JP6269226B2 - Interior decorative sheet - Google Patents

Description

  The present invention is an interior decorative sheet used for the interior of a building and used on the surface of furniture, fittings, etc., and in particular, is a non-vinyl chloride based decorative sheet, which is difficult to adhere to indoor dust and dust and is easy to wipe off. Furthermore, the present invention relates to a decorative sheet for interiors having excellent surface contamination resistance and durability.

  Conventionally, vinyl chloride resin has been frequently used as a base sheet for decorative sheets. However, in recent years, vinyl chloride resin products have been avoided because of consideration for the global environment. Therefore, non-vinyl chloride resins such as polyolefin resins are typically used instead of vinyl chloride resins. It has come to be. (Patent Document 1)

  However, the decorative sheet made of polyolefin resin is more likely to generate static electricity and more easily adhere to dust and dirt than the decorative sheet made of vinyl chloride resin. Therefore, a decorative sheet has been proposed in which an antistatic agent is added to the layer of the decorative sheet to improve the antistatic property. For example, a conductive sheet or an antistatic agent is added to the base sheet in which a conductive agent or an antistatic agent of inorganic particles is added, or in a second resin layer exposed on the surface of a two-layer base sheet. And the like. (Patent Document 2)

  However, as in Patent Document 2, in the case of a configuration without a surface protective layer of a curable resin, an antistatic agent can be sufficiently obtained by adding an antistatic agent to the base sheet exposed on the surface. Since it does not have a layer, it cannot be superior in surface strength or stain resistance. However, if an antistatic agent is added to the base sheet and a surface protective layer of a curable resin is provided thereon, the surface strength and stain resistance can be improved. In the decorative sheet having such a laminate, since the antistatic agent is added to the lower layer of the decorative sheet, the antistatic effect due to the antistatic agent is hardly produced. Then, the antistatic agent may be added to the surface protective layer, but in this case, the surface strength of the surface protective layer made of a curable resin can be obtained, but the stain resistance is reduced, for example, in blue ink. On the other hand, the stain resistance for use around the kitchen is remarkably inferior. In addition, there is a problem that the appearance is whitened over time and the weather resistance is poor.

  Then, the decorative sheet which laminated | stacked the antistatic layer and the surface protective layer at least in this order on the base material sheet | seat consisting of an olefin resin was considered. (Patent Document 3)

  However, even in these configurations, the adhesion of dust has not been suppressed, and furthermore, since it is difficult to wipe off, cleaning is not easy.

JP 06-16832 A JP 10-250013 A Japanese Patent No. 4304016

  The present invention has been made to solve such problems, that is, the subject is a non-vinyl chloride decorative sheet, indoor dust and dust are difficult to adhere, and easy to wipe off, Another object of the present invention is to provide an interior decorative sheet having excellent surface contamination resistance and durability.

  The present invention solves this problem, that is, the invention according to claim 1 is a decorative sheet in which an antistatic layer and a surface protective layer are laminated at least in this order on a base sheet made of an olefin resin. The antistatic layer is made of a urethane curable resin containing 80% by weight or more of a cationic acrylic polymer having a layer thickness of 0.5 to 5 μm, and the surface protective layer is a urethane resin or ionizing radiation curable type having a layer thickness of 5 to 20 μm. An interior decorative sheet comprising an acrylic resin.

  According to the present invention, by limiting the constituent materials and layer thicknesses of the antistatic layer and the surface protective layer according to the first aspect of the present invention, indoor dust and dust are less likely to adhere as compared with the conventional one, and In addition, the surface is excellent in stain resistance and durability, and has the effect of being easy to clean.

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

  Hereinafter, the present invention will be described in detail based on the drawings. FIG. 1 shows a cross-sectional structure of one embodiment of the interior decorative sheet of the present invention. A pattern layer 2 and a transparent resin layer 3 are appropriately provided on the substrate sheet 1, and an antistatic layer 4 and a surface protective layer 5 are provided.

  As the base material sheet 1 in the present invention, one made of an olefin resin is used. A conventional vinyl chloride resin thermoplastic resin should not be used in consideration of environmental problems. Olefin resins are excellent in cost. Olefinic resins are likely to be electrostatically charged, but this point is solved by the present invention.

  The substrate sheet 1 may be a single-layer resin sheet, but may be a plurality of resin sheets. Further, it may be appropriately colored. Furthermore, it is good also as a colored sheet by making a base material sheet 1 contain a coloring pigment etc., and in the case of the multilayer base material sheet 1, each layer is good also as the same resin composition, and it is good also as a different resin composition. Alternatively, a colored concealing layer (not shown) may be provided on any surface of the base sheet 1 by solid printing, and the pattern layer 2 may be provided on the surface side. As the thickness of the base sheet 1, one having a thickness of about 50 to 200 μm is preferably used.

