasticizers, epoxy plasticizers,
Polymeric plasticizers such as polyester plasticizers typified by polypropylene adipate, and general plasticizers such as chlorinated paraffin can be used, and these can be used alone or in combination of two or more. In addition to these general plasticizers, reactive plasticizers such as DAP, acrylic monomers and acrylic oligomers, tributoxyethyl phosphate, butyl diglycol adipate, Sansocizer C-1100 (trade name, manufactured by New Nippon Rika) , AM-801
Antistatic plasticizers such as A and AM-801B (trade name of Sekisui Chemical Co., Ltd.), secondary plasticizers of dodecylbenzene derivative, and the like can also be used.

The mixture ratio of the above-mentioned vinyl chloride resin for paste, coarse particle vinyl chloride resin and vinyl chloride suspension polymer and the plasticizer is the kind of the plasticizer, the kind of the synthetic resin, and the ratio of the synthetic resin. The optimum ratio is appropriately selected according to, etc., but generally 20 to 100 parts by weight of the plasticizer for 100 parts by weight of the total amount of the vinyl chloride resin for paste, the coarse particle vinyl chloride resin and the vinyl chloride suspension polymer. It is preferable that the amount is about a part.

Further, in the composition of the present invention, in addition to the above plasticizer, a stabilizer, a foaming agent, a filler, a foam stabilizer, a viscosity modifier,
Additives such as an ultraviolet absorber, an antistatic agent and a coloring agent can also be added.

As the stabilizer, any stabilizer can be used as long as it is usually used for vinyl chloride resins. Specifically, cadmium, zinc, barium, calcium,
In addition to metal stabilizers such as strontium, aluminum, magnesium, cerium, sodium, lead and tin, organic phosphite compounds, polyhydric alcohols, epoxy compounds and the like can be used alone or in combination of two or more.

As the foaming agent, any one can be used as long as it is a compound usually used for vinyl chloride resins.
Here is an example. N, N'-dinitrosopentamethylenetetramine, N, N'-dimethyl-N, N'-dinitrosoterephthalamide, azodicarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, P, P'-oxybis (Benzenesulfonyl hydrazide), benzene-
In addition to decomposing foaming agents such as 1,3-disulfonyl hydrazide and toluenesulfonyl hydrazide, liquid hydrocarbons such as butane and isobutane that are vaporized by heating are encapsulated in thermoplastic synthetic resin microcapsules. Agents can be used.

As the filler, any one can be used as long as it is an inorganic and / or organic filler having excellent heat resistance which does not cause physical or chemical changes such as melting or decomposition at the processing temperature. , The following is an example. Calcium carbonate, magnesium carbonate, clay, talc, silica, diatomaceous earth, silica sand, pumice powder, slate powder, mica powder, asbestos, aluminum hydroxide, magnesium hydroxide, aluminum oxide, aluminum sulfate, barium sulfate, calcium sulfate, Glass spheres, foamed glass spheres, fly ash spheres, volcanic glass hollow bodies (shirasu balloons), inorganic fillers such as glass fibers and inorganic fibers such as carbon fibers, powdered fibrin (cellulose powder), organic fibers such as polyvinyl alcohol fibers Organic fillers such as cork powder, wood powder, thermosetting resin powder, thermosetting resin hollow spheres and crosslinked thermoplastic resin powder can be used.

When a foam layer is formed by mechanical foaming, it is preferable to use a foam stabilizer, and this foam stabilizer is
Any commonly used one can be used, for example, a silicon-based foam stabilizer such as methylsiloxane emulsion and methylsiloxane solution, a fluorine-based foam stabilizer,
Fatty acid condensates, alkylallyl sulfonates, metal soaps of oleic acid and ricinoleic acid, guanidine salts, quaternary ammonium compounds, aldehyde-amine condensation products and the like can be used.

Viscosity modifiers are roughly classified into thickeners and thickeners. As the thinning agent, those generally used can be used, and examples thereof will be given below. Volatile diluents such as gasoline, octane, benzene, xylene, naphtha, dodecylbenzene derivative, methyl ethyl ketone and methyl isobutyl ketone, and various surfactants are used. As the thickener, those generally used can be used, and examples thereof will be given below. Metal soaps such as aluminum stearate, aluminum oleate and zinc stearate, silica,
Bentonite, polymerized oil, etc. can be used. When adjusting the viscosity of the vinyl chloride resin paste composition to a viscosity suitable for processing, these viscosity modifiers are used by adding an appropriate amount as necessary.

