JPH04337345A - Gloss-controlling resin composition - Google Patents

Abstract

PURPOSE:To obtain a gloss-controlling resin composition capable of forming a surface layer having appearance close to that of ceramic and porcelain ware, etc., by using a vinyl chloride resin for paste, coarse particles of a vinyl chloride resin and a vinyl chloride suspension polymer. CONSTITUTION:The objective gloss-controlling resin composition is produced by compounding (A) 30-80 pts.wt. of vinyl chloride resin particles for paste produced by emulsion polymerization or microsuspension polymerization and having particle diameter of 0.02-20mum, (B) 60-10 pts.wt. of coarse vinyl chloride resin particles produced by microsuspension polymerization and having particle diameter of 10-60mum and (C) 50-10 pts.wt. of a vinyl chloride suspension polymer produced by suspension polymerization and having particle diameter of 50-200mum (the sum of A to C is 100 pts. wt.) and compounding 100 pts. wt. of the obtained vinyl chloride resin with (D) 20-100 pts. wt. of a plasticizer (e.g. a phthalate, phosphate or epoxy-type plasticizer) and, as necessary, (E) stabilizers, foaming agents, fillers, foam stabilizers, etc. A laminate having matte appearance can be produced by forming a layer of the composition on a backing material.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a resin composition suitably used in 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

[Prior art] Traditionally, architecture (ceiling materials, wall materials, floor materials, etc.)
Decorative sheets made of synthetic resin are widely used as surface materials for furniture, vehicles, electrical products, footwear, bags, etc.

[0003] Generally, such decorative sheets include:
As shown in Figure 1, backing material 1 such as woven fabric, knitted fabric or paper
On top, a hollow layer 2 of foamed or non-foamed vinyl chloride resin, etc.
A predetermined pattern is printed on the hollow layer 2 using printing ink such as foamed or non-foamed vinyl chloride resin by various printing methods such as rotary screen method and gravure method. It is known that a so-called printed layer 3 is formed in this way, and a transparent surface layer 4 is further formed.

By the way, the above-mentioned transparent layer 4 has conventionally been made by adding a stabilizer and, if necessary, a coloring agent to a so-called plastisol made by mixing a polyvinyl chloride resin for paste with a plasticizer, and then rolling it. It is formed by coating on the printing layer 3 by an appropriate method such as a coating method, a doctor knife coating method, a rotary screen method, or a gravure method.

[0005]

[Problems to be Solved by the Invention] However, the above-mentioned plastisol uses a vinyl chloride resin for paste with an extremely fine particle size obtained by so-called emulsion polymerization, and this is applied onto the backing material 1. After application, when heated to gel, the extremely fine resin particles make the surface of the coating highly smooth and mirror-like, resulting in a glossy surface that is unsuitable for use as an interior material. .

[0006] For this reason, an attempt was made to adjust the luster by mixing a coarse-grained vinyl chloride resin with the paste vinyl chloride resin, but the product had a matte effect and had a rough appearance like ceramics or pottery. was not obtainable.

[0007] Taking the above points into consideration, the present invention aims to provide a resin composition that can be used not only for forming the transparent layer in the above-mentioned decorative sheet but also for forming the surface layer of various materials. .

[0008]

[Means for Solving the Problems] The present inventor has discovered that while the vinyl chloride resin for paste has an extremely fine particle size as described above, the coarse particle vinyl chloride resin has a relatively small particle size. If this PVC resin for paste is used in combination with coarse-particle PVC resin, a product with a matte effect can be obtained, but it will not be as rough as ceramic or pottery. It was not possible to obtain a product with a rough matte appearance. As a result of repeated research to achieve the above object, the inventor has found that
By using a combination of paste-grade vinyl chloride resin, coarse-grained vinyl chloride resin, and vinyl chloride suspension polymer in a specific range of proportions, it is possible to create a rough matte finish that has a rough appearance similar to ceramic or pottery. The present inventors have discovered that a similar product can be obtained, and have completed the present invention.

