JP2001058375A - Wall facing sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a wall facing sheet friendly to a human being or environment and enhance antifouling properties, scratch resistance, workability or the like by forming a surface protective layer from a non-halogen type amorphous thermoplastic resin. SOLUTION: A surface protective layer 5 is formed from a compsn. based on a non-halogen type amorphous thermoplastic resin. That is, a foamed resin layer based on a foaming agent and an olefinic or acrylic resin is formed on the upper surface of a base material layer 2 and a pattern layer 4 is formed thereon and the surface protective layer 5 is formed thereon by a heating melt extrusion coating method and uneven patterns 6 are applied from the surface protective layer 5 to the foamed resin layer 3. The surface protective layer 5 is formed from a polyacrylonitrile type amorphous thermoplastic resin, for example, a graft copolymer based on acrylonitrile and consisting of a copolymer component such as acrylic ester and a butadiene elastomer and the thickness thereof is set to 5-20 μm from an aspect of surface properties or processability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet for interior to be attached to a wall surface or a ceiling surface of a house or the like, and more particularly, to an inexpensive and excellent surface physical property such as stain resistance and scratch resistance. To a wall-mounted seat.

[0002]

2. Description of the Related Art Conventionally, as a wall covering sheet, a vinyl chloride resin layer is formed on a base material and a picture layer is provided on the vinyl chloride resin layer by printing or the like, or the vinyl chloride resin A PVC decorative sheet represented by a so-called PVC wallpaper, such as a foamed layer and an embossed pattern or the like, is widely used. However, this PVC decorative sheet generates harmful gas such as hydrogen chloride gas during combustion, so it cannot be incinerated in general incinerators. There is a problem of poisoning due to harm, and it has been avoided to use it.

[0003] Further, in these wall covering sheets, dirt adhering to the surface of the wall covering sheet tends to permeate and is difficult to remove, and there is a problem that the surface strength of the wall covering sheet is weak and easily broken. There is. this is,
In order for the wall covering sheet to be made of vinyl chloride resin with problems of contamination and abrasion, and for the purpose of enhancing workability and design, in order to perform processing to form foam and uneven patterns, This is because fine irregularities and voids are generated on the surface of the wall covering sheet.

[0004] In order to solve the above problem, a method of providing a surface protective layer on the surface of a wall covering sheet has conventionally been adopted. That is, (1) a method of applying, for example, an acrylic resin or the like to the surface of the wall covering sheet to form a surface protective layer, and (2) a method of coating the surface of the wall covering sheet with stain resistance, scratch resistance, and the like. A method has been adopted in which an excellent film, for example, a fluorine-based film or a saponified ethylene-vinyl acetate copolymer film or the like is bonded with an adhesive or the like to form a surface protective layer.

However, since the method (1) is adjusted to a relatively low viscosity by using a solvent such as an organic solvent or water in consideration of processability, a method suitable for providing a thin surface protective layer. However, when a thick surface protective layer is provided, the operation becomes complicated, for example, the number of processing steps increases. In addition, the surface protective layer provided in this manner, when performing processing to form a foam or an uneven pattern, it is not possible to follow the foam or the uneven pattern, and the thickness of the surface protective layer varies, and in extreme cases, There is a problem that the surface protective layer is partially cracked and the foamed layer is exposed.

In the method (2), since the surface protective layer is made of a film, the surface physical properties itself are good. However, for example, the foamed layer is foamed to form an uneven pattern on the foamed layer, and then the film is formed. When the surface protective layer is formed by bonding together, it is difficult to apply the film in a state where the film is fitted to the foamed layer. When processing is performed, there occurs a problem that an uneven pattern is not formed sharply. In addition, in this method, in addition to the step of bonding a film to be used as a surface protective layer using an adhesive or the like, this film needs to be formed in advance,
Due to the restrictions on film formation, it is necessary to use a layer having a thickness greater than the required thickness as the surface protective layer, which inevitably results in high cost. Further, the wall-mounting sheet of the method (2) has such a tendency that the wrinkles are hard to disappear and the curl is easily generated, and the waist is too strong to stick to the wall or the like (poor workability). Problems arise.