As the ultraviolet absorber, 2-hydroxy-4-
Methoxybenzphenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybezophenone, 2-
Hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxybenzoyloxybezophenone, 2,2'-dihydroxy-4-methoxy Benzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone, bis- (2-methoxy-
4-hydroxy-5-benzoylphenyl) benzophenone-based UV absorbers such as methane, 2- (2'-hydroxyphenyl)
Benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid butyl ester benzotriazole, 2- (2'- Hydroxy-5'-methylphenyl) -5,6-dichlorobenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-ethylsulfonebenzotriazole, 2-
(2'-hydroxy-5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5 ' -Aminophenyl) benzotriazole, 2- (2'-hydroxy-3 ',
5'-dimethylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dimethylphenyl) -5-methoxybenzotriazole, 2- (2'-methyl-4'-hydroxyphenyl) benzotriazole, 2- (2'-stearyloxy-3 ', 5'-dimethylphenyl) -5-methylbenzotriazole, 2- (2'-
Hydroxy-5-carboxylic acid phenyl) benzotriazole ethyl ester, 2- (2'-hydroxy-3'-methyl-5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-
3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-
5'-methoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-cyclohexylphenyl) benzotriazole, 2- (2'-hydroxy-4 ', 5'-dimethylphenyl) -5-carboxylic acid benzotriazole Butyl ester, 2- (2'-hydroxy-3 ', 5'-dichlorophenyl) benzotriazole, 2- (2'-hydroxy-4', 5'-dichlorophenyl) benzotriazole, 2- (2 ' -Hydroxy-3 ', 5'-dimethylphenyl) -5-ethylsulfone benzotriazole, 2- (2'-hydroxy-4'-octoxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-methoxy Phenyl) -5-methylbenzotriazole, 2- (2'-hydroxy-5'-methylphenyl) -5-carboxylic acid ester benzotriazole, 2-
Benzotriazole-based UV absorbers such as (2'-acetoxy-5'-methylphenyl) benzotriazole can be used.

As the antistatic agent, any of the commonly used antistatic agents can be used, but nonionic antistatic agents are particularly preferable, and examples thereof will be given below. Ether type compounds such as polyoxyethylene alkyl ether, polyoxyethylene alkylaryl ether, polyoxyethylene polyoxypropylene ether,
Ester type compounds such as polyoxyethylene alkyl ester, polyhydric alcohol and partial ester compound of fatty acid,
An ether type of polyoxyethylene alkylamine etc., polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester,
Examples thereof include ether ester type ones such as polyoxyethylene mannitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, and polyoxyethylene propylene glycol monofatty acid ester. Specifically, the number of added moles of a partial ester of a polyhydric alcohol such as sorbitan, sorbitol, mannitol, mannitol, glycerin, diglycerin, pentaerythritol and a fatty acid having 12 to 22 carbon atoms, ethylene oxide or propylene oxide is 1 ~ 20, polyhydric alcohol is sorbitan, sorbitol, mannitol, mannitol,
Glycerin, diglycerin, pentaerythritol,
A polyoxyalkylene polyhydric alcohol fatty acid ester in which the fatty acid has 12 to 22 carbon atoms.

The composition of the present invention comprises the above-mentioned vinyl chloride resin for paste, coarse particle vinyl chloride resin and vinyl chloride suspension polymer in an appropriate combination (ie,
The vinyl chloride resin for paste, the coarse particle vinyl chloride resin, and the synthetic resin that constitutes the vinyl chloride suspension polymer may be the same or different, but if they are different, when the coating film is formed. Of which the heat treatment temperature is about the same, or those which are familiar and have no problem in film strength after forming a coating film, etc.) are mixed.

At this time, if the mixing ratio of the vinyl chloride type suspension polymer is too small, the delustering effect of the coating film is not sufficient (a rough delustering effect like the appearance of ceramics or pottery cannot be obtained. ), On the contrary, if the amount is too large, not only the mechanical strength of the coating film decreases, but also the tensile strength, tear strength, etc. decrease, and not only the elongation rate decreases, but also the viscosity of plastisol increases, and workability increases. Will get worse. In addition, if the mixing ratio of the coarse particle vinyl chloride resin is too low, the matte effect of the coating film will not be sufficient (they will have a rough luster with a bottom glow), and conversely if it is too high, the vinyl chloride resin As in the case where the mixing ratio of the suspension polymer is too large, the mechanical strength of the coating film decreases,
Not only the tensile strength and tear strength decrease, the elongation also decreases, but the viscosity of plastisol increases and the workability deteriorates. Further, the composition of the present invention can be used by adding a foaming agent, but if there is too much vinyl chloride-based suspension polymer, there is a problem that the foamed cells obtained by foaming become rough. From such a point, in the composition of the present invention, the mixing ratio of the vinyl chloride resin for paste, the coarse particle vinyl chloride resin, and the suspension polymer of vinyl chloride is set to the vinyl chloride resin for paste: coarse particle vinyl chloride resin: The vinyl chloride suspension polymer is 30 to 80 parts by weight: 60 to 10 parts by weight: 50 to 10.