That is, 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-grained vinyl chloride resin, and 50 to 10 parts by weight of vinyl chloride suspension polymer. The object of the present invention is to provide a resin composition for gloss adjustment, which is characterized by being blended so as to have the following properties.

The vinyl chloride resin for paste in the composition of the present invention is extremely fine polymer particles, and the particles are generally about 0.02 to 20 μm in size. Vinyl chloride resins for pastes are usually called paste resins, and can be made into plastisols by adding plasticizers. Generally, methyl methacrylate, methacrylic ester, acrylic ester, higher vinyl ether, etc.
The emulsion polymerization method involves radical polymerization using a water-soluble polymerization initiator, or the monomers are mechanically dispersed uniformly in water using an oil-based polymerization initiator using a homogenizer, etc. Examples include polymers obtained by a microsuspension polymerization method. These can be used alone or in combination.

The coarse-grained vinyl chloride resin (blending resin) in the composition of the present invention is fine polymer particles, but they are coarser than the particles of the vinyl chloride resin for paste, and have a particle size of about 10 to 60 μm. Common. Coarse particle vinyl chloride resin is usually obtained by a microsuspension polymerization method, and synthetic resins constituting this coarse particle vinyl chloride resin include those similar to the above-mentioned vinyl chloride resin for paste. These coarse particle vinyl chloride resins can be used alone or in combination.

[0012] As is well known, the above-mentioned vinyl chloride-based suspension polymer refers to vinyl chloride and other monomers that can be copolymerized with vinyl chloride, and these monomers and polymers (
In other words, it refers to a vinyl chloride polymer obtained by a suspension polymerization method in which the vinyl chloride polymer (vinyl chloride polymer) is dispersed by mechanical stirring in a liquid phase (generally water) in which both are hardly dissolved. Alternatively, the particle size of the copolymer is about 50 to 200 μm, which is several tens to hundreds of times larger than the particle size of the above-mentioned vinyl chloride resin for paste. The synthetic resins constituting this vinyl chloride suspension polymer include those similar to the above-mentioned vinyl chloride resin for paste, and these vinyl chloride suspension polymers may be used alone or in combination. be able to.

This mixture of vinyl chloride resin for paste, coarse particle vinyl chloride resin, and vinyl chloride suspension polymer is blended with a plasticizer, a solvent, etc., 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), and diundecyl phthalate (DINP). General phthalate ester plasticizers such as DUP), general fatty acid ester plasticizers such as dioctyl adipate (DOA), dioctyl sebacate (DOS), and dioctyl azelaate (DOZ). , trimellitic acid ester plasticizers represented by trioctyl trimellitate (TOTM), phosphate ester plasticizers represented by tricresyl phosphate (TCP), epoxy plasticizers,
Polymer 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. In addition to these general plasticizers, we also use reactive plasticizers such as DAP, acrylic monomers, and acrylic oligomers, tributoxyethyl phosphate, butyl diglycol adipate, and Sansocizer C-1100 (trade name manufactured by Shin Nippon Rika). , AM-801A
, AM-801B (trade name, manufactured by Sekisui Chemical Co., Ltd.), and secondary plasticizers such as dodecylbenzene derivatives can also be used.

The mixing ratio of the above mixture of vinyl chloride resin for paste, coarse particle vinyl chloride resin, and vinyl chloride suspension polymer and plasticizer depends on the type of plasticizer, the type of synthetic resin, and the mixing ratio of synthetic resin. The optimum ratio is selected depending on the situation, but in general, 20 to 100 parts by weight of plasticizer per 100 parts by weight of the total amount of vinyl chloride resin for paste, coarse-grained vinyl chloride resin, and vinyl chloride suspension polymer. It is preferable to set it to about 1.5 parts.

In addition to the above-mentioned plasticizer, the composition of the present invention also contains stabilizers, foaming agents, fillers, foam stabilizers, viscosity modifiers,
Additives such as ultraviolet absorbers, antistatic agents, and colorants may also be added.

