KR100889673B1 - Decorative sheet - Google Patents

Abstract

The present invention effectively provides a cosmetic sheet having excellent rebound performance (pollution resistance) and durability. This invention is a decorative sheet specifically for laminating | stacking and using to a to-be-adhered material, (1) The said sheet has at least a base material sheet, a pattern layer, a transparent resin layer, and a surface protective layer in order, (2) the said surface protective layer A cosmetic sheet is formed by a composition comprising a) an ionizing radiation polymerizable oligomer and b) a reactive silicone acrylate.

Cosmetic sheet, ionizing radiation polymerizable oligomer, reactive silicone acrylate

Description

Makeup sheet {DECORATIVE SHEET}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet engraved with a pattern effective as a surface decorative material for building materials such as furniture and windows, and a decorative plate on which the decorative sheet is laminated.

A decorative sheet is used by sticking to the surface of a to-be-adhered material for the purpose of surface protection, decoration, etc. of to-be-adhered materials, such as a wooden board. And the decorative board obtained by sticking a makeup sheet to a to-be-adhered material is used for various building materials, furniture, etc.

The cosmetic sheet is provided with a surface protective layer to protect the outermost surface. The surface protective layer needs to be excellent in wear resistance, scratch resistance, and the like. The surface protective layer also needs to have stain resistance (antifouling) against contamination from the outside.

As a cosmetic sheet excellent in wear resistance, stain resistance, etc., the synthetic | combination differs from the layer (2) containing a coloring agent, the synthetic resin layer (3), and the said synthetic resin layer (3), for example on one side of the base film (1). There is a makeup sheet formed by laminating the resin layer 4 in this order (Patent Document 1).

In addition, there is also a stain-resistant cosmetic material characterized by a stain-resistant cosmetic material provided with an antifouling layer on the base material, wherein the stain-resistant layer comprises a silicone-modified acrylic urethane resin having an organopolysiloxy group introduced into the side chain of the acrylic urethane resin (patent) Document 2).

Patent Document 1: Japanese Patent Application Laid-Open No. 11-58614

Patent Document 2: Japanese Patent Laid-Open No. 2004-17617

However, the cosmetic sheet of patent document 1 uses the silicone resin, fluorine resin, etc. with low surface tension as a synthetic resin layer of outermost surface. Therefore, there is a problem in terms of durability.

In general, the makeup sheet is stored in a roll or laminated state, but if there are many silicone resins bleeding on the surface of the makeup sheet, the makeup sheet is easily adhered to the back surface of one makeup sheet. In the makeup sheet of Patent Document 1, there is a fear that a relatively large amount of silicone resin is bleeded. If the back surface of the makeup sheet is contaminated with silicone resin, there is a fear that the predetermined adhesiveness may not be obtained when the makeup sheet is adhered to plywood or the like.

The cosmetic sheet of patent document 2 uses a silicone modified resin as an antifouling layer, and obtains stain resistance (especially resistance to contamination by writing instruments, contamination by food, etc.) by bleeding the silicone modified resin on the surface of the makeup sheet. Therefore, similarly to the said patent document 1, the problem by the bleeding of a silicone modified resin arises.

In addition, since the cosmetic sheet of patent document 2 wipes the surface, the silicone modified resin which forms the antifouling layer on the surface is also wiped off simultaneously, and therefore, it is difficult to maintain contamination resistance for a long time.

Therefore, the main objective of this invention is to provide the cosmetic sheet which has the outstanding repulsion performance (pollution resistance) and durability.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in view of the problem of the prior art, this inventor discovered that the said objective can be achieved by using the laminated body which has a specific structure as a makeup sheet, and came to complete this invention.

That is, this invention relates to the following cosmetic sheet.

[1] a cosmetic sheet for laminating onto an adherend,

(1) the sheet has at least a base sheet, a pattern layer, a transparent resin layer and a surface protective layer in order;

(2) the surface protective layer is formed of a composition comprising a) an ionizing radiation polymerizable oligomer and b) a reactive silicone acrylate.

Cosmetic sheet, characterized in that.

[2] the above-mentioned [1], wherein the cosmetic sheet further has a primer layer between the transparent resin layer and the surface protective layer,

(1) the primer layer contains an antistatic agent,

(2) A cosmetic sheet wherein said surface protective layer is formed of a composition comprising a) an ionizing radiation polymerizable oligomer, b) a reactive silicone acrylate and c) spherical particles having an apparent specific gravity of 0.3 to 1 g / cm 3.

[3] The makeup sheet according to the above [2], wherein the spherical particles have a pore capacity of 0.5 ml / g or less.

[4] The cosmetic sheet according to any one of [1] to [3], wherein the surface protective layer contains a mat agent.

[5] The makeup sheet according to any one of [2] to [4], wherein part or all of the spherical particles are silica particles.

[6] The cosmetic sheet according to any one of [1] to [5], wherein the surface protective layer has irregularities by embossing.

[7] The urethane (meth) acrylate oligomer and (B) 1 according to any one of the above [1] to [6], wherein the ionizing radiation polymerizable oligomer has two radically polymerizable unsaturated groups in (A) one molecule. A cosmetic sheet comprising an aliphatic urethane (meth) acrylate oligomer having 3 to 15 radically polymerizable unsaturated groups in a molecule.