As a method for solving these problems,
(3) A method is proposed in which the surface protective layer is formed by a hot melt extrusion coating method using a T-die extruder. By forming the surface protective layer by this method, the method of the above (1) or (2) is applied. Although the above problems that occur when a surface protective layer is formed could be solved, it is usually necessary to form an uneven pattern on the surface of these wall covering sheets in order to improve added value such as designability and workability. In the case where a thermoplastic resin is used as the resin for the surface protective layer, a method is usually employed in which the sheet is preheated, and then the pattern is transferred by pressing a surface uneven pattern roll (emboss roll). In the above, the surface protective layer formed by the hot melt extrusion coating method is heated again. At this time, if the resin forming the surface protective layer has crystallinity, the melt-extruded resin layer (surface protective layer) that has been oriented and crystallized at the time of the heat-melt extrusion coating tends to relieve stress and reorient. However, since the resin is already fixed to the foamed resin layer, the curling and warping of the wall covering sheet, the heat-melted extruded resin layer at a minute level, and the like are generated, and the problem of poor contamination resistance is further increased. Occurred.

[0008]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above problems, and an object of the present invention is to provide an inexpensive and inexpensive human or environmentally friendly wall covering sheet. Another object of the present invention is to provide a wall covering sheet having excellent surface properties such as stain resistance and scratch resistance, and also having excellent workability.

[0009]

Means for Solving the Problems To achieve the above object, a sheet for wall covering of the present invention comprises, on a base material layer, a foaming resin layer mainly comprising a foaming agent and an olefin resin or an acrylic resin; In a wall covering sheet provided with a pattern layer and a surface protection layer made of a thermoplastic resin in order, the surface protection layer is a non-halogen thermoplastic resin, and is made of an amorphous resin. is there. With this configuration, it is friendly to humans and the environment, is inexpensive, and has no minute-level defects in the surface protective layer even after reheating such as embossing, and is resistant to contamination and abrasion. It can be used as a wall covering sheet having excellent surface properties.

[0010] Further, an uneven pattern is formed on the surface protective layer side. By doing so, it is possible to obtain a wall covering sheet having a sharp uneven pattern and excellent in design.

Further, the amorphous resin forming the surface protective layer is mainly composed of an acrylonitrile resin or an acrylic resin. By doing so, a surface layer having excellent surface properties can be formed, and the minimum thickness required for the surface properties, or, since the surface layer can be formed with a thickness close to this, It can be inexpensive, and a sharp uneven pattern can be obtained.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. FIG. 1 is a cross-sectional view showing a laminated structure of a wall mounting sheet of the present invention, wherein 1 is a wall mounting sheet, 2 is a base material layer, 3 is a foamed resin layer, 4 is a pattern layer,
Denotes a surface protective layer, and 6 denotes an uneven pattern.

FIG. 1 is a layer configuration diagram showing one embodiment of the wall covering sheet of the present invention. The wall covering sheet 1 of the present invention has a foaming agent and an olefin resin or acrylic resin on the upper surface of a base material layer 2. A foamed resin layer 3 mainly composed of a resin is formed, and a pattern layer 4 is formed on the foamed resin layer 3.
A non-halogen thermoplastic resin and a surface protective layer 5 made of an amorphous resin are formed thereon, and an uneven pattern 6 is formed from the surface protective layer 5 side to the foamed resin layer 3. The feature of the constitution is that the surface protective layer 5 is a non-halogen thermoplastic resin formed by a hot melt extrusion coating method,
In addition, it is made of an amorphous resin.

The base material layer 2 used in the present invention is mainly composed of cellulose fibers and, if necessary, appropriately blended with synthetic fibers, inorganic fibers, synthetic pulp, etc., and contains a self-extinguishing filler, other fillers,
Dry paper strength agent, wet paper strength agent, colorant, sizing agent,
It is obtained by appropriately adding a fixing agent and the like to make paper.
Thick having a basis weight of to 150 g / m ² 0.10 to 0.3
A flame-retardant paper for 0 mm wallpaper is preferably used.

Next, the foamed resin layer 3 of the present invention is composed of a composition mainly comprising a foaming agent and an olefin resin or an acrylic resin. Examples of the olefin resin include polyethylene, polypropylene, and the like. Copolymers of one or more polyolefins such as polybutene, polybutadiene and polyisoprene to two or more olefins such as ethylene, propylene, butene, butadiene and isoprene, or copolymers of α-olefins having 4 or more carbon atoms (linear Low-density polyethylene), or ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, or ethylene-acrylic acid copolymer,
Examples thereof include an ethylene-methacrylic acid copolymer, an ethylene-methyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, an eye monomer, and a mixed resin thereof.