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

As the blowing agent, any foaming agent that is normally used for vinyl chloride resins can be used.
The following is an example. N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, azodicarbonamide, azobisisobutyronitrile, benzenesulfonylhydrazide, P,P'-oxybis (benzenesulfonylhydrazide), benzene-1,3-disulfonylhydrazide,
In addition to decomposable blowing agents such as toluenesulfonyl hydrazide,
A microcapsule blowing agent can be used in which a liquid that vaporizes when heated, such as liquid hydrocarbons such as butane and isobutane, is encapsulated in microcapsules made of thermoplastic synthetic resin.

As the filler, any inorganic and/or organic filler with excellent heat resistance that does not cause physical or chemical changes such as melting or decomposition at the processing temperature can be used. , Here are some examples: 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 bulb, foam glass bulb, fly ash bulb, volcanic glass hollow body (shirasu balloon), glass fiber,
Inorganic fillers such as inorganic fibers such as carbon fibers, powdered cellulose (cellulose powder), organic fibers such as polyvinyl alcohol fibers, cork powder, wood powder, thermosetting resin powder, thermosetting resin hollow spheres, crosslinked Organic fillers such as thermoplastic resin powder can be used.

[0020] When forming a foam layer by mechanical foaming, it is preferable to use a foam stabilizer;
Any commonly used foam stabilizer can be used, such as silicone foam stabilizers such as methylsiloxane emulsion and methylsiloxane solution, fluorine foam stabilizers,
Fatty acid condensates, alkylaryl sulfonates, metal soaps of oleic acid and ricinoleic acid, guanidine salts, quaternary ammonium compounds, aldehyde-amine condensation products, etc. can be used.

Viscosity modifiers are broadly classified into thinners and thickeners. Commonly used thinners can be used, examples of which are listed below. Volatile diluents such as gasoline, octane, benzene, xylene, naphtha, dodecylbenzene derivatives, methyl ethyl ketone, methyl isobutyl ketone, and various surfactants are used. As the thickener, commonly used thickeners can be used, examples of which are listed below. Metal soaps such as aluminum stearate, aluminum oleate, and zinc stearate, silica, bentonite, and polymerized oils can be used. These viscosity modifiers are used by adding an appropriate amount as necessary when adjusting the viscosity of the vinyl chloride resin paste composition to a viscosity suitable for processing.

As the ultraviolet absorber, 2-hydroxy-
4-methoxybenzophenone, 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-methoxybenzophenone, 2-
Hydroxy-4-methoxy-5-sulfonebenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2-hydroxy-5-chlorobenzophenone, bis-(2-methoxy-4-hydroxy-5-benzoylphenyl)methane Benzophenone ultraviolet absorbers such as 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-ethylsulfonebenzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-methoxyphenyl)-5-methylbenzo Benzotriazole UV absorbers such as triazole, 2-(2'-hydroxy-5'-methylphenyl)-5-carboxylic acid ester benzotriazole, 2-(2'-acetoxy-5'-methylphenyl)benzotriazole, etc. Can be used.

As the antistatic agent, any commonly used antistatic agent can be used, but nonionic antistatic agents are particularly preferred, examples of which are listed below. Ether types such as polyoxyethylene alkylether, polyoxyethylene markylaryl ether, polyoxyethylene polyoxypropylene ether, ester types such as polyoxyethylene alkyl ester, partial ester compounds of polyhydric alcohol and fatty acid, Network ether type products such as polyoxyethylene alkylamine, polyoxyethylene sorbitan fatty acid ester,
Examples include ether ester types such as polyoxyethylene sorbitol fatty acid ester, polyoxyethylene mannitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, and polyoxyethylene propylene glycol monofatty acid ester. in particular,
■ Partial ester of polyhydric alcohol such as sorbitan, sorbitol, mannitan, mannitol, glycerin, diglycerin, pentaerythritol, etc. and fatty acid having 12 to 22 carbon atoms; ■ Added mole number of ethylene oxide or propylene oxide is 1 to 20; It is a polyoxyalkylene polyhydric alcohol fatty acid ester in which the polyhydric alcohol is sorbitan, sorbitol, mannitan, mannitol, glycerin, diglycerin, or pentaerythritol, and 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 (that is,
The synthetic resins that make up the vinyl chloride resin for paste, the coarse vinyl chloride resin, and the vinyl chloride suspension polymer may be of the same type or different types, but if they are of different types, the A mixture of materials that have approximately the same heat treatment temperature, or materials that are compatible with each other and do not cause any problems in film strength after film formation, etc.).