[8] The urethane (meth) acrylate oligomer according to any one of [1] to [6], wherein the ionizing radiation polymerizable oligomer has two radically polymerizable unsaturated groups in one molecule of (A). And (B) 60 to 20% by weight of an aliphatic urethane (meth) acrylate oligomer having 3 to 15 radically polymerizable unsaturated groups in one molecule.

[9] The makeup sheet according to any one of [1] to [8], wherein at least one of the transparent resin layer and the base sheet is a polyolefin resin.

[10] A decorative plate, wherein the sheet is laminated on the adherend so that the surface protective layer of the decorative sheet according to any one of [1] to [9] is an outermost surface layer.

Best Mode for Carrying Out the Invention

The makeup sheet of the present invention is a makeup sheet for laminating and using on an adherend,

(1) the sheet has at least a base sheet, a pattern layer, a transparent resin layer and a surface protective layer in order;

(2) The surface protective layer is formed of a composition containing a) an ionizing radiation polymerizable oligomer and b) a reactive silicone acrylate.

Hereinafter, each layer is demonstrated.

Substrate sheet

As the base sheet, for example, paper, a nonwoven fabric, a thermoplastic resin sheet or a composite material thereof is used.

Examples of the paper include thin paper, kraft paper, fine paper, linter paper, baritaji, sulfate paper and Japanese paper.

Moreover, as a nonwoven fabric, the nonwoven fabric containing fiber, such as polyester resin, an acrylic resin, nylon, vinylon, and glass, is mentioned, for example. The basis weight of the paper or nonwoven fabric is usually about 20 to 100 g / m 2. In addition, the paper or nonwoven fabric is added with a resin such as acrylic resin, styrene butadiene rubber, melamine resin, urethane resin, etc., in order to prevent the reinforcement of interlaminar strength between the fibers or other layers and to prevent fluff. The resin may be impregnated after (iii) or may be subjected to electric shock at the time of first evaporation. In addition, the cosmetic sheet which used the paper (or nonwoven fabric) for a base material sheet becomes a toilet paper.

Examples of the thermoplastic resin sheet include acrylic resins, polyester resins, polyolefin resins, polyvinyl chloride resins, polystyrenes, ABS resins, polycarbonate resins, and polyamide resins. Specifically, following (1)-(4) is mentioned.

(1) Polyolefin resins such as polyethylene (high density, medium density and low density), polypropylene (isotactic type and syndiotactic type), polybutene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer and olefin thermoplastic elastomer

As the olefin thermoplastic elastomer, elastomers such as hard segments containing crystalline polyolefin resin, ethylene-propylene rubber, ethylene-propylene-diene rubber, atactic polypropylene, styrene-butadiene rubber and hydrogenated styrene-butadiene rubber Made by mixing the containing soft segments. The mixing ratio of the hard segment and the soft segment is about [soft segment / hard segment] = 5/95 to 40/60 (mass ratio). If necessary, the elastomer component is crosslinked by known crosslinking agents such as sulfur and hydrogen peroxide.

(2) acrylic resins such as polymethyl (meth) acrylate, polybutyl (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, and methyl (meth) acrylate-styrene copolymer [ However, (meth) acrylate means acrylate or methacrylate]

(3) polyester resins such as polyethylene terephthalate, polybutylene terephthalate, ethylene-terephthalate-isophthalate copolymer, polyethylene naphthalate, polyester-based thermoplastic elastomers and amorphous polyesters

Examples of the polyester-based thermoplastic elastomers include aromatic polyesters having high crystallinity and high melting point for hard segments, and amorphous polymers having a glass transition temperature of -70 ° C or less for soft segments. For example, polybutylene terephthalate is used for the highly crystalline and high melting | fusing point aromatic polyester, and polytetramethylene glycol is used for the said amorphous polyether, for example. Typical amorphous polyesters include ethylene glycol-1,4-cyclohexanedimethanol-terephthalic acid copolymers.

(4) other resin

For example, polycarbonate resin, polyvinyl chloride resin, polyamide resin, polyphenylene sulfide, polyether ether ketone, etc. are mentioned.

The base sheet can be used by laminating the above-mentioned paper, nonwoven fabric and thermoplastic resin sheet in a single layer or two or more layers.

Although the thickness (total thickness in the case of a laminated body) of a base material sheet is not limited, Generally, it is about 25-500 micrometers.

Pattern

The patterned layer includes letters, symbols, drawings, and the like, in addition to the patterns of natural materials such as wood grains and wrinkles.

The formation method of a pattern layer, a material, a kind of pattern, etc. are not specifically limited. The pattern layer can be formed by gravure printing, silk screen printing, offset printing, gravure offset printing, inkjet printing, or the like using ink. The pattern includes, for example, wood grain, stone grain, sand grain, cloth texture, tile adhesiveness, brick layered form, skin pattern, letter, symbol, and geometric form. You may combine these shapes 2 or more types.

The ink used for the patterned layer is various additives such as 1) a vehicle containing a binder and the like, 2) colorants such as pigments and dyes, and 3) sieving pigments, stabilizers, plasticizers, catalysts and curing agents suitably added as optional components. It is composed.

As resin of a binder, it can select from a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin suitably according to a requested physical property, printability, etc. For example, Cellulose resins, such as nitrocellulose, cellulose acetate, and a cellulose acetate propionate; Acrylic resins such as poly (methyl) acrylate, poly (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate and hydroxyethyl (meth) acrylate; A single substance such as a urethane resin, vinyl chloride-vinyl acetate copolymer, polyester resin and alkyd resin or a mixture containing them can be used.

