JP5339069B2 - Decorative sheet and decorative material on which it is laminated - Google Patents

Abstract

The invention provides a decoration slice with a solidification type resin layer on the outermost surface, concretely the invention provides a decoration slice with good impact resistance, scratch resistance, alkali resistance, sealing performance with the polishing compound (such as wax, lacquer). The decoration slice comprises a solidification type resin layer composed of the activation energy solidification type resin on the outermost surface and the solidification type resin layer is formed on a thermoplastic resin basis material slice, characterized in that: the solidification type resin layer contains silicon dioxide and the hydrophobic degree of the solidification type resin layer based on methanol titration method is above 40 and below 60.

Description

  The present invention has a curable resin layer composed of an active energy ray-curable resin containing silica on the outermost surface, and has excellent adhesion to a polishing agent (wax, lacquer, etc.), alkali resistance, stain resistance, etc. Regarding the sheet.

  A decorative sheet having a curable resin layer made of an active energy ray curable resin on the outermost surface has excellent physical properties such as abrasion resistance, impact resistance, contamination resistance, and scratch resistance. It is suitably used as a decorative sheet for use. Here, the curable resin layer appropriately contains a prepolymer, an oligomer and / or a monomer containing a radically polymerizable double bond capable of undergoing a polymerization crosslinking reaction by irradiation with active energy rays such as ultraviolet rays and electron beams. It is. Such a decorative sheet is disclosed in Patent Documents 1 and 2, for example.

  The active energy ray-curable resin layer formed on the outermost surface may contain silica for the purpose of matting effect. In addition, the active energy ray curable resin layer is excellent in physical properties such as abrasion resistance and scratch resistance as it is, but in consideration of transportation of the decorative sheet, the wear resistance and scratch resistance are further considered. In order to improve this, there are cases where specific spherical particles (such as silica) are contained. Such a decorative sheet is disclosed in Patent Document 3, for example.

  However, when untreated silica is added to the active energy ray-curable resin layer as in Patent Document 3, there is a problem that alkali resistance is lowered. Specifically, whitening is a problem when a detergent, medicine, or the like containing an alkaline component comes into contact.

  Therefore, the curable resin layer has excellent wear resistance and scratch resistance, satisfies alkali resistance, and considers maintenance such as coating a polishing agent (wax, lacquer, etc.) on the surface. There is room for further improvement so that the performance of adhesion such as a polish can be satisfied.

JP 2001-260282 A JP 2003-276133 A JP-A-2005-313600

  The present invention provides a decorative sheet having a curable resin layer on the outermost surface, which is excellent in abrasion resistance and scratch resistance, as well as in alkali resistance and adhesion such as a polishing agent. The purpose is that.

As a result of intensive studies, the present inventor has found that the object can be achieved when the curable resin layer contains silica having specific physical properties, and has completed the present invention.
That is, the present invention relates to the following decorative sheet and a decorative material on which the decorative sheet is laminated.
1. A decorative sheet in which a curable resin layer made of an active energy ray-curable resin is formed on an outermost surface on a thermoplastic resin base sheet, the curable resin layer comprising a bifunctional urethane (meth) acrylate oligomer and A silica containing a cured product layer composed of a mixture containing an aliphatic urethane (meth) acrylate oligomer having 3 to 15 radically polymerizable unsaturated groups in one molecule and treated with a silicone oil; Has a hydrophobization degree of 40 or more and 60 or less by a methanol titration method , has alkali resistance and is excellent in adhesion to a polishing agent coated on the surface as a maintenance after making a cosmetic material .
2. The weight ratio of the bifunctional urethane (meth) acrylate oligomer to the aliphatic urethane (meth) acrylate oligomer is the bifunctional urethane (meth) acrylate oligomer / the aliphatic urethane (meth) acrylate oligomer = 80 parts by weight / The makeup according to claim 1, wherein the amount of the silica is 20 to 65 parts by weight / 35 parts by weight, and the content of the silica is 8 to 20 parts by weight with respect to 100 parts by weight of the curable resin composition. Sheet .
3. The decorative sheet according to any one of claims 1 and 2, wherein the bifunctional urethane (meth) acrylate oligomer has a weight average molecular weight of 1000 to 4000 .
4). The decorative sheet according to any one of claims 1 to 3, wherein the thermoplastic resin base sheet is made of a polyolefin resin sheet .
5). A decorative material obtained by laminating the decorative sheet according to any one of claims 1 to 4 on an adherend such that the curable resin layer is an outermost surface layer .

  The decorative sheet of the present invention is excellent in abrasion resistance and scratch resistance as well as being polished by optimizing the hydrophobicity of silica contained in the curable resin layer made of the outermost active energy ray curable resin. Whitening can be prevented or suppressed even when an alkaline cleaning agent, chemical or the like comes into contact with the surface of the decorative sheet while maintaining the adhesion of the agent (wax, lacquer, etc.)

It is sectional drawing which shows an example of the decorative sheet concerning this invention. It is sectional drawing which shows an example of the decorative sheet concerning this invention. It is sectional drawing which shows an example of the cosmetics concerning this invention.

  Hereinafter, the decorative sheet of the present invention will be described in detail.

The decorative sheet of the present invention is a decorative sheet in which an active energy ray-curable resin layer is formed on the outermost surface of a thermoplastic resin substrate sheet made of polyolefin resin or the like, as shown in FIG. The mold resin layer contains silica, and the silica contains silica having a degree of hydrophobicity of 40 or more and 60 or less by methanol titration.

  A decorative sheet 1 illustrated in FIG. 1 is obtained by providing a primer layer 4 on the surface of a thermoplastic resin base sheet 2 and laminating an active energy ray-curable resin layer 3. In addition, the pattern printing layer 6 and the solid printing layer 7 are printed on the back side of the thermoplastic resin base sheet 2 via the back side primer layer 5. This embodiment is a so-called “back printed sheet” type decorative sheet.