The above foaming agent which can be added to the composition of the present invention is usually used for paste vinyl chloride resins, coarse-grain vinyl chloride resins and vinyl chloride suspension polymers. The thing can be used as it is.

In order to form a matte surface layer with the composition of the present invention, as in the case of the conventional plastisol, for example, in the case of a decorative sheet, a backing material (if necessary, a backing material having an intermediate coating layer formed) is used. After applying the composition of the present invention to (), heat treatment may be performed. At this time, a coating film forming means similar to the case of the conventional plastisol, for example, an appropriate means such as a doctor knife coating method, a rotary screen method or a gravure method can be adopted. Examples of the backing material include non-woven fabrics, woven fabrics, and knitted fabrics made of one or more types of foamed or non-foamed synthetic resin sheets, glass fibers, organic fibers, pulp, etc., and these non-woven fabrics, woven fabrics, and knitted fabrics. A sheet-like material obtained by coating or impregnating a cloth with a synthetic resin and substantially having a colored or colorless transparent, semitransparent, or opaque synthetic resin layer can be used. Then, it is gelled by heat treatment, and when a foaming agent is mixed, it is heated and foamed subsequently.

[0028]

In the composition of the present invention, the vinyl chloride resin for paste, the coarse particle vinyl chloride resin, and the vinyl chloride suspension polymer are mixed in a specific ratio, so that the composition has a rough appearance similar to that of ceramics and pottery pottery. It has a matte appearance with a good appearance, and the gloss can be adjusted freely according to the mixing ratio.

Moreover, the layer formed from the composition of the present invention has improved resistance to heat discoloration. For this reason, when a layer is formed by mixing a colorant with the composition of the present invention, the above-mentioned surface layer is formed by the composition of the present invention even during the heat treatment after coating the composition of the present invention. Even when the heating element comes into contact with the decorative sheet as a wall material, floor material, or the like, the layer does not discolor, and the coloring at the beginning of the layer formation is stably maintained.

[0030]

EXAMPLES Example 1 (Preparation of Composition of the Present Invention) Polyvinyl chloride obtained by emulsion polymerization (polyvinyl chloride for paste), coarse particle vinyl chloride resin obtained by microsuspension polymerization, and suspension Polyvinyl chloride (vinyl chloride suspension polymer: maximum particle size 150 μm) obtained by polymerization was mixed at the mixing ratio shown in Table 1.
The composition of the present invention for the surface layer was prepared by blending with a stabilizer and stirring and mixing with a stirrer.

[0031]

[Table 1]

(Production of Decorative Sheet) Using the composition of the present invention prepared as described above, the composition of FIG.
The decorative sheet (floor material) shown in 1 was prepared on a normal factory production scale. That is, the composition for the intermediate layer in Table 1 was applied onto a long backing material 1 by a doctor knife coating method to give a coating thickness of 0.
After coating so as to have a thickness of 4 mm, it was heat-treated at 180 ° C. for 3 minutes to be gelated to form an intermediate layer 2. A printing ink is used to print a predetermined pattern on the intermediate coating layer 2 by a gravure printing method, and this is dried, and then the composition of the present invention for a transparent surface layer is applied by a doctor knife coating method to a coating thickness of 0. It was applied so as to have a thickness of 0.2 mm, heated at 180 ° C. for 3 minutes to gel, and then heat-treated at 210 ° C. for 3 minutes to foam.

The surface layer 4 obtained as described above was visually inspected over the entire length of the flooring material, and it was preferable that the surface layer 4 had a rough matte surface having a rough texture like a ceramic.

Example 2 A flooring material was produced in the same manner as in Example 1 except that 50 parts by weight of vinyl chloride resin for paste, 40 parts by weight of coarse particle vinyl vinyl chloride resin and 10 parts by weight of vinyl chloride suspension polymer were used.

The surface layer 3 of the obtained flooring material was examined in the same manner as in Example 1. As a result, the surface layer 3 of the flooring material of Example 1 was slightly less rough in the matte state, but was ceramic-like. It was preferable in the matte state having the appearance of.

Example 3, Comparative Examples 1 to 5 The vinyl chloride resin for paste, the coarse particle vinyl chloride resin and the vinyl chloride suspension polymer prepared in Example 1 were used, blended in a mixing ratio shown in Table 2, and mixed by a stirrer. The composition of the present invention and the comparative composition were prepared by mixing with stirring. Using these compositions, a flooring material was manufactured in the same manner as in Example 1.