Examples of the colorant include inorganic pigments such as titanium white, carbon black, iron black, colcothar, sulfur lead, and ultramarine; Organic pigments such as aniline black, quinacridone red, isoindolinone yellow and phthalocyanine blue; Various dyes can be used in addition to bright pigments such as titanium dioxide coated mica and aluminum.

Adhesive layer

The makeup sheet of the present invention preferably has an adhesive layer between the pattern layer and the transparent resin layer.

An adhesive agent can be suitably selected from a well-known adhesive agent according to the component etc. which comprise a pattern layer or a transparent resin layer. For example, thermosetting resins, such as polyester resin, a polyurethane resin, and an epoxy resin, are mentioned besides polyolefin resin, such as polyethylene and a polypropylene.

In this invention, a urethane type resin adhesive agent is preferable at the point which can raise heat resistance etc. more. Examples of the urethane-based resin adhesive include two-component curable urethane resins having polyols as main agents and isocyanates as crosslinking agents (curing agents).

The polyol has two or more hydroxyl groups in the molecule. For example, polyethylene glycol, polypropylene glycol, acryl polyol, polyester polyol, polyether polyol, polycarbonate polyol and the like are used.

Moreover, as said isocyanate, the polyhydric isocyanate which has two or more isocyanate groups in a molecule | numerator is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate and 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated diisocyanate. Aliphatic (or alicyclic) isocyanates such as phenylmethane diisocyanate are used. Moreover, the adduct or multimer of the said isocyanate can also be used. For example, the adduct of tolylene diisocyanate, the trimer of tolylene diisocyanate, etc. are mentioned.

Moreover, if necessary, well-known easy adhesion | attachment processes, such as corona discharge treatment, a plasma treatment, a degreasing treatment, and a surface roughening process, can also be given to an adhesive surface.

As an adhesion method, it can select according to the kind etc. of adhesive agents to be used. For example, polyolefin-based resins such as polyethylene and polypropylene are used, and a method of coating onto a pattern layer by melt extrusion (extrusion coating method), and thermosetting resins such as polyester-based resins, polyurethane-based resins, and epoxy-based resins. A crosslinking agent such as isocyanate and amine, a polymerization initiator such as methyl ethyl ketone peroxide, hydroperoxide and azabisisobutyronitrile, a polymerization accelerator such as cobalt naphthenate and dimethylaniline, etc. Dry lamination and the like can be used. Moreover, in this invention, a patterned layer and a transparent resin layer can also be laminated | stacked by thermocompression bonding using the adhesive which can be thermally crimped | bonded.

Although the thickness of an adhesive bond layer differs according to the kind of transparency protective layer, the kind of adhesive agent, etc., it is about 0.1-30 micrometers normally.

Transparency resin layer

The transparency resin layer is not limited as long as it is transparent. Thus, it includes all colorless transparent, colored transparent and translucent and the like.

As the transparent resin layer, one formed of a thermoplastic resin is preferable. Specifically, soft, semi-rigid or hard polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester air Copolymer, ionomer, acrylic acid ester, methacrylic acid ester, etc. are mentioned. In this invention, polyolefin resin, such as polypropylene, is especially preferable as a transparency resin layer.

The transparent resin layer may be colored as necessary. A coloring material (pigment or dye) can be added and colored with respect to a thermoplastic resin. As a coloring material, a well-known pigment or dye can be used suitably. These can select 1 type, or 2 or more types. Moreover, the addition amount of a coloring material can also be set suitably according to a desired color tone.

The transparent resin layer may contain various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, radical scavengers, and soft components (for example, rubbers) as necessary. It may be.

The flame retardant is added to impart flame resistance. For example, paraffin chloride, tricresyl phosphate, chlorinated oil, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, tetrabromobisphenol A, dibromopropyl phosphate, tri (2,3-dibromopropyl) phosphate, Antimony oxide, hydrous alumina, barium borate, etc. can be used preferably.

Antioxidants are added to inhibit or prevent oxidative degradation. For example, alkylphenols, amines, quinones, etc. are preferable.

An ultraviolet absorber absorbs the ultraviolet-ray of the wavelength 280-450 nm area | region which causes deterioration of resin (especially polyolefin resin). For example, each ultraviolet absorber, such as a benzophenone system, a salicylate system, a benzotriazole system, and an acrylonitrile system, is mentioned.

The radical scavenger improves weather resistance by preventing discoloration, cracking, whitening and deterioration of strength due to sunlight. As the radical scavenger, in addition to bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, for example, a hindered amine system disclosed in JP-A 4-82625 Radical scavengers, piperidyl radical scavengers, and the like.

The transparent resin layer is laminated with, for example, a method of laminating a preformed sheet or film to an adjacent layer, a method of coating on an adjacent layer by melt extruding a resin composition capable of forming a transparent resin layer, and an adjacent layer. All of the methods can be used. In this invention, it is especially preferable to form a transparency resin layer by melt extrusion. It is preferable that especially a transparency resin layer coats polyolefin resin by melt extrusion.

Specifically, a transparent resin layer can be preferably formed by previously forming an adhesive bond layer on a pattern layer, and melt-extruding and coating a polypropylene thermoplastic elastomer on an adhesive bond layer. As a method of melt extrusion, there is a known method using a T die or the like, for example.