  FIG. 2 shows another example of the decorative sheet of the present invention. The decorative sheet shown in FIG. 2 is provided with a primer layer 8 on the surface of a thermoplastic resin base material sheet 22, and a solid printing layer 7 and a pattern printing layer 6 are formed by printing. The resin sheet 21 is laminated, the primer layer 4 is provided on the surface, and the active energy ray curable resin layer 3 is formed. This embodiment is a so-called “doubling sheet” type decorative sheet. As the thermoplastic resin base sheet 22, a colored resin sheet is generally used, but an uncolored sheet may be used.

  As another aspect, the pattern printing layer is formed on the thermoplastic resin base material sheet 22, and also the aspect which laminates | stacks a transparent adhesive layer, a transparent resin layer, and a curable resin layer on it further is mentioned. In this embodiment, if necessary, a primer layer may be further provided on the front and back of the thermoplastic resin base sheet 22, and a primer layer may be further provided between the transparent resin layer and the curable resin layer. .

-Curable resin layer The decorative sheet of the present invention is provided with an active energy ray-curable resin layer containing silica having the above specific physical properties as a curable resin layer on the outermost surface, thereby providing abrasion resistance and scratch resistance. In addition to excellent properties, the alkali resistance and adhesion of polishing agents (wax, lacquer, etc.) are also excellent.

  The curable resin layer comprises a urethane (meth) acrylate oligomer (A) having a weight average molecular weight of 1000 to 4000 having two radical polymerizable unsaturated groups in one molecule, and 3 to 15 radicals in one molecule. It is a hardened | cured material layer which consists of a mixture containing the aliphatic urethane (meth) acrylate oligomer (B) which has a polymerizable unsaturated group.

  The urethane (meth) acrylate oligomer (A) used in the curable resin layer is a so-called bifunctional urethane acrylate oligomer having two radical polymerizable unsaturated groups in one molecule, and is composed of diisocyanate and one molecule. A weight average molecular weight of 1000, which is formed by bonding a polyhydric alcohol having two or more hydroxyl groups and having a weight average molecular weight of 500 to 2000 and a (meth) acrylate compound having a hydroxyl group at the terminal and a radically polymerizable unsaturated group. ~ 4000 oligomers.

  If the weight average molecular weight of the urethane (meth) acrylate oligomer (A) is less than 1000, the flexibility of the urethane (meth) acrylate in the cured resin layer cannot be fully exhibited, and bending workability such as V-cut processing and lapping processing is not possible. And embossability is reduced. On the other hand, when the weight average molecular weight exceeds 4000, the characteristics such as contamination resistance deteriorate.

  The diisocyanate is an aliphatic, alicyclic or aromatic isocyanate having two or more isocyanate groups in one molecule. For example, 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,6 -Hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like.

  Examples of the polyhydric alcohol having a weight average molecular weight of 500 to 2000 include polyester polyol, polyether polyol, polycarbonate polyol, and acrylic polyol having hydroxyl groups at both ends. Examples of the polyester polyol include (a) an addition reaction product of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or a derivative thereof or an epoxy compound, and (b) a condensation product of a polybasic acid and an alkylene glycol. And (c) a ring-opening polyester compound derived from a cyclic ester compound, and these can be used alone or in admixture of two or more. Examples of the polyether polyol include polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol. The polyester diol having a hydroxyl group at both ends having a weight average molecular weight of 500 to 2000 obtained as a condensation product with an alkylene glycol using adipic acid as the polybasic acid (b) above has good physical properties. Preferably used.

  A (meth) acrylate having a hydroxyl group at the terminal and a radically polymerizable unsaturated group is an ester compound of acrylic acid, methacrylic acid or a derivative thereof, and has a hydroxyl group at the terminal. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate (Meth) acrylic acid ester compounds having one polymerizable unsaturated group such as 2-hydroxy-3-phenyloxypropyl acrylate, and (meth) acrylic having two or more polymerizable unsaturated groups in one molecule Examples include acid ester compounds.

  In the urethane (meth) acrylate oligomer (A), preferably, the polyhydric alcohol component is a polyester polyol having a weight average molecular weight of 500 to 2000 formed from alkylene glycol and adipic acid, and the diisocyanate component is isophorone diisocyanate. An oligomer having a weight average molecular weight of 1000 to 3000, which is obtained by reacting (polyaddition reaction) these components with hydroxyethyl (meth) acrylate as a component, is desirable.

  The aliphatic urethane (meth) acrylate oligomer (B) used in the curable resin layer has a radically polymerizable unsaturated group such as 3 to 15 (meth) acryloyl groups in one molecule, It is a polyfunctional (3-15 functional) urethane acrylate obtained by reacting an aliphatic diisocyanate, a polyfunctional polyol, and a (meth) acrylate having a hydroxyl group at the terminal and a radically polymerizable unsaturated group.

Examples of the aliphatic diisocyanate include 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.
The (meth) acrylate having a hydroxyl group and a radically polymerizable unsaturated group is 2-hydroxyethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy. Examples thereof include (meth) acrylic acid ester compounds having one polymerizable unsaturated group such as cyclohexyl (meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, 2-hydroxy-3-phenyloxypropyl acrylate and the like.

  Specifically, the aliphatic urethane (meth) acrylate oligomer (B) is a commercially available product such as UA-306H (hexafunctional aliphatic urethane acrylate manufactured by Kyoeisha Chemical), U-15HA (15 functional urethane manufactured by Shin-Nakamura Chemical Co., Ltd.). Acrylate oligomer), purple light UV7550 (trifunctional aliphatic urethane acrylate manufactured by Nippon Synthetic Chemical), and the like are available.