[0025] At this time, if the mixing ratio of the vinyl chloride suspension polymer is too small, the matte effect of the coating film will not be sufficient (it will not be possible to obtain a rough matte effect similar to the appearance of ceramics or pottery). ), on the other hand, if the amount is too high, the mechanical strength of the coating will decrease, resulting in a decrease in tensile strength, tear strength, etc., as well as a decrease in elongation rate, as well as an increase in the viscosity of plastisol, resulting in poor workability. becomes worse. In addition, if the mixing ratio of coarse-grained vinyl chloride resin is too small, the matting effect of the coating film will not be sufficient (resulting in a rough glossy state with a shiny bottom); on the other hand, if it is too large, In the same way as when the mixing ratio of suspension polymer is too high, the mechanical strength of the coating film decreases, and the tensile strength, tear strength, etc. not only decrease, but also the elongation rate decreases, and the viscosity of the plastisol decreases. rise,
Workability will deteriorate. Further, the composition of the present invention can be used with the addition of a foaming agent, but if too much vinyl chloride suspension polymer is added, there are problems such as roughness of the foamed cells obtained by foaming. From this point of view, in the composition of the present invention, the mixing ratio of the vinyl chloride resin for paste, the coarse-grained vinyl chloride resin, and the vinyl chloride-based suspension polymer is adjusted to be: vinyl chloride resin for paste: coarse-grained vinyl chloride resin: Vinyl chloride suspension polymer = 30-80 parts by weight: 60-10 parts by weight: 5
It is set as 0 to 10.

The above-mentioned blowing agents that can be added to the composition of the present invention include those commonly used in vinyl chloride resins for pastes, coarse-particle vinyl chloride resins, and vinyl chloride suspension polymers. You can use things as they are.

[0027] In order to form a matte surface layer using the above composition of the present invention, as in the case of conventional plastisols, for example, in the case of a decorative sheet, a backing material (on which a hollowing layer is formed if necessary) is used. ) may be heat-treated after applying the composition of the present invention. At this time, the same coating film forming means as in the case of conventional plastisols can be employed, such as a doctor knife coating method, a rotary screen method, a gravure method, and the like. Examples of the backing material include foamed or non-foamed synthetic resin sheets, nonwoven fabrics, woven fabrics, and knitted fabrics made of one or more of glass fibers, organic fibers, and pulp, and nonwoven fabrics, woven fabrics, and knitted fabrics of these. A sheet-like material made of cloth coated or impregnated with a synthetic resin, in which a colored or colorless transparent, translucent, or opaque synthetic resin layer is substantially formed, can be used. Then, it is gelled by heat treatment, and if a foaming agent is mixed, it is then heated and foamed.

[0028]

[Function] In the composition of the present invention, since the vinyl chloride resin for paste, the coarse-grained vinyl chloride resin, and the vinyl chloride suspension polymer are mixed in a specific ratio, the composition resembles the rough appearance of ceramics, pottery, etc. It becomes a matte state with a glossy appearance, and the gloss can be freely adjusted according to the mixing ratio.

Moreover, the layer formed by the composition of the present invention has improved resistance to heat discoloration. Therefore, when forming a layer by mixing a coloring agent with the composition of the present invention, the above-mentioned surface layer may be formed by the composition of the present invention also during the heat treatment after application of the composition of the present invention. Even when the decorative sheet is brought into contact with a heating element while being used as a wall material, flooring material, etc., the layer does not discolor, and the coloring originally formed at the time of layer formation is stably maintained.