Although the thickness of a transparency resin layer can be suitably set according to the use of a final product, a usage method, etc., it is generally 50-250 micrometers, especially about 20-200 micrometers.

Corona discharge treatment may be performed to the front surface (front surface) and / or back surface of a transparency resin layer as needed in order to improve adhesiveness with an adjacent layer. The method and conditions of corona discharge treatment can be followed by a well-known method.

Primer layer

It is preferable to form a primer layer on the front surface (front surface) and / or rear surface of a transparency resin layer.

Examples of the material for forming the primer layer include resins such as polyester resins, polyurethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, and nitrocellulose resins. In addition, compounds, such as alkyl titanate and ethyleneimine, can also be used. In particular, the use of a two-component curable urethane resin is preferable as the primer layer. When fatty acid isocyanate (aliphatic isocyanate), such as hexamethylene diisocyanate (HMDI), is used as an isocyanate, and an acryl polyol is used as a polyol, respectively, more excellent weather resistance, adhesiveness, etc. are obtained.

A primer layer can be formed according to a well-known printing method, a coating method, etc. using the said material as it is, or in the state dissolving or disperse | distributing to a solvent.

As a primer layer formed between a transparency resin layer and a surface protection layer, it is preferable to contain an antistatic agent. Hereinafter, the primer layer containing such an antistatic agent is demonstrated.

Examples of the antistatic agent include, but are not limited to, cationic, anionic, nonionic, and amphoteric types. Moreover, if it distinguishes according to molecular weight, there exists a high molecular type antistatic agent called antistatic resin which is a polymers, such as a copolymer, in addition to what is called a low molecular type antistatic agent. The antistatic agent is appropriately selected depending on the required physical properties and the use.

Among these antistatic agents, a cationic type is preferable because strong antistatic property is easily obtained. Specifically as a cationic system, a quaternary ammonium salt etc. are mentioned. The polymer type is preferable because the physical properties such as compatibility can be easily adjusted by appropriately selecting the copolymerized monomer, for example, compared to the low molecular type. As the antistatic agent, a cationic polymer type is preferable, and a cationic polymer antistatic agent having a quaternary ammonium salt is preferable.

The addition amount of antistatic agent can be suitably set according to a use, required physical property, the kind of antistatic agent, etc. As addition amount, a polymer type is generally added more compared with a low molecular type. The addition amount of antistatic agent is 30 to 120 weight% with respect to resin powder, for example.

Although there is a conductive agent in terms of providing antistatic performance, carbon powder and the like have a problem of impairing the designability because the appearance of the makeup sheet is black. In addition, antimony-doped tin oxide (ITO) powder, tin oxide treated titanium oxide powder, and the like have problems of high cloudiness and high cost. These inorganic compounds are generally not preferred as antistatic agents for makeup sheets.

When a specific extender pigment is added to the primer layer as an inorganic filler together with the antistatic agent, the antistatic property can be further improved. Moreover, if the antistatic performance equivalent to the addition of the extender pigment can be obtained, not only the addition amount of the antistatic agent is reduced, but also the resin content is reduced, so that the desired performance can be realized at a lower cost. As an extender pigment (antistatic adjuvant), barium sulfate is preferable, for example. When it contains barium sulfate, not only antistatic property but also weatherproof adhesiveness can be improved. On the other hand, although calcium carbonate of an extender pigment improves antistatic property, it is difficult to use for a cosmetic sheet because of poor weather resistance.

Although the addition amount of the said barium sulfate is not limited, For example, it is about 50 to 500 weight% normally with respect to resin powder. When there is too much addition amount, the effect of roughening a primer layer surface and reducing adhesiveness may arise.

Although the thickness of a primer layer changes with a use etc., about 1-10 micrometers is preferable normally.

Surface protective layer

In the present invention, the surface protective layer is provided as the outermost surface layer. The surface protective layer may be colored as long as it is transparent. The pattern layer may be translucent within the range that can be visually recognized. The surface protective layer protects scratches from occurring on the surface of the makeup sheet and improves scratch resistance.

In the cosmetic sheet of the present invention, the surface protective layer is formed by a composition comprising a) ionizing radiation polymerizable oligomer and b) reactive silicone acrylate.

(Ionizing Radiation Polymerizable Oligomer)

The ionizing radiation polymerizable oligomer can apply what is used for well-known ionizing radiation hardening type resin. Specifically, polyester acrylate, epoxy acrylate, polyurethane acrylate, polyether acrylate, polyol acrylate, etc. are mentioned.

As the ionizing radiation polymerizable oligomer in the present invention, (A) an urethane (meth) acrylate oligomer having two radically polymerizable unsaturated groups in one molecule and (B) an aliphatic urethane having 3 to 15 radically polymerizable unsaturated groups in one molecule It is preferable to include a (meth) acrylate oligomer.

