JP5369575B2 - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a face sheet having various resistances such as anti-staining property and anti-injuring property on its surface as well as a good design thanks to excellent well-controlled gloss. <P>SOLUTION: A face sheet comprises at least a patterned layer, a transparent rein layer, a gloss-controlling layer and a surface protecting layer in this order on a colored resin layer, wherein the gloss controlling layer comprises a urethane resin as a main ingredient and particles of an indeterminate inorganic compound, and the surface protecting layer comprises a urethane resin containing silicone as a main ingredient and 1 to 3 wt.% of spherical particles having an average particle size of 1 to 2 &mu;m which is made of an inorganic compound. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a decorative sheet used for the interior and exterior of building materials, particularly for horizontal surfaces such as tables, dining tables, kitchens, etc., having a design by gloss / matte gloss adjustment, and various surfaces The present invention relates to a decorative sheet having excellent resistance.

  As a structure of the decorative sheet for the above-mentioned use, there is known a structure in which a pattern layer is provided on a colored resin as a base, and a transparent resin layer and a surface protective layer for imparting various resistances are provided. As the colored resin layer and the transparent resin layer, a composite olefin resin film or the like is preferably used instead of the vinyl chloride resin because of recent tendency to place importance on environmental problems. As the pattern layer, many designs such as grain are provided as an ink layer by gravure printing, but there are also those expressing a geometric pattern called an abstract pattern.

  Such a decorative sheet can be appropriately provided with a gloss adjusting layer for adjusting gloss that is glossy / matte. In this way, the gloss adjusting layer is provided on the pattern layer and coated with a resin to which an appropriate amount of additive has been added so that the pattern layer can be visually recognized by adjusting the coating thickness. Can be adjusted.

  However, when such a gloss adjusting layer is provided on the surface side, there is a problem in the antifouling property and the scratch resistance of the decorative sheet surface due to the influence of the additive floating on the surface.

  The present invention has been made in order to solve such problems, that is, the problem is that the surface has anti-staining properties, scratch resistance, etc. while having a design with excellent gloss adjustment. The object is to provide a decorative sheet having various resistances.

The present invention solves this problem. That is, the invention according to claim 1 is a makeup in which a pattern layer, a transparent resin layer, a gloss adjusting layer, and a surface protective layer are provided in this order on a colored resin layer. In the sheet, the gloss adjusting layer contains an amorphous inorganic compound particle containing a urethane resin as a main ingredient, and the amorphous inorganic compound particle is an inorganic oxide and the particle shape is not a spherical particle, but the amorphous shape. The average particle diameter as an average of the maximum diameter portion and the minimum diameter portion of the outer shape of the inorganic compound particles is 3 to 10 μm, and the surface protective layer is a spherical particle having an average particle diameter of 1 to 2 μm mainly composed of a urethane-based resin containing silicone. A decorative sheet comprising 1 to 3% by weight of inorganic compound particles.

  According to the first aspect of the present invention, the type of the inorganic compound particles added to the gloss adjusting layer and the surface protective layer is different, and by adding silicone to the surface protective layer, the surface contamination resistance is improved. It has various resistances such as scratch resistance and has an excellent design by adjusting gloss. In addition, it is possible to obtain a decorative sheet that has a high interlayer strength between the gloss adjusting layer and the surface protective layer and is easy to manufacture.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows the cross-sectional shape of one embodiment of the decorative sheet of the present invention. A pattern layer 2, a transparent resin layer 3, a gloss adjustment layer 4, and a surface protective layer 5 are provided on the colored resin layer 1.

  The colored resin layer 1 in the present invention is preferably a film made of a thermoplastic resin and appropriately applied with a pigment, an antioxidant and a weather resistance formulation. The thermoplastic resin itself is not particularly limited as a raw material. For example, an acrylic film, an olefin film, a vinyl chloride film, a polyester film, an ethylene vinyl acetate film, a polyimide film, and the like can be given. Further, depending on the film, it is assumed that the decorative sheet of the present invention is adhered to the wood material, and the primer treatment may be performed on the back surface as necessary to improve the adhesion. The thickness is not particularly limited, but about 10 to 300 μm is most commonly used.