[0030]

[Examples] Example 1 (Preparation of the 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,
A 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]

(Manufacture of decorative sheet) Using the composition of the present invention prepared as described above, the composition shown in FIG.
The decorative sheet (flooring material) shown in is prepared on a normal factory production scale. That is, on the long backing material 1, the composition for the hollow coating layer shown in Table 1 was coated to a thickness of 0.05 mm using the doctor knife coating method.
After coating to a thickness of 4 mm, it was heated at 180° C. for 3 minutes to form a gel, thereby forming a hollow layer 2. A predetermined pattern is printed on this middle coating layer 2 using a printing ink by a gravure printing method, and after drying, the composition of the present invention for a transparent surface layer is applied to a thickness of 0 by a doctor knife coating method. It was coated to a thickness of .2 mm, heated at 180°C for 3 minutes to gel, and then heated at 210°C for 3 minutes to foam.

When the surface layer 4 obtained as described above was visually inspected over the entire length of the flooring material, it was found to have a preferable rough matte surface with a ceramic-like rough appearance.

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-grained vinyl chloride resin, and 10 parts by weight of vinyl chloride suspension polymer were used.

When the surface layer 3 of the obtained flooring material was examined in the same manner as in Example 1, it was found that it was in a slightly matte state with less roughness than the matte state of the flooring material in Example 1, but it was ceramic-like. It had a desirable matte appearance.

Example 3, Comparative Examples 1 to 5 The vinyl chloride resin for paste prepared in Example 1, the coarse particle vinyl chloride resin, and the vinyl chloride suspension polymer were mixed at the mixing ratios shown in Table 2, and mixed using a stirrer. A composition of the present invention and a comparative composition were prepared by stirring and mixing. Flooring materials were manufactured in the same manner as in Example 1 using these compositions.

[0037]

[Table 2]

[0038] As a result of observing the flooring material obtained in the above manner,
The flooring material of Example 3 was preferable as it had a matte state similar to the appearance of coarse pottery pottery than that of Example 1, but Comparative Examples 1 and 5 had a strong surface gloss and a matte appearance. It was not possible to obtain the desired appearance. Furthermore, Comparative Example 2,
No. 4 gave a matte appearance, but did not have a rough matte appearance like ceramic appearance. Furthermore, in Comparative Example 3, the amount of vinyl chloride resin for paste was too small to prepare a paste that could be coated.

[0039]

Effects of the Invention As detailed above, according to the composition of the present invention, synthetic resin particles with extremely fine particle diameters of vinyl chloride resin for paste, and particles of a vinyl chloride resin for paste that are slightly smaller than those of the vinyl chloride resin for paste. By mixing a coarse-grained vinyl chloride resin with a large particle size and a synthetic resin particle with a large particle size of a vinyl chloride-based suspension polymer in a specific ratio, the surface gloss of the layer formed by the composition of the present invention can be improved. It is possible to achieve a glossy state similar to the appearance of ceramics, pottery, etc. As a result, it is possible to express a rough matte state with a rough appearance similar to that of ceramics or pottery without using a special surface treatment agent. Therefore, if 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, it will not become mirror-like and shiny like the surface layer with high smoothness made by conventional plastisol. , the surface does not become scratchy, and a rough matte surface layer that cannot be obtained by using a mixture of paste-grade vinyl chloride resin and coarse-grained vinyl chloride resin can be obtained, and the product value increases. This provides high-quality flooring. In particular, in the case where a printed layer is interposed between the backing material or synthetic resin intermediate layer and the layer made of the gloss-adjusting resin composition of the present invention, as the amount of the vinyl chloride-based suspension polymer increases, This provides a flooring material with an attractive appearance in which the pattern appears.

In addition, vinyl chloride-based suspension polymers and coarse-grained vinyl chloride-based resins are lower in cost than vinyl chloride-based resins for pastes, so vinyl chloride-based suspension polymers, coarse-grained vinyl chloride-based resins, and pastes are used. According to the composition of the present invention, which is a mixture with a vinyl chloride-based resin, the manufacturing cost of the above-mentioned decorative sheet can be significantly reduced.