The said urethane (meth) acrylate oligomer (A) is what has two radically polymerizable unsaturated groups in 1 molecule (so-called bifunctional urethane acrylate oligomer). This is, for example, a) a diisocyanate, b) a polyhydric alcohol having two or more hydroxyl groups in one molecule (preferably having a weight average molecular weight of 500 to 2000), and c) a hydroxyl group at the terminal and a radically polymerizable unsaturated group. The oligomer which the (meth) acrylate compound which has is couple | bonded is mentioned. It is preferable that this oligomer is 1000-4000 by weight average molecular weight. When the said molecular weight is less than 1000, there exists a possibility that the flexibility which a urethane (meth) acrylate has in the resin layer after hardening cannot fully be exhibited. Moreover, the workability at the time of bending processing and embossing, such as V cutting processing and lapping processing, falls. Moreover, when the said molecular weight exceeds 4000, there exists a possibility that the characteristics, such as pollution resistance, may fall.

The diisocyanate a) 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, etc. are mentioned.

As said polyhydric alcohol b), there exists a polyester polyol, a polyether polyol, a polycarbonate polyol, an acryl polyol, etc. which have a hydroxyl group at both ends. As said polyester polyol, (A) addition reaction product of the diol compound which has aromatic or spiro ring skeleton, lactone compound or its derivative (s), or epoxy compound, (B) condensation product of polybasic acid and alkylene glycol, and (C) There are ring-opening polyester compounds derived from cyclic ester compounds, and these may be used alone or in combination of two or more thereof. For example, adipic acid is used as the polybasic acid of the above (b), and polyester diols (particularly a weight average molecular weight of 500 to 2000) having hydroxyl groups at both ends obtained as condensation products with alkylene glycol have good various physical properties. It is used preferably because it is. Examples of the polyether polyol include polytetramethylene ether glycol, polyethylene glycol, and polypropylene glycol.

Said (meth) acrylate c) is an ester compound of acrylic acid or methacrylic acid or these derivatives, and has a hydroxyl group at the terminal. Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl (meth) acrylate, 5 (Meth) acrylic acid ester compound which has one polymerizable unsaturated group, such as -hydroxycyclooctyl (meth) acrylate and 2-hydroxy-3-phenyloxypropyl acrylate, or another molecule | numerator in a 1 molecule. The (meth) acrylic acid ester compound which has more than two is illustrated.

In the present invention, the urethane (meth) acrylate oligomer (A) is preferably a polyester polyol having a weight average molecular weight of 500 to 2000, wherein the polyhydric alcohol component is formed of alkylene glycol and adipic acid. An oligomer having a weight average molecular weight of 1000 to 3000, which is made of phorone diisocyanate, and whose acrylate component is hydroxyethyl (meth) acrylic acid ester, is obtained.

The aliphatic urethane (meth) acrylate oligomer (B) has a radical polymerizable unsaturated group such as 3 to 15 (meth) acryloyl groups in one molecule. This is a polyfunctional (3-15 functional) urethane acrylate obtained by reacting a) an aliphatic diisocyanate, b) a polyfunctional polyol, and c) terminal with a (meth) acrylate having a hydroxyl group and a radically polymerizable unsaturated group. .

As said aliphatic diisocyanate a), 1, 6- hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. are mentioned, for example.

As said polyfunctional polyol b), what has the said polyhydric alcohol as a basic skeleton, and has two or more functional groups can be used.

As said (meth) acrylate c), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxycyclohexyl ( (Meth) acrylic acid ester compound which has one polymerizable unsaturated group, such as a meth) acrylate, 5-hydroxycyclooctyl (meth) acrylate, and 2-hydroxy-3-phenyloxypropyl acrylate.

As an ionizing radiation polymerizable oligomer of this invention, it is an ionizing radiation polymerizable oligomer, (A) 40-80 weight% of urethane (meth) acrylate oligomer which has two radically polymerizable unsaturated groups in 1 molecule, and (B) 1 molecule. Preference is given to using a mixture comprising 60 to 20% by weight of an aliphatic urethane (meth) acrylate oligomer having 3 to 15 radically polymerizable unsaturated groups.

When said (A) becomes less than 40 weight%, the flexibility, malleability, etc. of a curable resin layer may become inadequate, and there exists a possibility that impact resistance may fall. Moreover, when said (A) exceeds 80 weight%, there exists a possibility that abrasion resistance and contamination resistance may fall. In addition, the compounding quantity of the said urethane (meth) acrylate oligomer (A) and aliphatic urethane (meth) acrylate oligomer (B) is said oligomer (A) and oligomer (B) in the coating composition which forms a curable resin layer. The weight% of each component with respect to the total weight of is shown.

(Reactive silicone acrylate)

Although it does not specifically limit as reactive silicone acrylate, It is preferable to react with said electron beam radiation polymerizable oligomer. The said silicone acrylate has a dimethylsiloxane structure. Kind of functional group: In particular, in consideration of EB curing (electron beam irradiation), a methacryl group, an acryl group and a mercapto group are preferable.

In addition, although the silicone acrylate mentioned above may exist as it is in the mixture with an electron beam curing polymeric oligomer, it may be copolymerized with the said oligomer to some extent, and this invention also includes this aspect.

Although content of reactive silicone acrylate can be suitably determined according to the kind of ionizing radiation polymerizable oligomer, etc., it is usually 5 weight% or less in the said mixture, 0.1-3.0 weight% is preferable, and 0.5-2.0 weight% of The range is more preferable.

(Sphere particle)

It is preferable that the composition for forming a surface protective layer contains spherical particle further.

As spherical particles, those having an apparent specific gravity of 0.3 to 1 g / cm 3 and preferably 0.65 to 0.85 g / cm 3 are used. By including spherical particles in this range, the scratch resistance of the surface protective layer is sufficiently obtained.