  The curable resin layer includes silica having a hydrophobization degree of 40 or more and 60 or less by the methanol titration method together with the active energy ray curable resin. When the degree of hydrophobicity is less than 40, the alkali resistance is not improved, and when the degree of hydrophobicity exceeds 60, the adhesion of a polishing agent or the like (wax, lacquer, etc.) decreases. By including silica having such a specific value of hydrophobicity, it is excellent in abrasion resistance and scratch resistance and has both alkali resistance and adhesion of a polishing agent (wax, lacquer, etc.). Characteristics can be improved. The content of silica having a degree of hydrophobicity of 40 or more and 60 or less by the methanol titration method is not particularly limited, but is 0.1 to 50 parts by weight with respect to 100 parts by weight of the total amount of oligomer (A) and oligomer (B), Preferably it is about 5-30 weight part.

  A method for obtaining silica having a hydrophobization degree of 40 or more and 60 or less by the methanol titration method is a cleaning agent or chemical agent containing an alkali component on the silica surface while maintaining the adhesion of a polishing agent (wax, lacquer, etc.). Even when is attached, there is no limitation as long as it is a method capable of preventing or suppressing silica modification. For example, a method of reacting polysiloxane with silica in the presence of amines and water under heating and pressure, performing a drying treatment, and covering at least a part of the silica surface with silicon oil (so-called silicone oil treatment), Hydrophobing by adsorbing silane coupling agents, glycol-based processing agents, and other hydrocarbon-based processing agents (including processing agents used for wax processing) to at least some of the silanol groups present on the surface of the treated silica And the like. These methods can be used alone or in combination of two or more.

The measurement of the degree of hydrophobicity will be described below.
0.2 g of inorganic oxide for measuring the degree of hydrophobicity is added to a glass container having an inner diameter of 7 cm and a capacity of 2 L or more containing 100 ml of ion-exchanged water, and stirred with a magnetic stirrer. The tip of a burette containing methanol is put into the liquid, 20 ml of methanol is added dropwise with stirring, stirring is stopped after 30 seconds, and the state after 1 minute from stirring is observed. Repeat this operation. When the total amount of methanol added when the inorganic oxide does not float on the water surface 1 minute after the stirring is stopped is Y (ml), the value obtained by the following formula is calculated as the degree of hydrophobicity. The water temperature in the beaker (glass container) is adjusted to 20 ° C. ± 1 ° C. and the measurement is performed.
Hydrophobicity = [Y / (100 + Y)] × 100]

The average particle diameter of silica is not particularly limited, and can be appropriately set according to the use of silica, the thickness of the curable resin layer, and the like. Usually, the average particle diameter (by the laser diffraction method) can be set from 1 to 30 μm depending on the thickness of the curable resin layer. Among them, when the decorative sheet is used for flooring, about 1 to 25 μm is preferable, and about 1 to 15 μm is more preferable.
The BET specific surface area is preferably about 50 to 500 m ² / g, about 100 to 400 m ² / g is more preferable.

  In addition to the silica, for the purpose of further improving matting and scratch resistance, inorganic particles such as α-alumina, silica, chromium oxide, iron oxide and diamond, and synthetic resin beads such as crosslinked acrylic A powder having an average particle size of about 1 μm to 30 μm, such as organic resin particles, may be added. Various particle shapes of these powders are used. Particularly, when using a spherical shape or a similar shape to a spherical shape, the scratch resistance is good, the coating suitability is good, and the touch feeling is not rough. preferable. The addition amount of the powder is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the oligomer (A) and the oligomer (B).

  A lubricant can be added to the curable resin layer in order to improve surface slippage. Examples of the lubricant include polyethylene wax, tetrafluoroethylene resin powder, metal soaps, plastic beads, and silicone oil. The addition amount of the lubricant is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total amount of the oligomer (A) and the oligomer (B).

  Further, in order to improve the weather resistance, it is preferable to add an ultraviolet absorber such as benzotriazole, benzophenone, salicylate, or triazine to the curable resin layer. When adding an ultraviolet absorber, an electron beam is irradiated and a resin layer is hardened. Further, when the resin layer is cured by irradiating with ultraviolet rays, as photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-amino oxime ester, tetramethylthiuram monosulfide, thioxanthones, aromatic As photopolymerization accelerators (sensitizers) such as diazonium salts, aromatic sulfonium salts, metallocenes, n-butylamine, triethylamine, tri-n-butylphosphine and the like are used.

  An antibacterial agent may be added to the curable resin layer in order to impart antibacterial properties. Antibacterial agents include inorganic antibacterial agents and organic antibacterial agents. In particular, inorganic antibacterial agents are desirable because they are generally safer than organic antibacterial agents and are excellent in durability and heat resistance. Inorganic antibacterial agents are those in which antibacterial metals such as silver, copper and zinc are supported on various inorganic carriers. The addition amount of the antibacterial agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the oligomer (A) and the oligomer (B).

  The curable resin layer is coated with a coating composition containing each of the above components by an appropriate means, and is cured by irradiation with an active energy ray such as an electron beam or ultraviolet ray. In this coating composition, various additives such as colorants such as solvents, dyes and pigments, fillers such as gloss adjusters and extenders, antifoaming agents, leveling agents, and thixotropy imparting agents as necessary. Can be added.

The irradiation amount of an electron beam is usually 100 to 1000 keV, preferably 100 to 300 keV. The electron beam is irradiated at an irradiation amount of about 0.1 to 30 Mrad. When the irradiation amount is less than 0.1 Mrad, curing may be insufficient, and when the irradiation amount exceeds 30 Mrad, the cured coating film or the substrate may be damaged. Moreover, the irradiation dose in the case of curing with ultraviolet rays is preferably 50 to 1000 mJ / cm ² . If the irradiation amount of ultraviolet rays is less than 50 mJ / cm ² , curing may be insufficient, and if the irradiation amount exceeds 1000 mJ / cm ² , the cured coating film may change yellow.