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

The composition of the present invention is suitably used not only for forming transparent surface layers of decorative sheets as described above, but also for forming colored, opaque, and matte surface layers on various materials, such as ceramics and pottery. It can also be suitably used for wall materials with a rough matte state similar to the appearance of ceramics, vinyl chloride resin leather, etc.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram 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

Claims (14)

[Claims] Claim 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-grained vinyl chloride resin, and 50 to 10 parts by weight of vinyl chloride suspension polymer. A gloss-adjusting resin composition comprising a vinyl chloride resin and 20 to 100 parts by weight of a plasticizer. Claim 2: The plasticizer is di-2-ethylhexyl phthalate (DOP), diisononyl phthalate (
DINP), butyl benzyl phthalate ester (BBP)
), general phthalate ester plasticizers such as diisodecyl phthalate (DIDP), diundecyl phthalate (DUP), dioctyl adipate (DOA), dioctyl sebacate (
DOS), azelaic acid dioctyl ester (DOZ)
General fatty acid ester plasticizers represented by , trimellitate ester plasticizers represented by trioctyl trimellitate (TOTM), phosphate ester plasticizers represented by tricresyl phosphate (TCP), etc. Plasticizers, epoxy plasticizers, polymer plasticizers such as polyester plasticizers such as polypropylene adipate, general plasticizers such as chlorinated paraffin, and/or DAP, acrylic monomers, acrylic oligomers Reactive plasticizers such as tributoxyethyl phosphate, butyl diglycol adipate, Sansocizer C-
1100 (product name manufactured by Shin Nippon Rika), AM-801A, A
The gloss-adjusting resin composition according to claim 1, which is one or more selected from antistatic plasticizers such as M-801B (trade name, manufactured by Sekisui Chemical Co., Ltd.) and secondary plasticizers such as dodecylbenzene derivatives. 3. The composition according to claims 1 to 2, wherein at least one selected from stabilizers, blowing agents, fillers, foam stabilizers, viscosity modifiers, ultraviolet absorbers, antistatic agents, and colorants is blended. The gloss-adjusting resin composition according to any one of the above. 4. The stabilizer is a metal stabilizer such as cadmium, zinc, barium, calcium, strontium, aluminum, magnesium, cerium, sodium, lead, or tin;
The gloss-adjusting resin composition according to claim 3, which is one or more selected from organic phosphorous acid compounds, polyhydric alcohols, and epoxy compounds. 5. The blowing agent is N,N'-dinitrosopentamethylenetetramine, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, azodicarbonamide, azobisisobutyronitrile, benzenesulfonyl. hydrazide, P,P'-oxybis(benzenesulfonylhydrazide), benzene-1,3-disulfonylhydrazide,
The claim is one or more types of blowing agents selected from decomposable blowing agents such as toluenesulfonyl hydrazide, and microcapsule blowing agents in which a liquid that vaporizes when heated, such as liquid hydrocarbons such as butane and isobutane, is encapsulated in microcapsules made of thermoplastic synthetic resin. Item 3. The gloss-adjusting resin composition according to item 3. 6. The filler is calcium carbonate, magnesium carbonate, clay, talc, silica, diatomaceous earth, silica sand, pumice powder, slate powder, mica powder, asbestos, aluminum hydroxide, magnesium hydroxide, aluminum oxide, Inorganic fillers such as aluminum sulfate, barium sulfate, calcium sulfate, glass bulbs, foamed glass bulbs, fly ash bulbs, volcanic glass hollow bodies (shirasu balloons), inorganic fibers such as glass fibers and carbon fibers, powdered cellulose (cellulose powder) ), organic fibers such as polyvinyl alcohol fibers,