In addition, the apparent specific gravity of the spherical particle in this specification is the value measured by the method based on JISK5101.

Although the average particle diameter of a spherical particle is not limited, In general, it is preferable to set it as 5 micrometers or less in average particle diameter.

It is preferable that oil absorption amount is 50 ml / 100g or less of a spherical particle. That is, the use of higher density spherical particles makes it easier to improve scratch resistance.

It is preferable to make the specific surface area (BET specific surface area) of a spherical particle normally about 0-50 m <2> / g.

The pore capacity of the spherical particles is usually preferably 0.5 ml / g or less, more preferably about 0.1 to 0.4 ml / g. That is, using a higher density particle | grains becomes easier to improve scratch resistance.

The spherical particles are not limited as long as they are materials having the above-described physical properties. For example, resin particles such as acrylic may be used in addition to inorganic particles such as silica, wollastonite and alumina. In this invention, a silica particle can be used preferably, It is preferable to set so that one part or all part of a spherical particle may become a silica particle.

The content of the spherical particles is not particularly limited and can be appropriately determined depending on the type of the ionizing radiation polymerizable oligomer or the like, but usually about 1 to 10% by weight of the mixture is preferable, and particularly preferably 3 to 5% by weight.

(Other additives)

The cosmetic sheet of this invention may contain arbitrary additives in a surface protection layer. For example, a well-known mat agent may be included in order to raise the mat feeling of the outermost surface of a makeup sheet.

As a mat agent, For example, inorganic particles, such as a silica and a silicone resin (powder and beads); Organic material powders and beads such as crosslinked alkyl, crosslinked styrene, artificial guanamine resin, urea-formaldehyde resin, phenol resin, polyethylene and nylon, and the like. Among these, especially silica can be used preferably. It is also preferable to use untreated silica. The reason is that the waxed organic treated silica is likely to bleed from the sheet surface in combination with those having liquid repellency.

Examples of the mat agent include particles having an oil absorption amount of 100 ml / 100 g or more (particularly 200 to 400 ml / 100 g), particles having a pore capacity of 0.6 ml / g or more (particularly 1 to 1.7 ml / g), and specific gravity of 0.08 to Particles that are 0.4 g / cm 3 are preferred. By using such relatively dense particles, a desired mat feel can be imparted to the surface of the makeup sheet.

The particle size of the mat agent is also not limited, and can be appropriately determined depending on the use and the like. Generally, about 0.1-30 micrometers of particle diameters are preferable, and the range of particle diameters 3-6 micrometers is especially preferable.

Although content of a mat agent is not limited, It is preferable to set it as 3-20 weight part, especially 5-15 weight part with respect to 100 weight part of said mixtures.

The said composition can be manufactured by mixing each of these components uniformly. The formation method of the surface protection layer by this composition can also follow a well-known method, For example, it can form a coating film by the said composition, and can carry out crosslinking hardening of a coating film by electron beam irradiation on well-known use conditions.

As an electron beam source of ionizing radiation, 100-1000 keV, Preferably it uses various electron beam accelerators, such as a cockcroft walton type, a half-degraft type | mold, a resonance transformer type | mold, an insulation core transformer type | mold, a linear type | mold dynamtron type | mold, and a high frequency type | mold. Electrons having an energy of 200 to 300 keV can be irradiated. As the ultraviolet source, for example, light sources such as ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc lamp, black light and metal halide lamp can be used.

The surface protective layer (that is, the outermost surface of the makeup sheet) is preferably inscribed with an uneven shape by embossing or the like. More preferably, a wiping process is performed in which the ink is filled in the embossed recess, and the surface is coated (overcoating) with a two-component curable urethane resin (primer layer) and an ionizing radiation polymerizable oligomer. .

Embossing is performed in order to provide a desired texture, such as a wooden board surface, to a makeup sheet. For example, after heating and softening the surface of the makeup sheet (olefin resin) on a heating drum, it is further heated to 160 to 180 DEG C with an infrared radiation heater, pressurized and shaped with an embossed plate provided with a desired concavo-convex shape, Form by cooling fixed. Embossing can use a well-known sheet | leaf or rotation type embossing machine. Examples of the uneven shape include wood grain conduit grooves, embossed shapes, and hair lines, sand grains, checkered patterns, and the like. You can choose.

Wiping process means the process which fills ink, wiping the surface with the doctor blade in the recessed part provided in the embossing process. As the wiping ink, an ink containing a two-component curable acrylic urethane copolymer resin as a binder can be generally used. In the wiping process, the grain value of the product can be increased by expressing a design closer to the actual grain of wood by performing the grain-shaped conduit groove irregularities.

Substrate

The adherend to which the makeup sheet is applied is not limited, and the same one as the known makeup sheet can be used. For example, wood materials, metals, ceramics, plastics, glass, etc. are mentioned. The makeup sheet of the present invention can be preferably applied to wood materials. Wood materials include, for example, a top plate made of various materials such as cedar, cypress, zelkova, pine, nawang, teak and melapi, wood veneer, wood plywood, particle board and medium density fiberboard (MDF). Etc. can be mentioned.

On the substrate  For lamination

The decorative sheet is laminated on various adherends and the like to form a decorative plate. A lamination method is not limited, For example, lamination | stacking can be carried out by adhering a makeup sheet to an adherend with an adhesive agent. An adhesive agent can be selected from a well-known adhesive agent according to the kind of adherend, etc. For example, butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, and the like, in addition to polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer and the like.