  As the pattern layer 2 in the present invention, it is ink that forms the pattern, and the pigment and the binder may be appropriately selected. A raw material may be appropriately selected in consideration of adhesiveness with the film. For example, a coating liquid in which an isocyanate curing agent and a binder having active hydrogen are mixed is superior in terms of adhesiveness. Conventionally, the gravure printing performed conventionally is suitable for the method of applying the pattern pattern layer, but the printing method is not particularly limited, such as screen printing, offset printing, gravure offset printing, flexographic printing.

  The transparent resin layer 3 in the present invention is not particularly limited as long as it is a thermoplastic resin film. Olefin-based films, vinyl chloride-based films, and amorphous polyester films are suitable because they have various processability by heat softening. Although thickness is not limited, 10 micrometers-300 micrometers are suitable. The method of laminating the colored resin layer 1 provided with the pattern layer 2 and the transparent resin layer 3 is not particularly limited, and may be appropriately laminated according to the selected resin or ink. For example, when a vinyl chloride film is printed with a vinyl chloride vinyl acetate copolymer resin ink, the transparent vinyl chloride may be laminated with heat pressure. Moreover, what is necessary is just to laminate | stack with a transparent printing olefin film with a urethane-type dry laminate adhesive, when printing on the olefin-type film with urethane-type ink.

  The gloss adjusting layer 4 in the present invention contains an amorphous inorganic compound particle with a urethane resin as a main ingredient. The urethane resin is a reaction product of an acrylic polyol and an isocyanate compound that requires moderate flexibility so that the amorphous inorganic compound particles can be prevented from falling off and retained in the coating film, and an acrylic urethane resin is used. It is desirable.

  Examples of the acrylic polyol include (meth) acrylate monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and the like. A hydroxyl group-containing (meth) acrylate monomer and a copolymerizable monomer such as (meth) acrylonitrile, (meth) acrylic acid, styrene, α-methylstyrene, vinyltoluene, etc. This polymer is a polymer having an acrylic skeleton as the main chain and a hydroxyl group in the side chain.

  Examples of the isocyanate compound include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and the like. .

  As the amorphous inorganic compound particles, inorganic oxides such as silica and alumina are preferably used, and the particle shape is not limited to spherical particles, and can be used as appropriate, such as scaly and polygonal shapes, but is not particularly limited. It is not something. If it is a spherical particle, the effect of adjusting the gloss cannot be sufficiently exhibited, and it becomes difficult to adjust the gloss within a suitable amount of addition. The average particle diameter is difficult to measure if it is indefinite, but it can be considered as an average of the maximum diameter portion and the minimum diameter portion of the outer shape, and the average particle size is 3 to 10 μm. If it deviates from this, it will become difficult to adjust the gloss within a suitable amount of addition.

  As the surface protective layer 5 in the present invention, one containing 1 to 3% by weight of spherical inorganic compound particles having an average particle diameter of 1 to 2 [mu] m with the urethane-based resin containing silicone as a main ingredient is used.

  The urethane resin to which the silicone is added is not particularly limited as long as the silicone component is exposed on the surface layer. For example, by adding silicone oil to the urethane resin and bleed on the surface. A surface protective layer having stain resistance can be produced. Also, when the urethane resin is molded, an organopolysiloxane group is introduced into the side chain of the acrylic polyol and crosslinked with the polyisocyanate compound, thereby creating a silicone-modified acrylic urethane layer. The surface protective layer which has can be created.

  The spherical inorganic compound particles having an average particle diameter of 1 to 2 μm are preferably silicon compounds, and if they have hydration properties, the compatibility with the silicone-modified resin tends to decrease. The addition amount is preferably in the range of 1 to 3% by weight, and the thickness of the surface protective layer may be adjusted by the particle size and the addition amount.

  In addition to the gloss adjusting layer 4 and the surface protective layer 5, an ultraviolet absorber (benzotriazole, triazine, benzophenone, etc.) or a hindered amine light stabilizer is appropriately added in order to perform weather resistance prescription. The added part may be added according to the desired weather resistance, but is 0.1% to 50%, preferably 1% to 30%, based on the resin solid content.

  Examples of the benzotriazole ultraviolet absorber include 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy −3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2- (3-t- Butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5- Di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazo And the like, mixtures thereof, modified products, polymers, and derivatives.

  Examples of triazine ultraviolet absorbers include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4-[( 2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2- Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4dimethylphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethyl) Phenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine and the like, and mixtures, modified products, polymers, and derivatives thereof.