  Examples of the olefin resin include high crystalline non-crystalline materials such as polyethylene (low density, medium density, or high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer. An elastomeric polyolefin resin or the like can be used.

  In the base sheet 1, various known additives such as a colorant, a filler, a flame retardant, a lubricant, an antioxidant, and a light stabilizer (ultraviolet absorber, radical scavenger) are added as necessary. It may be added. Further, in terms of antistatic properties on the surface of the decorative sheet, an antistatic agent may be added to the base sheet 1, although not as much as the antistatic layer 4 described later.

  The pattern layer 2 provided as appropriate may be formed on the surface of the base sheet 1 by printing or the like. As a printing method or a coating method, it can be formed by a known printing method such as gravure printing, silk screen printing, offset printing, letterpress printing, flexographic printing, electrostatic printing, ink jet printing, or transfer printing. When the pattern of the pattern pattern layer 2 is solid all over, it can be formed by a known coating method such as roll coating.

  The pattern of the pattern layer 2 may be, for example, a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, etc. , An abstract pattern, or a solid surface, etc., which can be appropriately combined and is not particularly limited.

  The ink (or) paint used for forming the pattern layer 2 is made of, for example, polyester resin, urethane resin, acrylic resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, cellulose resin, etc. One kind or a mixture of two or more kinds may be used. Among these, urethane resin is suitably used as one of resins preferable in terms of adhesion and the like.

  Examples of the colorant for the ink include known colorants such as titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone yellow. , Hansa Yellow A, Quinacridone Red, Permanent Red 4R, Phthalocyanine Blue, Indanthrene Blue RS, Aniline Black and other organic pigments (or dyes), metallic pigments made of metal powders such as aluminum and brass, titanium dioxide coated mica A pearl luster (pearl) pigment, a fluorescent pigment or the like made of foil powder such as basic lead carbonate is used alone or in combination.

  The transparent resin layer 3 provided as appropriate is provided to give a thickness between the pattern pattern layer 2 and the decorative sheet surface, and may be provided with an uneven pattern as appropriate. As the resin used for the transparent resin layer 3, an olefin resin can be used, and the same type of resin as the olefin resin used in the base sheet 1 can be suitably used. The thickness of the transparent resin layer 3 is preferably about 50 to 200 μm.

  As the antistatic layer 4 in the present invention, a urethane curable resin containing 80% by weight or more of a cationic acrylic polymer known as an antistatic agent is used. Examples of the cationic acrylic polymer include quaternary ammonium salts. Particularly, a polymer type is preferable because it is easy to obtain antistatic properties and physical properties and the like can be easily adjusted. Specifically, “Antistatic Varnish (B26)” manufactured by Tokyo Ink Co., Ltd. and “Elecond” (B-149) (PQ-10) (PQ-50B) manufactured by Soken Chemical Co., Ltd. can be used. The cationic acrylic polymer is added in an amount of 80% by weight or more based on the resin content. If it is less than 80% by weight, sufficient antistatic properties cannot be maintained.

  As a resin used for the antistatic layer, a urethane curable resin capable of obtaining adhesion to the base sheet 1 and a surface protective layer 5 described later is used. As the urethane curable resin, for example, a two-component curable urethane resin can be used, and an acrylic-urethane block copolymer is preferably used as the polyol component. As the two-component curable urethane resin, it is preferable in terms of weather resistance adhesion to use an aliphatic isocyanate or an alicyclic isocyanate as the isocyanate component. As for the acrylic-urethane block copolymer, the isocyanate component in the urethane part is preferably an aliphatic isocyanate or an alicyclic isocyanate in terms of weather resistance.

  In addition, you may use together alicyclic isocyanate and aliphatic isocyanate. As the alicyclic isocyanate, for example, IPDI (isophorone diisocyanate), hydrogenated MDI (hydrogenated diphenylmethane diisocyanate) or the like can be used. As the aliphatic isocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, or the like can be used.

  By the way, the said acrylic-urethane block copolymer is a copolymer containing both the block of an acrylic polymer component and a urethane part. By including the acrylic polymer component, the adhesion between the surface protective layer 5 and the antistatic layer 4 using an ionizing radiation curable resin, specifically, an acrylate ionizing radiation curable resin is improved. Further, by including a urethane portion, the adhesion between the surface protective layer 5 and the antistatic layer 4 when using a two-component curable urethane resin is improved, and in particular, a urethane acrylate ionizing radiation curable resin. The adhesion between the surface protective layer 5 and the antistatic layer 4 is improved.