As the acrylic resin, acrylic resin (including methacrylic acid) whose main component is acrylamide or acrylonitrile, which is a derivative thereof, is obtained by polymerizing acrylamide, acrylonitrile, other acrylates, styrene and the like. And poly (meth) acrylate, ethyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate- (meth) acrylic acid Butyl copolymer, methyl (meth) acrylate- (meth)
2-hydroxyethyl acrylate copolymer, butyl (meth) acrylate-2-hydroxyethyl (meth) acrylate copolymer, methyl (meth) acrylate-2-hydroxypropyl (meth) acrylate copolymer, Methyl (meth) acrylate-butyl (meth) acrylate- (meth)
2-hydroxyethyl acrylate copolymer, ethylene-
Examples thereof include those composed of a homo- or copolymer containing a (meth) acrylate such as a methyl (meth) acrylate copolymer and a styrene-methyl (meth) acrylate copolymer. Here, (meth) acrylic acid is used in the meaning of acrylic acid and methacrylic acid.

The foamed resin layer 3 may be provided on the base material layer 2 by a known heat-melt extrusion method, a calendering method, or by using a non-halogenated thermoplastic resin in a solvent such as water or an organic solvent. Applying a solution that has been emulsified with, for example, a roll coating method,
Any coating method such as an air knife coating method and a comma doctor coating method can be adopted.

The foaming agent used for the foamed resin layer 3 of the present invention may be a low-boiling hydrocarbon, a thermally expanding capsule foaming agent containing a volatile substance such as chlorofluorocarbon or petroleum ether, or azo. Either or any of thermally decomposable foaming agents such as dicarbonamide and oxybisbenzenesulfonyl hydrazide can be used, but in order to obtain smoothness, thermally expanded capsule foaming agents are more preferable. Further, the amount of the foaming agent mixed with the non-halogen thermoplastic resin may be appropriately determined according to the type of the non-halogen thermoplastic resin and its coating amount, or the required design property. An appropriate amount is 0.5 to 20 parts by weight based on 100 parts by weight of the system resin.

In addition, the picture pattern layer 4 of the present invention can be generally formed of ink by a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet. Examples of the print pattern include a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and a print pattern such as a solid image. As the vehicle, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, acrylic, vinyl acetate, vinyl chloride-vinyl acetate copolymer, cellulose resin, polyamide resin These may be used as a mixture of one or more kinds, and pigments, solvents, various auxiliaries, etc. may be added thereto to form an ink. However, for the purpose of the present invention, polyesters, isocyanates and polyols may be used. Polyurethane, acrylic, vinyl acetate, cellulose resin, polyamide resin, etc.
A non-halogen thermoplastic resin in which two or more kinds are mixed is preferable.

Next, the surface protective layer 5 of the present invention is formed by applying a hot-melt extrusion coating method to a composition mainly composed of a non-halogen thermoplastic resin and an amorphous resin.
By using the surface protective layer 5 having such a configuration, even if a post-processing process involving heating such as foaming and embossing is performed, the workability such as curling and warping of the wall covering sheet 1 may be reduced. Since it does not cause defects or the like at a minute level, it is necessary to provide the wall mounting sheet 1 having excellent physical properties required for the wall mounting sheet, that is, excellent in chemical resistance, stain resistance, scratch resistance and the like. Can be.

The non-halogen thermoplastic resin used for the surface protective layer 5 is, for example, an acrylonitrile or acrylic resin as a main component, and is a resin which can be heated and melt extruded by a T-die extruder. And, for example, a polyacrylonitrile-based amorphous thermoplastic resin, having acrylonitrile as a main component, a copolymer component such as an acrylate ester and an elastic body of butadiene, and a so-called graft copolymer. Is used. The thickness of the surface protective layer 5 is in the range of 5 to 20 μm, more preferably 6 to 15 μm, from the viewpoint of surface physical properties, workability, cost effectiveness and the like. The acrylonitrile-based material has a higher flexural modulus, and therefore has better rigidity, and is suitable for being easily thinned as compared with other base materials. When the thickness is less than 5 μm, the surface properties required for a wall covering sheet cannot be obtained, and it is difficult to form a film by controlling the thickness with a T-die extruder. Not only can not form the pattern,
When the sheet is used as a wall-mounting sheet, there is a possibility that curling and creases in the sheet are conspicuous and construction problems may occur.