  The active energy ray irradiation device used to cure the curable resin layer is a cockroft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type when irradiating an electron beam. Various electron beam accelerators such as a high-frequency type are used, and when irradiating ultraviolet rays, a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a black light lamp, or a metal halide lamp is used.

  As the above-mentioned solvent, those usually used for paints, inks and the like can be used. Specific examples include aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, acetic acid Examples thereof include acetates such as ethyl, isopropyl acetate and amyl acetate, alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, ethers such as dioxane, tetrahydrofuran and diisopropyl ether, and mixtures of two or more thereof.

  The method for forming a layer of the coating composition is 1) a direct coating method in which the coating composition is directly coated, or 2) a resin layer is formed in advance on the surface of the peelable substrate, and then the layer is transferred. A transfer coating method or the like is used.

  The direct coating method of 1) above includes gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheeler coating, dip coating, silk screen solid coating, wire bar coating, flow coating, A comma coat, a flow coat, a brush coat, a spray coat or the like can be used, but a gravure coat is preferred.

  The transfer coating method 2) is a method in which after a coating film is once formed on a thin sheet (film), the coating film is crosslinked and cured, and then the cured coating film is transferred to a desired site. In addition, as a means for forming the curable resin layer on a thin sheet, the same various coating means as in the direct coating method can be used. The following (a) to (c) can be used as the transfer coating method.

(A) Injection molding simultaneous transfer method as disclosed in JP-B-2-42080, JP-B-4-19924 and the like. Alternatively, an injection molding simultaneous laminating method as disclosed in Japanese Patent Publication No. 50-19132.
(B) A vacuum forming simultaneous transfer method as disclosed in JP-A-4-288214 and JP-A-5-57786. Alternatively, a vacuum forming simultaneous laminating method as disclosed in Japanese Patent Publication No. 56-45768.
(C) A lapping simultaneous transfer method or a lapping simultaneous laminating method as disclosed in JP-B-59-51900, JP-B-61-5895, JP-B-3-2666, and the like.

  The thickness of the curable resin layer is not particularly limited and can be appropriately set, but is usually about 1 to 30 μm, and particularly preferably about 5 to 25 μm.

-As a resin that constitutes thermoplastic resin base sheet, transparent thermoplastic resin sheet thermoplastic resin base sheet, transparent thermoplastic resin sheet, etc., because it has excellent processability and does not generate harmful gas during combustion, etc. Polyolefin thermoplastic resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyarylate, and other thermoplastic ester resins, polymethyl methacrylate, polymethacrylate, Acrylic thermoplastic resins such as polyethyl acrylate and polybutyl acrylate, polyamide thermoplastic resins such as nylon-6 and nylon-66, polyimide, polyurethane, polystyrene, acrylonitrile-butadiene-styrene resin, etc. , And the like non-halogen type thermoplastic resin. These thermoplastic resins may be used alone or as a mixture of two or more. However, suitability for providing a pattern printing layer or a concave pattern as a design, and combustion that has become a problem in recent years. A polyolefin resin sheet is preferably used in view of the fact that sometimes no harmful gas is generated or the cost is comprehensively considered.

  The polyolefin resin is not limited. For example, polyethylene (low density, high density), polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer. , Ethylene-propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyolefin-based thermoplastic elastomer, and the like. Among these, polypropylene, ethylene-propylene-butene copolymer, polyolefin-based thermoplastic elastomer and the like are particularly preferable.

  Homopolypropylene as a main component or a copolymer is also preferable, and examples thereof include homopolypropylene resins, random polypropylene resins, block polypropylene resins, and α-olefins having 2 to 20 carbon atoms other than propylene having a polypropylene crystal part. In addition, a propylene-α-olefin copolymer containing 15 mol% or more of a comonomer of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 is also preferable.

  The above-mentioned polyolefin-based thermoplastic elastomer is composed of either 1) high-density polyethylene or polypropylene whose main raw material is a hard segment, and an elastomer and an inorganic filler as a soft segment added thereto. A mixture of isotactic polypropylene, which is a hard segment, and atactic polypropylene, which is a soft segment, described in JP-A-6-23278; 3) JP-A-9-1111055 and JP-A-5-77371; A typical one is an ethylene-propylene-butene copolymer described in, for example, Kaihei 7-316358.

  The thermoplastic resin base sheet, the resin constituting the transparent thermoplastic resin sheet, etc. are formed into a film by a conventional method such as a calendar method, an inflation method, a T-die extrusion method, etc. And a thermoplastic resin sheet can be obtained. In addition, when using a composition to which a colorant, an inorganic filler, or both are added as a thermoplastic resin, and forming a film by the melt extrusion method, if the film is formed into a thin film, the film-forming suitability is lowered, and the surface is finished smoothly. Absent. Generally, this tendency is conspicuous when a total of about 10 parts by weight or more of a coloring agent is added to form a film having a thickness of 80 μm or less. Therefore, in such a case, it is preferable to perform three-layer extrusion, add a colorant only to the center layer, and add no pigment or the like to the outermost layers on the front and back sides.

  The thermoplastic resin base sheet and the transparent thermoplastic resin sheet may be in an unstretched state or a stretched state in a uniaxial or biaxial direction. In the case of a transparent thermoplastic resin, an unstretched sheet is better in formability such as V-cut processing. Moreover, it may be in a state where two or more layers are laminated, and various configurations can be taken as appropriate. Although thickness is not specifically limited, Although it can set according to a product characteristic, it is about 5-300 micrometers normally.