  Examples of the benzophenone-based ultraviolet absorber include octabenzone, modified products, polymers, and derivatives. In addition, since a bond with a resin component can be expected by crosslinking by addition of an isocyanate, a UV absorber having a hydroxyl group is suitable.

  In addition, a hindered amine light stabilizer is appropriately added in order to prevent the resin itself from being deteriorated by light, heat, water or the like. The added part may be added according to the desired weather resistance, but is 0.1 to 50% by weight, preferably 1 to 30% by weight, based on the resin solid content. Specifically, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate Bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-popperidinyl) sebacate, bis (2,2, decanedioic acid) 6,6-tetramethyl-1 (octyloxy) -4-piperidinyl) ester and the like, mixtures thereof, modified products, polymers, derivatives and the like.

  As a colored resin layer, a transparent resin layer is formed on a colored polyolefin film having a thickness of 70 μm with a two-component curable urethane resin gravure ink and a wood pattern patterned layer and a two-component curable polyester urethane adhesive. A transparent polyolefin resin having a thickness of 80 μm was laminated by co-extrusion, and at the same time as extrusion, the surface was embossed with a conduit handle.

A coating liquid containing 100 parts by weight of an acrylic polyol, 5 parts by weight of an isocyanate curing agent, and 2.5 parts by weight of amorphous silica as a matting agent is dried with a gravure coat on the transparent resin layer. The coating was performed so that the subsequent coating amount was 3.0 g / m ² .

A gravure coating is a coating liquid in which 100 parts by weight of an acrylic polyol, 5 parts by weight of an isocyanate curing agent, 3 parts by weight of silicone oil, and 2 parts by weight of spherical silica having an average particle diameter of 2 μm are blended as a protective layer on the gloss adjusting layer. Then, coating was performed such that the coating amount after drying was 3.0 g / m ² to obtain a decorative sheet.

<Comparative Example 1>
In Example 1, a decorative sheet was obtained in the same manner as Example 1 except that the inorganic compound silica was not added to the protective layer.

<Comparative example 2>
A decorative sheet was obtained in the same manner as in Example 1 except that the average particle size of spherical silica added to the protective layer in Example 1 was 6 μm.

<Making a decorative board>
On the surface of a 2.7 mm thick MDF (medium density fiberboard), a two-component aqueous emulsion adhesive (“Rikabond” (“BA-10L” and “BA-11B” manufactured by Chuo Rika Kogyo Co., Ltd.) is used as an adhesive. (Parts by weight: mixed at 5 parts by weight) was applied in a wet state to 70 g / m ² , and then bonded to the decorative sheet Example 1, Comparative Example 1, and Comparative Example 2 with a laminator to obtain a decorative board.

<Performance evaluation method>
Performance evaluation evaluated the decorative plate obtained in each Example and the comparative example by wiping off magic ink and resistance to steel wool.

<Magic ink wiping>
A line having a width of 10 mm was drawn on the surface of the decorative board with a black quick-drying ink (fast-drying writing instrument <specified in JIS S 6037 (1964)>), left for 1 minute, and then wiped with tissue paper. After the process was performed five times, the wiping condition of the magic was visually confirmed. ○: No magic remaining, ×: Evaluation with magic remaining

<Steel wool resistance test>
It is made to reciprocate 20 times with the steel wool (# 0000) of a 50-g load on the surface of a decorative board. Then, visually check the degree of damage. ○: No scratch, ×: Scratched.
The results are summarized in Table 1.

  The decorative sheet of the present invention can be used particularly for horizontal surfaces such as tables, dining tables, and kitchens.

It is explanatory drawing which shows the shape of the cross section of one Example of the decorative sheet of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Colored resin layer 2 ... Pattern pattern layer 3 ... Transparent resin layer 4 ... Gloss adjustment layer 5 ... Surface protective layer

Claims (1)

In a decorative sheet in which a pattern layer, a transparent resin layer, a gloss adjustment layer, and a surface protective layer are provided in this order on the colored resin layer, the gloss adjustment layer contains amorphous inorganic compound particles mainly composed of a urethane resin. The amorphous inorganic compound particles are inorganic oxides, and the particle shape is not spherical particles, and the average particle size is 3 as the average of the maximum diameter portion and the minimum diameter portion of the external shape of the amorphous inorganic compound particles. 10 to 10 μm, and the surface protective layer contains 1 to 3 wt% of spherical inorganic compound particles having an average particle diameter of 1 to 2 μm based on a urethane-based resin containing silicone. Sheet.