  Examples of the acrylic-urethane block copolymer include (A) a hydroxyl group-containing acrylic polymer portion containing an acrylic monomer in the main chain and having a hydroxyl group at the terminal or side chain, and (B) a polyester urethane. A polymer component or / and a polyether urethane polymer component, (C) a diisocyanate, a three-component reaction product, reacting these three components to produce a prepolymer, Those obtained by reacting a chain extender such as diamine to extend the chain can be preferably used.

  The polyester urethane polymer component and the polyether urethane polymer component (B) may be used alone or in combination. The polyester-based urethane polymer component includes (1) adding a diamine compound to the polyester polyol component to urea a part of the urethane skeleton, (2) introducing a phenyl group into the polyester polyol component, (3) alcohol A polymer made by adding a diamine compound to a polyester polyol component having a polycarbonate component as a component to urea a part of the urethane skeleton can be used.

  In addition, although the ratio of the acrylic polymer component of the acrylic-urethane block copolymer and the urethane polymer component may be adjusted as appropriate, 40/60 to 60/40 in terms of mass ratio is a good adhesion performance. preferable.

  Moreover, a thermoplastic urethane resin can also be used as a urethane polymer component. The thermoplastic urethane resin is typically a resin obtained by reacting a diisocyanate, a high molecular polyol, and a low molecular polyfunctional active hydrogen compound such as a low molecular diol if necessary.

  Examples of the diisocyanate include (1) aromatic diisocyanate [for example, 4,4′-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate, 1,5-naphthalene diisocyanate, n-isocyanate phenylsulfonyl isocyanate, m -Or p-isocyanate phenylsulfonyl isocyanate, etc.], (2) aliphatic diisocyanate [eg, 1,6-hexamethylene diisocyanate, etc.], (3) alicyclic diisocyanate [eg, isophorone diisocyanate (IPDI), hydrogenated xylylene diene Isocyanate, hydrogenated diphenylmethane diisocyanate, etc.]. Alternatively, there are multimers or adducts of these diisocyanates. These diisocyanates may be used in combination of two or more species.

  Moreover, as said polymer polyol (a polymer here is a counter word with respect to a low molecular polyfunctional active hydrogen compound, molecular weight is less than 10,000), they are polyester polyol, polyether polyol, etc., alone or 2 types or more Used mixed. In terms of weather resistance adhesion, polyester polyol is preferable to polyether polyol.

  Examples of the polyester polyol include a condensed polyester diol obtained by reacting a low molecular diol and a dicarboxylic acid, a polylactone diol obtained by ring-opening polymerization of a lactone, a polycarbonate diol, and the like.

  Examples of the low molecular diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, or a cyclic group. Examples of low molecular weight diols having bis (hydroxymethyl) cyclohexane, m or p-xylene glycol, bis (hydroxymethyl) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4-bis (2- Hydroxyethoxy) -diphenylpropane (ethylene oxide adduct of bisphenol A) or the like may be used alone or in combination of two or more.

  Examples of the dicarboxylic acid include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, maleic acid and fumaric acid, and aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid. Used or two or more types. Moreover, (epsilon) -caprolactone etc. are used for the said lactone.

  Specific examples of the polyester polyol include polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, polyethylene butylene adipate, polybutylene hexabutylene adipate, polydiethylene adipate, poly (polytetramethylene ether) Examples include adipate, polyethylene azate, polyethylene sebacate, polybutylene azate, polybutylene sebacate, polyhexamethylene carbonate diol, and the like. These may be used alone or in combination of two or more.

  The antistatic layer 4 may be formed on the base sheet 1 by a conventionally known coating method such as roll coating. At that time, the surface on which the antistatic layer 4 is formed may be appropriately subjected to surface easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment or the like as necessary. The thickness of the antistatic layer is 0.5 to 5 μm. If it is thinner than 0.5 μm, an antistatic function cannot be obtained, and if it is thicker than 5 μm, various surface resistances are lowered.

  As the surface protective layer 5 in the present invention, a layer made of urethane resin or ionizing radiation curable acrylic resin having a layer thickness of 5 to 20 μm is used. As the urethane resin, those similar to those used for the antistatic layer 4 can be used, and as the ionizing radiation curable acrylic resin, acrylate-based and urethane acrylate-based ionizing radiation curable resins can be used.