  An additive may be mix | blended with a thermoplastic resin base material sheet and a transparent thermoplastic resin sheet as needed. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, ultraviolet absorbers, light stabilizers, antioxidants, lubricants, foaming agents, and coloring agents (see below). It is done. The blending amount of the additive can be appropriately set according to the product characteristics.

  It does not specifically limit as a coloring agent, Well-known coloring agents, such as a pigment and dye, can be used. For example, inorganic pigments such as titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black; isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene Organic pigments (including dyes) such as blue RS and aniline black; metal pigments such as aluminum and brass; pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. The coloring mode of the base sheet includes transparent coloring and opaque coloring (hiding coloring), and these can be arbitrarily selected. For example, in the case of imparting a color concealing action of an adherend (a base material for a decorative material such as lauan) to a thermoplastic resin base sheet, opaque coloring may be selected. On the other hand, in order to make the ground pattern of the adherend visible, transparent coloring may be selected.

One or both sides of the thermoplastic resin substrate sheet and the transparent thermoplastic resin sheet are subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, as necessary. May be. For example, when the corona discharge treatment is performed, the surface tension of the substrate sheet surface may be 30 dyne or more, preferably 40 dyne or more. The surface treatment may be performed according to a conventional method for each treatment.
By performing such easy adhesion treatment, functional groups containing active hydrogen atoms such as hydroxyl groups and carboxyl groups can be generated on the surface of the thermoplastic resin sheet. In the case where a polyolefin resin sheet is formed by melt extrusion, a certain amount of these polar functional groups are generated on the surface during film formation. Therefore, if the polar functional group generated at the time of film formation is sufficient, the easy adhesion treatment may be omitted.

  A primer layer may be provided on one side or both sides of the thermoplastic resin base sheet and the transparent thermoplastic resin sheet, if necessary. If a primer layer is formed, interlayer adhesion with an adjacent layer can be increased. A primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of a base material sheet.

Adhesive Layer In the case of the decorative sheet shown in FIG. 2, the transparent thermoplastic resin sheet 21 can be laminated on the thermoplastic resin base sheet 22 via the adhesive layer 9. It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet.

Examples of the adhesive known in the field of decorative sheets include thermoplastic resins such as polyamide resin, acrylic resin and vinyl acetate resin, and curable resins such as thermosetting urethane resin. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied. Although the thickness of an adhesive bond layer is not specifically limited, Usually, it is about 0.1-30 micrometers.
In addition to the above method, a method in which a transparent thermoplastic resin sheet 21 made of a polyolefin-based resin is melt extrusion coated (exclusion coating) on a thermoplastic resin base sheet and laminated at the same time as sheet formation is used. May be.

Primer layer The primer layer 4 is a layer for laminating a curable resin layer on a thermoplastic resin sheet with good adhesion. As the primer layer, a solution of vinyl chloride-vinyl acetate copolymer, acrylic resin, polyester resin, polyurethane resin (two-component curing type consisting of an isocyanate curing agent and various polyols), chlorinated polypropylene, chlorinated polyethylene, etc. is applied. Formed. A two-component curable polyurethane resin is preferred because the adhesion between both layers is enhanced, and the weather resistance is enhanced and the adhesiveness hardly decreases with time. Moreover, even if embossing is performed on the curable resin layer after the curable resin layer is formed, there is an advantage that the curable resin layer is hardly peeled off.

  The two-component curable polyurethane resin used for the primer layer 4 is preferably a two-component curable urethane resin having an acrylic-urethane block copolymer as a main component and isocyanate as a curing agent. The acrylic-urethane block copolymer is preferably a polymer in which the isocyanate component in the urethane portion is an aliphatic isocyanate and / or an alicyclic isocyanate. Moreover, aliphatic isocyanate and / or alicyclic isocyanate are also used as isocyanate as a curing agent.

  Adhesiveness with a curable resin layer made of urethane acrylate-based active energy curable resin can be obtained by using a polymer containing both acrylic and urethane blocks, called acrylic-urethane block copolymer, as the main agent. Get better. In addition, for the isocyanate component used in the urethane portion, an aliphatic or alicyclic isocyanate is used, and for the isocyanate of the curing agent, an aliphatic or alicyclic isocyanate is used so that the isocyanate itself is resistant. Since it is excellent in hydrolyzability, heat resistance, etc., the weather resistance of the primer layer itself is improved. Therefore, the weather resistance of the effect of improving the adhesion between the thermoplastic resin sheet and the curable resin layer by the primer layer is also obtained, and the deterioration of the adhesion over time can be prevented.

  The acrylic-urethane block copolymer has a chain part (acrylic component) (A) of an acrylic monomer obtained by a polymerization reaction of an acrylic monomer, and a chain of acrylic monomers ( Or a chain by copolymerization with another monomer) may be partially included, but at least a chain portion other than a chain of acrylic monomer (or a chain by copolymerization with another monomer) is included. It is a compound which has a urethane bond containing part (urethane component) (D) obtained by reaction (urethane reaction) with a hydroxyl group containing compound (B) and an isocyanate group containing compound (C).

  The hydroxyl group-containing compound (B) may be a so-called acrylic polyol obtained by utilizing a polymerization reaction of an acrylic monomer, but the physical properties are adjusted by using other polyols (for example, polycarbonate polyol). Thus, a polymer suitable for a wider range of applications can be obtained.

  The acrylic-urethane block copolymer is obtained, for example, by a reaction between a polycarbonate polyurethane (D) obtained by reacting a polycarbonate polyol (B) and a polyisocyanate (C) with an acrylic polyol (A). In addition, it can be obtained by reacting three compounds of acrylic polyol (A), polycarbonate polyol (B) and polyisocyanate (C).