The decorative board can be preferably applied to, for example, interior materials of buildings such as walls, ceilings and floors, surface decorative plates of windows and doors such as window frames, doors and railings, and surface decorative plates of furniture or cabinets such as pharmacopoeia and OA devices. Can be.

An Example is shown to the following and the characteristics of this invention are demonstrated more clearly. However, this invention is not limited to the range of an Example.

Examples 1 to 3

As the base sheet, a polypropylene resin film (thickness 60 µm, transmittance 10%) was prepared. After giving the corona discharge treatment to this surface and back surface, the wood grain pattern layer was formed in the surface by gravure printing. On the other hand, the primer layer was formed by gravure printing on the back surface.

Next, a coating liquid containing a two-component curable urethane resin was coated on the pattern layer to form an adhesive layer (thickness 3 µm). In addition, a transparent resin layer (thickness: 80 µm) was formed by melt extrusion coating a polypropylene thermoplastic elastomer containing an ethylene-propylene-butene copolymer with a T die.

On the transparent resin layer, the two-component curable urethane-based resin containing an acrylic urethane block polymer (main agent) and hexamethylene diisocyanate (curing agent) was coated to form a primer layer (thickness 2 µm).

Next, the surface protective layer was formed using the composition containing the component shown in Table 1.

Each component of Table 1 used the following, respectively.

Oligomer (A): Urethane (meth) acrylate oligomer having two radically polymerizable unsaturated groups in one molecule

Oligomer (B): Aliphatic urethane (meth) acrylate oligomer having 3 to 15 radically polymerizable unsaturated groups in 1 molecule

Silica: average particle diameter of 5 mu m, surface untreated product (external specific gravity: 0.1 to 0.4) + average particle diameter of 4 mu m (external specific gravity: 0.45 to 0.85)

Repulsive component (reactive silicone acrylate): both terminal reactive silicone acrylate

After forming a coating film with each composition shown in Table 1, the surface film (5 micrometers in thickness) was formed by irradiating an electron beam on the conditions of 175 keV and 5 Mrad (50 kGy), and crosslinking-hardening the said coating film.

Finally, the surface protective layer side is heated with an infrared non-contact heater to soften the base sheet and the transparent resin layer, and then immediately embossed by hot pressure from the surface of the surface protective layer to form a concave-convex groove shape. By shaping | molding, the predetermined | prescribed makeup sheet was obtained.

Comparative Examples 1 to 3

A cosmetic sheet was produced in the same manner as in Example 1, except that the surface protective layer was formed by the composition shown in Table 1.

Test Example 1

The following physical properties of the makeup sheet obtained in the Example and the comparative example were investigated, respectively. The results are shown in Table 1.

(1) Repulsion performance (initial)

The repulsion characteristic at the time of writing on the surface protective layer of a makeup sheet was confirmed using the thick magic ink (Okoda oil-based ink). The ink was splashed, i.e., the state where the ink became the droplet was evaluated as "(circle)", and the ink was not splashed, and the favorable wet state was evaluated as "x".

(2) repulsion performance (color after wiping off)

After wiping the handwriting written in the above (1) with cotton, the residual color was observed. "(Circle)" and the case where ink was not wiped and the state which remained completely the same as the state before wiping were evaluated by "x". The results are shown in Table 1.

(3) repulsion performance (eraser)

The surface protective layer surface of the makeup sheet was rubbed with an eraser for 10 times, and then the surface was subjected to the test of (2). "(Circle)" and the case where ink was not wiped and the state which remained completely the same as the state before wiping were evaluated by "x". The results are shown in Table 1.

(4) Repulsion performance (after S-UV test)

The cosmetic sheet was tested in accordance with JIS-B-7350 as an accelerated weather resistance test. Using a sunshine carbon arc lamp weather resistance tester, it carried out for 200 hours in total on condition that black panel temperature 63 degreeC, irradiation amount 25.5 mW / cm <2> (365 nm), and rainfall time are 18 minutes among 120 minutes of irradiation. After the test, the test of (2) above was performed on this surface. The case where the state which was fully wiped was "(circle)" and the ink maintained in the same state as before the wiping without wiping was evaluated as "x". The results are shown in Table 1.

From the above result, it turned out that the cosmetic sheet of this invention has the outstanding resilience performance (pollution resistance) and durability.

Example 4

As a base material sheet, the polypropylene resin film (thickness 60 micrometers, transmittance 10%) was prepared. After giving the corona discharge treatment to this surface and back surface, the wood grain pattern layer was formed in the surface by gravure printing. On the other hand, the primer layer was formed by gravure printing on the back surface.

Next, a coating liquid containing a two-component curable urethane resin was coated on the pattern layer to form an adhesive layer (thickness 3 µm). In addition, a transparent resin layer (thickness: 80 µm) was formed by melt extrusion coating a polypropylene thermoplastic elastomer containing an ethylene-propylene-butene copolymer with a T die.

The primer layer was formed on the transparency resin layer. The primer layer is composed of an acrylic urethane block polymer (main agent) and a hexamethylene diisocyanate (curing agent) in a two-component curable urethane resin, containing 25% by weight of an antistatic agent (quaternary ammonium) and 30% by weight of an antistatic aid (sulfuric acid). Barium) was coated to form a primer layer (thickness 2 m).