  The surface protective layer 5 is applied on the surface on which the antistatic layer is formed by a known coating method such as gravure coating or roll coating using a coating liquid made of a curable resin, and then cured by curing the resin. It can be formed by making things. The surface protective layer is usually transparent (non-colored transparent, colored transparent, translucent) so that the pattern layer 3 can be seen through. The layer thickness of the surface protective layer 5 is 5 to 20 μm. If it is thinner than 5 μm, the stain resistance and various surface resistances cannot be obtained, and if it is thicker than 20 μm, the antistatic function deteriorates.

  A colored polyolefin resin sheet (manufactured by Riken Technos Co., Ltd .: “PP sheet”) having a thickness of 70 μm was used as the base sheet 1 and subjected to corona discharge treatment on one side, and then colored ink (manufactured by Toyo Ink Co., Ltd .: “ The grain pattern was applied by gravure printing using “Lamistor”) to form the pattern layer 2. Next, a transparent polyolefin resin sheet having a thickness of 80 μm (manufactured by Riken Technos Co., Ltd .: “PP Clear”) is pasted on the pattern layer 2 via an adhesive (manufactured by Toyo Morton Co., Ltd .: “TM Series”). In addition, after corona discharge treatment on the surface, urethane resin (DIC Graphics Co., Ltd .: “W480”) containing 80% by weight of a cationic acrylic polymer (Tokyo Ink Co., Ltd .: “LG Coat”). ) Is applied to the coating thickness after drying to be 0.5 μm to form the antistatic layer 4, and finally urethane resin (manufactured by DIC Graphics: “W480”) is applied at the coating thickness after drying. It applied so that it might be set to 10 micrometers, and the decorative sheet for interiors was obtained as the surface protective layer 5. FIG.

  An interior decorative sheet was obtained in the same manner as in Example 1 except that the antistatic layer was 3 μm.

  An interior decorative sheet was obtained in the same manner as in Example 2 except that the surface protective layer was 20 μm.

<Comparative Example 1>
An interior decorative sheet was obtained in the same manner as in Example 1 except that the antistatic layer was not provided.

<Comparative example 2>
An interior decorative sheet was obtained in the same manner as in Example 2 except that the surface protective layer was not provided.

<Comparative Example 3>
An interior decorative sheet was obtained in the same manner as in Example 1 except that the antistatic layer was 10 μm.

<Comparative Example 4>
An interior decorative sheet was obtained in the same manner as in Example 2 except that the surface protective layer was 25 μm.

<Comparative Example 5>
An interior decorative sheet was obtained in the same manner as in Example 2 except that the cationic acrylic polymer was changed to 60% by weight.

<Evaluation method>
The physical properties of the decorative sheets obtained in Examples 1 to 3 and Comparative Examples 1 to 5 were evaluated, and the results are shown in Table 1. Each evaluation item was as follows.

<Antistatic performance>
Surface specific resistance: The charging resistance value of the sheet was measured.
Half-life: Charge amount (KV) and half-time (s) were measured with a static Honest meter.
Adhesion of fine PS by electrification: Spherical polystyrene was brought into contact with the surface of the test body in a state where the test body was made vertical after reciprocating the surface of the test body 30 times with rubber gloves.
(○ = almost no adherence △ = 10-50 pieces attached × = a lot attached)

<Contamination resistance>
After drawing a line on the test specimen by JAS stain resistance test (black magic, red crayon, blue ink), the soil was removed with alcohol after 6 hours.
(○ No adhesion △ Slightly dirty × Dirty adhesion)

<Scratch resistance>
The scratched product after the steel wool rubbing test (200 g load × 20 reciprocations) was evaluated.
(○: no scratch △: slightly scratched ×: scratched)

<Durability>
Weather resistance: visually evaluated after 500 hours of sunshine weather meter Humidity resistance: visually evaluated after 500 hours at a temperature of 40 ° C and 90% humidity. Heat resistance: state after 500 hours at a temperature of 60 ° C (○: No change in appearance ×: Change in appearance such as peeling or discoloration)

  The interior decorative sheet of the present invention is used for interiors of buildings and can be used on the surface of furniture, fittings, and the like.

DESCRIPTION OF SYMBOLS 1 ... Base material sheet 2 ... Pattern pattern layer 3 ... Transparent resin layer 4 ... Antistatic layer 5 ... Surface protective layer

Claims (1)

In a decorative sheet formed by laminating an antistatic layer and a surface protective layer at least in this order on a base sheet made of an olefin resin,
The antistatic layer comprises a urethane curable resin containing a cationic acrylic polymer having a layer thickness of 0.5 to 5 μm in an amount of 80% by weight or more,
The decorative sheet for interior use, wherein the surface protective layer is made of urethane resin or ionizing radiation curable acrylic resin having a layer thickness of 5 to 20 μm.