  As the polyol component constituting the urethane component of the acrylic-urethane block copolymer, polycarbonate polyol, polyester polyol, polyether polyol, etc. may be used, and acrylic polyol may be used in combination therewith. Moreover, as an isocyanate component which comprises this urethane component, what has a weather resistance is preferable. As the isocyanate having weather resistance, alicyclic isocyanate and aliphatic isocyanate are preferable. 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. These are used alone or in combination of two or more.

  The acrylic component of the acrylic-urethane block copolymer includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and octyl (meth) acrylate. , (Meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxy-3-phenoxypropyl and other (meth) acrylic acid ester monomers, two or more of these monomers It is a chain part of an acrylic monomer such as a prepolymer composed of a body. In addition, (meth) acrylic acid means acrylic acid or methacrylic acid.

In addition to the resin, the primer layer 4 may contain a filler such as silica fine powder and an additive such as a light stabilizer. The primer layer is formed by applying these compositions and drying and curing as necessary. Specifically, the primer composition is formed by drying (curing) by a method such as gravure or roll coating. The coating amount of the primer layer 4 is preferably 1 to ²⁰ g / m ² (when dried), more preferably 1 to 5 g / m ² (when dried).

  The back surface primer layer 5 of the decorative sheet shown in FIG. 1 improves the adhesion between a thermoplastic resin base sheet 2 such as a polyolefin resin sheet and a printing layer such as a pattern printing layer 6 or a solid printing layer 7. It is preferable to use the same resin as that for the primer layer 4 on the surface side. Moreover, the back surface primer layer 5 can be formed by the same means as the front surface side primer layer 4. Further, the primer layer 8 of the decorative sheet shown in FIG. 2 improves the adhesion between the thermoplastic resin substrate sheet 2 and the printing layer such as the solid printing layer 7, and the transparent thermoplastic resin sheet is made of a polyolefin-based material. When the resin sheet is used, it is preferable to use the same material as that of the primer layer 4 described above. Further, the forming means can be similarly performed.

Embossing, wiping thermoplastic resin base sheet 2 (or transparent thermoplastic resin sheet 21), and the surface of the curable resin layer 3 is provided with a concavo-convex pattern by heating press or hairline processing, The concavo-convex pattern may be subjected to a wiping process, and the concave portion may be filled with wiping ink (not shown). The uneven pattern is, for example, a conduit groove, a stone plate surface unevenness (such as a granite cleaved surface), a cloth surface texture, a satin texture, a grain of grain, a hairline, a striated groove, and the like. In order to form the concavo-convex pattern, for example, there are an embossing method by heating and pressing, a hairline processing method, a shaping film method and the like. The embossing method heats and softens the thermoplastic resin substrate sheet 2 (or the transparent thermoplastic resin sheet 21) and the curable resin layer, and pressurizes the surface with an embossed plate to shape the uneven pattern of the embossed plate. Then, it is cooled and fixed, and a known single-wafer type or rotary type embossing machine or the like is used. For example, in the embossing process, the relief printing plate is transferred at a sheet temperature of 120 ° C. to 160 ° C. with a pressure of 10 to 40 kg / cm ^{2 on} the surface of the curable resin layer. Further, as described in Japanese Patent Publication No. 58-14312, the wiping process is performed by applying a colored ink on the concavo-convex pattern, wiping, and filling the concavo-convex pattern with the colored ink. .

  As another embossing and wiping processing method, at least the concave portion of the roll intaglio was filled with a liquid material of the curable resin, and a base sheet was stacked on the roll intaglio, and the curable resin was semi-cured by irradiation with ionizing radiation. After that, the base sheet is peeled off from the roll intaglio, and the curable resin layer having a concavo-convex pattern is transferred onto the base sheet. Alternatively, a method may be used in which colored ink is filled in the recesses and the curable resin layer is cured by reirradiating the semi-cured uneven pattern with ionizing radiation.

・ Pattern print layer, solid print layer The pattern print layer 6 is formed by printing patterns such as wood grain pattern, stone pattern, fabric pattern, crest pattern, geometric figure, character, symbol, line drawing, various abstract patterns, etc. is there. The solid print layer 7 is formed by solid printing with a coloring ink having a concealing property. These print layers may be composed only of the pattern print layer 6, may be composed only of the solid print layer 7, or may be composed of both the pattern print layer and the solid print layer.

  The pattern printing layer 6 and the solid printing layer 7 can be formed by printing or coating using a general pattern printing ink. The ink comprises a binder and a colorant. For example, as a binder, chlorinated polyolefin such as chlorinated polyethylene and chlorinated polypropylene, polyester resin, polyurethane resin (two-component curable urethane resin or thermoplastic urethane resin), A mixture of one or more of acrylic resin, polyvinyl acetate resin, vinyl chloride / vinyl acetate copolymer, cellulose resin and the like is used. Examples of the colorant include titanium white, carbon black, petal, yellow lead, ultramarine, phthalocyanine blue, quinacridone, isoindolinone and other pigments or dyes, aluminum, brass and other metal foil powders, and titanium dioxide-coated mica. What mixed the glitter pigment which consists of foil powders 1 type (s) or 2 or more types is mentioned. The pattern printing layer can be formed into a deep pattern by aligning the positions of the concave and convex patterns and the pattern with the colored ink in the concave portions.

  When the polyolefin resin sheet is used as the substrate sheet, it is preferable to use a polyurethane resin ink or a chlorinated polyolefin resin ink as the ink for the pattern printing layer. Moreover, you may form from a metal thin film besides printing and forming as a pattern printing layer and a solid printing layer. For example, a metal thin film is formed by a method such as vacuum deposition or sputtering using a metal such as aluminum, chromium, gold, silver, or copper. The metal thin film may be formed as a solid pattern, a solid pattern, or a pattern such as a pattern, or may be combined with the pattern printing layer and the solid printing layer.