Next, as a method of forming the embossed pattern 6 of the present invention, aside from the stage of manufacturing the wall covering sheet of the present invention, the method of forming the wall covering sheet is as follows. It can be formed by heating and pressing with an embossing plate from the outermost layer side facing the base material layer 2 at a temperature at which embossing can be performed by the means. A well-known single-wafer or rotary embossing machine is used for processing the uneven pattern 6, and the shape of the uneven pattern 6 includes a wood grain board conduit groove, a stone board surface unevenness, a cloth surface texture, a satin finish, a grain, There are hairline, line and groove.

Next, as a method of manufacturing the wall covering sheet 1, a foaming layer forming composition comprising a foaming agent and a non-halogen thermoplastic resin is applied onto the base material layer 2, and the foaming layer forming composition is applied. A non-halogen thermoplastic resin, which is heated and melted by a T-die extruder, is extruded and coated on the side of the pattern layer 4 of the laminate having the pattern layer 4 provided thereon to form a surface protective layer 5, and then a heating foaming furnace The foamed layer forming composition is foamed with
And by applying heat and pressure with an embossing plate from the surface protective layer 5 side, the wall covering sheet 1 having the uneven pattern 6 on the surface protective layer 5 side can be obtained.

If necessary, the base material layer 2 and the foamed resin layer 3 may be made of one of inorganic materials such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, barium carbonate, antimony trioxide and titanium oxide. An inorganic filler composed of a mixture of two or more kinds or a flame retardant may be added, and if necessary, a pigment or the like may be added for coloring. The coloring by adding the pigment may be transparent coloring or opaque (concealing) coloring.

Further, a radical scavenger and / or an ultraviolet absorber may be added to the foamed resin layer 3 as necessary. This is used for the purpose of preventing the foamed resin layer 3 from being deteriorated by ultraviolet rays and improving weather resistance. As the radical scavenger, a hindered amine-based radical scavenger is suitable. The reason is that the hindered amine-based radical scavenger has a tetraalkylpiperidine as a mother nucleus, has a radical scavenging action of scavenging radicals generated by ultraviolet rays, and has various action mechanisms such as an inactive action of hydroperoxide (ROOH). Is presumed to exert its effect, and excellent performance can be obtained as a multifunctional stabilizer. Specific examples of the hindered amine radical scavenger include bis- (2,2,6,6
-Tetramethyl-4-piperidyl) sebacate, bis-
(N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2,6,6-
Pentamethyl-4-piperidyl) sebacate, 1,2,2
2,6,6-pentamethyl-4-piperidyl-tridecyl-1,2,3,4-butanetetracarboxylate,
In addition to tetragis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like, for example, compounds disclosed in Japanese Patent Publication No. 4-82625 Hindered amine radical scavengers. Further, as the ultraviolet absorber, for example, 2- (2′-hydroxy-3 ′, 5′-
Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-
Methylphenyl) -5-chlorobenzotriazole, 2
2'-hydroxyphenyl-5-chlorobenzotriazole-based ultraviolet absorbers such as-(2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy −3 ′, 5′-di-te
rt-butylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-5'-methylphenyl) benzotriazole and other 2'-hydroxyphenylbenzotriazole ultraviolet absorbers, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'- 2,2'-dihydroxybenzophenone-based UV absorbers such as dimethoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; Hydroxybenzophenone UV absorbers,
Salicylic acid ester UV absorbers such as phenyl salicylate, 4-tert-butyl-phenyl-salicylate, 2-ethyl-hexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenyl Acrylate, octyl-2-cyano-3,3
Although cyanoacrylate UV absorbers such as diphenyl acrylate can be used, chlorine-free benzotriazole-based, benzophenone-based, or cyanoacrylate-based UV absorbers are suitable as the UV absorber used in the wall covering sheet of the present invention. It is. In addition, these foamed resin layers 3
May be added with various stabilizers as necessary.

The surface protective layer 5 may have an antibacterial property by adding an antibacterial agent. Examples of the antibacterial agent to be added to the surface protective layer 5 include inorganic adsorbents such as activated carbon, activated alumina and silica gel, zeolites,
Inorganic ion exchangers such as hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrated bismuth, hydrated zirconium, hydrotalside, etc. are used together with silver ion or silver ion as well as copper ion and zinc ion. Well-known silver-based antibacterial agents, or zinc oxide compounds obtained by combining antibacterial inorganic salts with zinc oxide particles.