[0037]

[Table 2]

As a result of observing the flooring material obtained as described above,
The flooring material of Example 3 was a preferred one having a matte state similar to that of pottery ware in which the matte state was rougher than that of Example 1, but Comparative Examples 1 and 5 had a strong surface gloss and a matte tone. Was not obtained. Furthermore, Comparative Example 2,
No. 4 had a matte appearance, but did not have a rough matte appearance like a ceramic appearance. In Comparative Example 3, the amount of the vinyl chloride resin for paste was too small to prepare a paste that could be applied.

[0039]

As described above in detail, according to the composition of the present invention, the synthetic resin particles having a very fine particle size of the vinyl chloride resin for paste and the particles of the vinyl chloride resin for paste are slightly more than the particles. Coarse-grained vinyl chloride resin having a large particle diameter and synthetic resin particles having a large particle diameter of the vinyl chloride-based suspension polymer are mixed in a specific ratio to give a gloss of the surface of the layer formed by the composition of the present invention. It can be in a glossy state close to the appearance of ceramics and pottery.
As a result, it is possible to express a rough matte state having a rough appearance such as ceramics and pottery without using a special surface treatment agent. Therefore, when the composition of the present invention is used as a composition for forming a surface layer of a decorative sheet such as a flooring material, like a conventional surface layer having a high smoothness due to plastisol, it is mirror-finished to give gloss. , The surface will not be scratched, and a rough matte surface layer that cannot be obtained with a mixture of a vinyl chloride resin for paste and a coarse particle vinyl chloride resin can be obtained. A high floor material can be obtained. In particular, when the printing layer is interposed between the backing material or the synthetic resin intermediate layer and the layer composed of the gloss-controlling resin composition of the present invention, a blurring effect is produced as the amount of the vinyl chloride suspension polymer increases. It is possible to obtain a flooring material having a tasteful appearance in which the above pattern appears.

In addition, since the vinyl chloride suspension polymer and the coarse particle vinyl chloride resin are lower in cost than the vinyl chloride resin for paste, the vinyl chloride suspension polymer, the coarse particle vinyl chloride resin and the paste are used. According to the composition of the present invention, which is a mixture with a vinyl chloride resin for use, the production cost of the above decorative sheet can be significantly reduced.

Further, the heat discoloration resistance of the layer formed by the composition of the present invention can be improved, and the thermal stability of the above decorative sheet can also be improved.

The composition of the present invention is not limited to the transparent surface layer of the decorative sheet as described above, and is preferably used for forming various materials and colored opaque matte surface layers, such as ceramics and ceramics. It can also be suitably used for rough matte wall materials, vinyl chloride resin leather, and the like, which are similar in appearance to earthenware.

[Brief description of drawings]

FIG. 1 is an explanatory view showing the structure of a decorative sheet such as a flooring material which is an example to which the composition of the present invention can be applied.

[Explanation of symbols]

 1 Backing material 2 Intermediate layer 3 Printing layer 4 Transparent surface layer

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Claims (5)

(57) [Claims] 1. A total of 100 parts by weight of 30 to 80 parts by weight of vinyl chloride resin for paste, 60 to 10 parts by weight of coarse particle vinyl chloride resin, and 50 to 10 parts by weight of vinyl chloride suspension polymer. A resin composition for gloss control, which comprises a vinyl chloride-based resin blended in the following manner and a plasticizer in an amount of 20 to 100 parts by weight. 2. A backing material comprising 30 to 80 parts by weight of vinyl chloride resin for paste, 60 to 10 parts by weight of coarse particle vinyl chloride resin, and 50 to 10 parts by weight of vinyl chloride suspension polymer. Vinyl chloride resin, which is compounded so as to be 100 parts by weight in total, and a plasticizer 20 to 100
A layer of a resin composition for gloss control, in which at least one selected from a weight part and a stabilizer, a foaming agent, a filler, a foam stabilizer, a viscosity modifier, an ultraviolet absorber, an antistatic agent, and a colorant is blended, A laminate having a matte appearance formed. 3. A printing eyebrow is formed on a backing material, and 30 to 80 parts by weight of a vinyl chloride resin for paste and 60 to 10 parts by weight of a coarse particle vinyl chloride resin are provided on the printing layer. 5
Vinyl chloride resin prepared by blending 0 to 10 parts by weight of a vinyl chloride suspension polymer so as to make a total of 100 parts by weight, a plasticizer 20 to 100 parts by weight, a stabilizer, a foaming agent, a filler, and a foam stabilizer. A laminate having a matte appearance, which is formed by forming a layer of a gloss-controlling resin composition containing at least one selected from an agent, a viscosity modifier, an ultraviolet absorber, an antistatic agent, and a colorant. 4. A laminate having a matte appearance according to claim 3, wherein a synthetic resin intermediate layer is interposed between the backing material and the printing layer. 5. A laminate having a matte appearance according to claim 2, wherein a synthetic resin balance layer is formed on the back surface of the backing material.