  Examples of the printing method used for forming the pattern printing layer 6 include a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an inkjet printing method. When forming a solid pattern printing layer, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating Various coating methods such as a coating method may be mentioned. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used or combined with other forming methods. Good.

The decorative sheet formed in this way is, for example, an adhesive layer with the solid printing layer side of the decorative sheet shown in FIG. 1 and the thermoplastic resin base sheet side of the decorative sheet shown in FIG. 10 and the like can be applied to form a decorative material. A decorative material using the decorative sheet shown in FIG. 2 is shown in FIG.

  The material of the adhesive layer 10 is appropriately selected depending on another base material 11 (hereinafter referred to as an adherend) on which a decorative sheet is pasted. For example, a vinyl chloride-vinyl acetate copolymer system having a hydroxyl group and a urethane-based adhesive are preferable. When the decorative sheet can be bonded to the adherend by means such as heat fusion, the adhesive layer may be omitted.

  There are no particular limitations on the decorative sheet adherent 11, such as veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF), or other wood material, metal material, plastic material, ceramic material, or the like. It is done. The decorative sheet can be applied to various materials by sticking the decorative sheet to the material and applying a predetermined molding process. For example, interior decorations for buildings such as walls, ceilings, floors, surface decorations for fittings such as window frames, door frames, doors and handrails, surface decorations for furniture such as bags, interior decorations such as automobiles, trains and aircraft Available.

  Although not shown, the decorative sheet 1 of the present invention is described with the adhesive layer 9 on the surface of the solid printed layer 7 shown in FIG. 1 or the surface of the colored sheet 22 made of synthetic resin shown in FIG. It is good also as a decorative sheet which laminated | stacked the backer material through the 2-component curable polyurethane-type adhesive which was made. As the backer material, a resin that does not contain a halogen element in the molecular structure is suitable in consideration of recent environmental problems. For example, polyethylene, polypropylene, ethylene-vinyl alcohol copolymer, polymethylene, polymethylpentene , Polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyarylate, polyethylene naphthalate-isophthalate copolymer, sheet made of resin such as polyimide, polystyrene, polyamide, ABS, crystalline polyethylene terephthalate sheet (so-called C-PET), non- Crystalline polyethylene terephthalate sheet (so-called A-PET), heat-resistant polyalkylene terephthalate sheet [so-called PET-G (trade name) manufactured by Eastman Chemical Company], etc. It can Shimesuru. A suitable thickness of the backer material is about 80 to 500 μm. These sheets may be a single layer or a multilayer. The resin used may be a single resin or a mixture, but a polyester sheet is preferred. Moreover, the said backer material can perform easy adhesion processes, such as a corona discharge process, an ozone process, a plasma process, on the required surface as needed.

Example 1
A decorative sheet for flooring was produced by the following steps.
The average particle size was measured by a laser diffraction method.

Corona discharge treatment was applied to the front and back surfaces of the base sheet made of colored polypropylene resin having a thickness of 60 μm. Thereafter, a solution obtained by dissolving a resin obtained by adding 8 parts by weight of hexamethylene diisocyanate to 100 parts by weight of a polyurethane resin and an acrylic polyol resin on the sheet surface was dissolved in a mixed solvent of methyl ethyl ketone and butyl acetate to obtain a solid content of 2 g / g by gravure printing. By applying to m ² , a 2 μm-thick primer layer for forming a picture print layer was formed. Also, a solution obtained by dissolving a resin obtained by adding 5 parts by weight of hexamethylene diisocyanate to 100 parts by weight of a urethane-based resin and a nitrified cotton resin on the surface opposite to the pattern printing layer of the base sheet in a mixed solvent of methyl ethyl ketone and butyl acetate. Was coated by gravure printing so that the solid content was 2 g / m ² to form a back primer layer having a thickness of 2 μm.

  Gravure printing on the primer layer for pattern print layer formation using a printing ink mainly composed of a two-component curable urethane resin (two-component curable printing ink comprising an acrylic polyol as a main component and an isocyanate as a curing agent). Coating was carried out by the method to form a 2 μm wood grain pattern print layer.

  On the pattern printing layer, a coating solution made of a two-component curable urethane resin was applied to form a transparent adhesive layer having a thickness of 2 μm.

  On the transparent adhesive layer, polypropylene thermoplastic elastomer mainly composed of ethylene-propylene-butene copolymer is heated and melt-extruded with a T-die extruder to form a transparent resin layer with a thickness of 80μm. did.

   On the transparent resin layer, a two-component curable urethane resin coating solution was applied to form a transparent primer layer having a thickness of 2 μm.