Although not shown, the substrate layer 2
To improve the interlayer adhesion between the foamed resin layer 3, or between the foamed resin layer 3 and the pattern layer 4, or between the pattern layer 4 and the surface protection layer 5. In addition, an adhesive force improving means such as adhesive application or corona discharge treatment may be used as appropriate.

[0028]

Example 1 First, a foamed resin layer forming composition (aqueous emulsion) having the composition shown in Table 1 was dried on a flame-retardant backing paper having a basis weight of 105 g / m ² (manufactured by Tokushu Paper Co., Ltd.). 170 g /
It was coated by a comma doctor coating method such that m ^2, and to produce an intermediate sheet A to form a design layer printed with a gravure printing method using an acrylic water-based ink on the coated surface. After applying a two-component curable urethane-based adhesive (base agent: polyester polyol) to the surface of the intermediate sheet A on which the pattern layer is formed so as to be 3 g / m ² after drying,
An acrylonitrile resin [Mitsui Chemicals, Inc., Barex, MFR: 3 g / 10
min] was extruded with a two-type three-layer T-die extruder to 10 μm
After forming the surface protective layer having a thickness, the foamed resin layer forming composition was heated and foamed, and embossed from the surface protective layer side to prepare a wall covering sheet.

[0029]

Comparative Example A polyolefin-based adhesive [UNISTOL P, manufactured by Mitsui Chemicals, Inc.] was applied to the surface of the intermediate sheet A on which the pattern layer was formed so as to be 3 g / m ² after drying. An olefin-based thermoplastic resin [Mon
tell-JPO Co., Ltd., homopolymer-based polypropylene, M
FR: 20 g / 10 min] was extruded with a two-type, three-layer T-die extruder to form a surface layer having a thickness of 10 μm, and then the foamed layer-forming composition was heated and foamed, and embossed from the surface layer side. Thus, a sheet for wall covering was produced.

Next, the Examples and Comparative Examples produced above were subjected to a stain resistance test in accordance with JIS K6902, and the results are summarized in Table 2.

[0032] * Test method: According to JIS K6902, 24 hours after adhering contaminants, left in an atmosphere of 25% and 60% RH, and visually observe the condition after wiping with a JK wiper. Evaluation method: ◎ The condition where dirt is completely removed A state in which dirt remained inconspicuous was evaluated as ○ A state in which dirt was slightly left was evaluated as △ A state in which dirt was left was evaluated as ×.

As is clear from Table 2, the sheet for wall covering of the present invention has extremely excellent performance in stain resistance.

[0034]

As described above, the wall covering sheet of the present invention does not generate harmful gases such as hydrogen chloride gas when incinerated, and has surface properties such as stain resistance and scratch resistance. In addition to being excellent in workability, it also has an excellent effect in workability. In addition, the minimum thickness required for the surface properties, or the surface layer can be formed with a thickness close to this, so that it can be inexpensive and obtain a sharp uneven pattern Therefore, it is possible to obtain an excellent effect in design.

[Brief description of the drawings]

FIG. 1 is a layer configuration diagram showing one embodiment of a wall covering sheet according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Wall covering sheet 2 Base material layer 3 Foam resin layer 4 Picture pattern layer 5 Surface protection layer 6 Uneven pattern

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AK01D AK03B AK25B AK25D AK27D AK51G AR00C AT00A BA04 BA07 BA10A BA10D CA01B CB00 CC00 DD01D DG10 DJ01B GB08 HB00C HB21D HB31 JA12D JB06D JL06

Claims (3)

[Claims] 1. A foamed resin layer mainly comprising a foaming agent and an olefin resin or an acrylic resin on a base material layer,
A wall covering sheet provided with a pattern layer and a surface protective layer made of a thermoplastic resin in order, wherein the surface protective layer is a non-halogen thermoplastic resin, and is made of an amorphous resin. Sheet. 2. The wall covering sheet according to claim 1, wherein an uneven pattern is formed on the surface protective layer side. 3. The wall covering sheet according to claim 1, wherein the amorphous resin forming the surface protective layer is mainly composed of an acrylonitrile resin or an acrylic resin.