The gloss-adjusting resin composition according to claim 3, which is one or more organic fillers selected from cork powder, wood flour, thermosetting resin powder, thermosetting resin hollow spheres, crosslinked thermoplastic resin powder, and the like. thing. [Claim 7] The foam stabilizer is a silicone foam stabilizer such as a methylsiloxane emulsion or a methylsiloxane solution, a fluorine foam stabilizer, a fatty acid condensate, an alkylaryl sulfonate type, a metal soap containing oleic acid or ricinoleic acid, or guanidine. The gloss-adjusting resin composition according to claim 3, which is one or more selected from salts, quaternary ammonium compounds, and aldehyde-amine condensation products. [Claim 8] The viscosity modifier is a volatile diluent such as gasoline, octane, benzene, xylene, naphtha, dodecylbenzene derivatives, methyl ethyl ketone, methyl isobutyl ketone, a thinner such as various surfactants, or aluminum stearate. 4. The luster-adjusting resin composition according to claim 3, wherein the resin composition is one or more selected from the group consisting of metal soaps such as aluminum oleate and zinc stearate, and thickeners such as silica, bentonite, and polymerized oil. 9. The ultraviolet absorber is 2-hydroxy-4-methoxybenzophenone, 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-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfonebenzophenone, 2
, 2'4,4'-tetrahydroxybenzophenone, 2
-Hydroxy-5-chlorobenzophenone, bis-(2
Benzophenone UV absorbers such as -methoxy-4-hydroxy-5-benzoylphenyl)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'-methyl) phenyl)-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)benzo Triazole, 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-ethylsulfonebenzotriazole, 2-(2'-hydroxy-4' -octoxyphenyl)benzotriazole, 2-(2'-hydroxy-
5'-methoxyphenyl)-5-methylbenzotriazole, 2-(2'-hydroxy-5'-methylphenyl)-5-carboxylic acid ester benzotriazole, 2-
The gloss-adjusting resin composition according to claim 3, which is one or more types selected from benzotriazole-based ultraviolet absorbers such as (2'-acetoxy-5'-methylphenyl)benzotriazole. Claim 10: The antistatic agent is an ether-type agent such as polyoxyethylene alkylether, polyoxyethylene markylaryl ether, polyoxyethylene polyoxypropylene ether, polyoxyethylene alkyl ester, polyhydric alcohol and fatty acid. Ester type compounds such as partial ester compounds, net ether type compounds such as polyoxyethylene alkylamine, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene mannitan fatty acid ester, polyoxyethylene glycerin The gloss-adjusting resin composition according to claim 3, which is one or more selected from fatty acid esters, ether ester types such as polyoxyethylene propylene glycol monofatty acid esters, and the like. 11. On the backing material, 30 to 80 parts by weight of a vinyl chloride resin for paste, 60 to 10 parts by weight of a coarse vinyl chloride resin, and 50 to 10 parts by weight of a vinyl chloride suspension polymer. A vinyl chloride resin made by blending 100 parts by weight in total, and 20 to 10 parts by weight of a plasticizer.
A layer of a gloss-adjusting resin composition containing 0 parts by weight and at least one or more selected from stabilizers, foaming agents, fillers, foam stabilizers, viscosity modifiers, ultraviolet absorbers, antistatic agents, and colorants. A laminate with a matte appearance formed by forming. 12. A printed layer is formed on the backing material, and on the printed layer, 30 to 80 parts by weight of a vinyl chloride resin for paste, and 60 to 10 parts by weight of a coarse-grained vinyl chloride resin,
A vinyl chloride resin prepared by blending 50 to 10 parts by weight of a vinyl chloride suspension polymer for a total of 100 parts by weight, 20 to 100 parts by weight of a plasticizer, a stabilizer, a blowing agent, a filler, and a foam stabilizer. 1. A laminate having a matte appearance, which is formed by forming a layer of a gloss-adjusting resin composition containing at least one selected from a viscosity modifier, a viscosity modifier, an ultraviolet absorber, an antistatic agent, and a colorant. 13. The laminate having a matte appearance according to claim 12, wherein a synthetic resin intermediate layer is interposed between the backing material and the printing layer. 14. The laminate having a matte appearance according to claim 11, wherein a balance layer of synthetic resin is formed on the back surface of the backing material.