From the top of the transparent primer layer of the sheet obtained in the above process, a coating liquid for forming an active energy ray-curable resin layer having the following coating liquid composition (a) has a solid content of 15 g / m ² by gravure coating. Then, coating and drying were performed to form an uncured active energy ray-curable resin. After that, under an atmosphere with an oxygen concentration of 100 ppm, the active resin is cured by irradiating the uncured resin layer with active energy rays under the conditions of an acceleration voltage of 175 kev and an absorbed dose of 5 Mrad (50 kGy), and the active energy ray curing type having a thickness of 15 μm. A resin was formed to produce a decorative sheet for flooring.
[Coating liquid composition of active energy ray-curable resin layer (a)]
-Bifunctional urethane acrylate oligomer 80 parts by weight-UA306H 20 parts by weight-Silica treated with silicone oil (BET value 300 m ² / g, average particle size 12 μm, hydrophobicity 50) 8 parts by weight [Preparation of bifunctional urethane acrylate oligomer and Coating]
Polyester diol (polyester diol consisting of ethylene glycol and adipic acid, manufactured by Asahi Denka Kogyo Co., Ltd .: Adeka New Ace F15-20, weight average) in a reaction vessel equipped with a bifunctional urethane acrylate oligomer synthesis stirrer, temperature controller, and condenser 1000 parts by weight of molecular weight 1000) and 444 parts by weight of isophorone diisocyanate were charged and reacted at 75 ° C. for 10 hours. Next, the reaction solution was cooled to 35 ° C, charged with 400 parts by weight of 2-hydroxyethyl acrylate, 0.5 parts by weight of methoquinone, and 0.2 parts by weight of dibutyltin dilaurate, and reacted at 75 ° C to 85 ° C. . It was made to react until a free isocyanate group became 0.1% or less, and the bifunctional urethane acrylate oligomer of the weight average molecular weight 1700 was obtained.
Example 2
A decorative sheet was prepared in the same manner as in Example 1 except that the following silica was used in place of Example 1 to obtain a decorative sheet for flooring.
Silica treated with silicone oil (BET value 300 m ² / g, average particle size 12 μm, hydrophobicity 60) 8 parts by weight
Example 3
A decorative sheet was prepared in the same manner as in Example 1 except that the following silica was used in place of Example 1 to obtain a decorative sheet for flooring.
Silica treated with silicone oil (BET value 300 m ² / g, average particle size 12 μm, hydrophobicity 40) 8 parts by weight
Example 4
Example 1 except that the active energy ray-curable resin layer coating solution (a) in Example 1 was formed using the following coating solution composition (b) and an active energy ray-curable resin having a thickness of 5 μm was formed. A decorative sheet was prepared in the same manner as described above to obtain a decorative sheet for joinery.
[Coating liquid composition of active energy ray-curable resin layer (b)]
-65 parts by weight of bifunctional urethane acrylate oligomer-35 parts by weight of UA306H-Silica treated with silicone oil (BET value 150 m ² / g, average particle size 6 μm, hydrophobization degree 50) 20 parts by weight
Comparative Example 1
A decorative sheet was prepared in the same manner as in Example 1 except that the following silica was used in place of Example 1 to obtain a decorative sheet for flooring.
Silica treated with silicone oil (BET value 300 m ² / g, average particle size 12 μm, hydrophobicity 30) 8 parts by weight
Comparative Example 2
A decorative sheet was prepared in the same manner as in Example 1 except that the following silica was used in place of Example 1 to obtain a decorative sheet for flooring.
Silica treated with silicone oil (BET value 300 m ² / g, average particle size 12 μm, hydrophobicity 70) 8 parts by weight
Comparative Example 3
A decorative sheet was prepared in the same manner as in Example 4 except that the following silica was used instead of the silica in Example 4 to obtain a decorative sheet for joinery.
Silica treated with silicone oil (BET value 150 m ² / g, average particle size 6 μm, hydrophobicity 30) 20 parts by weight
Comparative Example 4
A decorative sheet was prepared in the same manner as in Example 4 except that the following silica was used instead of the silica in Example 4 to obtain a decorative sheet for joinery.
Silica treated with silicone oil (BET value 150 m ² / g, average particle size 6 μm, hydrophobicity 70) 20 parts by weight
Test example 1
The following evaluation tests were carried out on the decorative sheets of Examples 1 to 4 and Comparative Examples 1 to 4 obtained above. The results are shown in Tables 1 and 2.
[Alkali resistance] A 5% aqueous sodium hydroxide solution was added dropwise and allowed to stand for 24 hours, and then the surface was observed to give ◯ (no whitening), Δ (slightly whitening or gloss change), and x (whitening).
[Wax Adhesion Test] Applying Linley All to the coating surface, curing for 24 hours, and then evaluating cellophane tape adhesion, ○ (no peeling), Δ (50% or less peeling), × (50% or more peeling) It was.
[Lacquer adhesion test] A Lloyd spray made of Lloyd is sprayed on the surface of the coating film, dried for 24 hours, and then subjected to a cellophane tape adhesion test, ○ (no peeling), Δ (50% or less peeling), × (50% or more peeling) ).

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 22 Thermoplastic resin base sheet 3 Curable resin layer 4 8 Primer layer 5 Back surface primer layer 6 Pattern printing layer 7 Solid printing layer 9 Adhesive layer 10 Adhesive layer 11 Adhering material 21 Transparent thermoplastic resin Sheet

Claims (5)

A decorative sheet in which a curable resin layer made of an active energy ray-curable resin is formed on an outermost surface on a thermoplastic resin base sheet, the curable resin layer comprising a bifunctional urethane (meth) acrylate oligomer and A silica containing a cured product layer composed of a mixture containing an aliphatic urethane (meth) acrylate oligomer having 3 to 15 radically polymerizable unsaturated groups in one molecule and treated with a silicone oil; Has a hydrophobization degree of 40 or more and 60 or less by a methanol titration method , has alkali resistance and is excellent in adhesion to a polishing agent coated on the surface as a maintenance after making a cosmetic material . The weight ratio of the bifunctional urethane (meth) acrylate oligomer to the aliphatic urethane (meth) acrylate oligomer is the bifunctional urethane (meth) acrylate oligomer / the aliphatic urethane (meth) acrylate oligomer = 80 parts by weight / The makeup according to claim 1, wherein the amount of the silica is 20 to 65 parts by weight / 35 parts by weight, and the content of the silica is 8 to 20 parts by weight with respect to 100 parts by weight of the curable resin composition. Sheet . The decorative sheet according to any one of claims 1 and 2, wherein the bifunctional urethane (meth) acrylate oligomer has a weight average molecular weight of 1000 to 4000 . The decorative sheet according to any one of claims 1 to 3, wherein the thermoplastic resin base sheet is made of a polyolefin resin sheet . A decorative material obtained by laminating the decorative sheet according to any one of claims 1 to 4 on an adherend such that the curable resin layer is an outermost surface layer .

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