Next, the surface protective layer was formed using the composition containing the component shown in Table 2.

In Table 2, a numerical value shows "weight%." The numerical value of an oligomer (A) and an oligomer (B) shows the weight ratio of each oligomer at the time of making the total weight of both into 100 weight%. The numerical value of silicone and spherical particle | grains shows the content rate in a coating composition.

Each component of Table 2 used the following, respectively.

Oligomer (A): Urethane (meth) acrylate oligomer having two radically polymerizable unsaturated groups in one molecule

Oligomer (B): Aliphatic urethane (meth) acrylate oligomer having 3 to 15 radically polymerizable unsaturated groups in 1 molecule

Silicone (reactive silicone acrylate): both terminal reactive silicone acrylates

ㆍ Spherical particle: Appearance specific gravity 0.65 to 0.85 g / cm 3, oil absorption 45 ml / 100 g, BET specific surface area 0 m 2 / g, average particle diameter 3.6 μm, pore capacity: 0.1 ml / g

After forming a coating film with each composition shown in Table 2, surface protection layer (5 micrometers in thickness) was formed by irradiating an electron beam on condition of 175 keV and 5 Mrad (50 kGy), and crosslinking-hardening the said coating film.

Finally, the surface protective layer side is heated with an infrared non-contact heater to soften the base sheet and the transparent resin layer, and then immediately embossed by hot pressure from the surface of the surface protective layer to form a concave-convex groove shape. By shaping | molding, the predetermined | prescribed makeup sheet was obtained.

Comparative Examples 4 to 7

A surface protective layer was formed with the composition shown in Table 2, and the comparative example 6 and 7 produced the cosmetic sheet similarly to Example 4 except not having used antistatic agent and antistatic auxiliary agent.

Test Example 2

The following physical properties of the makeup sheets obtained in Example 4 and Comparative Examples 4 to 7 were investigated, respectively. The results are shown in Table 3.

(1) antifouling properties (rebound test)

The repulsion characteristic at the time of writing on the surface protective layer of a makeup sheet was confirmed using the thick magic ink (black, blue and red, oil-based oil made by Yoko Uchida). The state of flipping the magic (that is, the magic droplets) was evaluated as good (○), and the wet state where the magic did not splash was poor (×).

(2) Antistatic property (cigarette ash test)

The surface of the makeup sheet was rubbed 20 times with cotton, and the ashes of tobacco were brought close to the charged sample to visually check the state of attachment of the ashes. No adhesion of ash was evaluated as good (○) and adhesion as poor (×).

(3) scratch resistance (steel wool test)

The surface of the makeup sheet was rubbed with steel wool 20 times (load: 300 g / cm 2) and rubbed, and the presence or absence of scratches was visually confirmed. The thing without a flaw was evaluated as good ((circle)) and the thing with a scratch as defect (x).

Since the surface protective layer is formed of the composition containing an ionizing radiation polymerizable oligomer and reactive silicone acrylate, the cosmetic sheet of this invention exhibits the outstanding repulsion performance (pollution resistance) and durability, avoiding the problem of bleeding. do.

That is, the cosmetic sheet of the present invention is hardly adhered to contaminants on the surface protective layer (the so-called repulsion property is excellent), and also has a long lasting effect, and thus exhibits excellent stain resistance and durability over a long period of time.

In addition, the cosmetic sheet of the present invention can exhibit superior designability (particularly, various gloss grades) when a mat agent is used.

Claims (10)

As a makeup sheet for laminating | stacking on a to-be-adhered material, (1) the sheet has at least a base sheet, a pattern layer, a transparent resin layer and a surface protective layer in order; (2) the surface protective layer is formed by a composition comprising a) an ionizing radiation polymerizable oligomer and b) a reactive silicone acrylate, (3) 40-80 weight% of said ionizing radiation polymerizable oligomers (A) urethane (meth) acrylate oligomer which has two radically polymerizable unsaturated groups, and (B) 3-15 radically polymerizable in 1 molecule 60 to 20% by weight of an aliphatic urethane (meth) acrylate oligomer having an unsaturated group The makeup sheet characterized by the above-mentioned. The method according to claim 1, wherein the cosmetic sheet further has a primer layer between the transparent resin layer and the surface protective layer, (1) the primer layer contains an antistatic agent, (2) a cosmetic sheet wherein said surface protective layer is formed by a composition comprising a) said ionizing radiation polymerizable oligomer, b) reactive silicone acrylate and c) spherical particles having an apparent specific gravity of 0.3 to 1 g / cm 3. . The cosmetic sheet according to claim 2, wherein the spherical particles have a pore capacity of 0.5 ml / g or less. The cosmetic sheet according to any one of claims 1 to 3, wherein the surface protective layer contains a mat agent. The cosmetic sheet according to claim 2 or 3, wherein part or all of the spherical particles are silica particles. The cosmetic sheet according to any one of claims 1 to 3, wherein the surface protective layer has irregularities by embossing. delete delete The cosmetic sheet according to any one of claims 1 to 3, wherein at least one of the transparent resin layer and the base sheet is a polyolefin resin. The cosmetic sheet which is laminated | stacked on the to-be-adhered material so that the surface protection layer of the cosmetic sheet as described in any one of Claims 1-3 may be an outermost surface layer.