KR101229720B1 - Antistatic Decorative Sheets with Inhibiting Whitening on Bending - Google Patents

Abstract

The present invention provides a cosmetic sheet containing a polymer antistatic agent, and provides a cosmetic sheet in which whitening during bending is suppressed.

In addition, the present invention provides a makeup sheet, which is a makeup sheet for laminating on an adherend, and has at least a polyolefin resin layer, and a polymer antistatic agent and an acid-modified polyolefin resin are contained in the polyolefin resin layer. do.

Cosmetic sheet, polymer type antistatic agent, whitening

Description

Antistatic cosmetic sheet with whitening suppressed during bending {Antistatic Decorative Sheets with Inhibiting Whitening on Bending}

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows an example of the laminated structure of the makeup sheet of this invention.

2 is a cross-sectional structural view of the makeup sheet prepared in Example 1. FIG.

It is a figure which shows the state of the outer surface after the bending test of the makeup sheet manufactured by the Example, the comparative example, and the reference example.

<Explanation of symbols for the main parts of the drawings>

1: polypropylene resin film 2: pattern layer

3: adhesive layer 4: polyolefin resin layer (lower layer)

5: polyolefin resin layer (surface layer) 6: primer layer

8: Surface protective layer 11: Polyolefin resin layer

12: adherend 13: outer surface

14: surface layer

[Document 1] Japanese Unexamined Patent Publication No. 2000-351182

[Document 2] Japanese Unexamined Patent Publication No. 2001-278985

[Document 3] Japanese Unexamined Patent Publication No. 2001-181413

[Patent 4] Japanese Patent Application Laid-Open No. 4-82625

The present invention relates to an antistatic makeup sheet in which whitening during bending is suppressed.

Cosmetic sheets are widely used for various interior and exterior building materials, as well as for decorating various surfaces of home appliances, office equipment, instruments, and the like. The cosmetic sheet is generally manufactured by laminating a printing layer, a synthetic resin layer, a surface protective layer, and the like on a base sheet. Conventionally, vinyl chloride-based resins have been used as synthetic resin layers and the like, but cosmetic sheets using vinyl chloride-based resins generate toxic gases such as hydrogen chloride gas during combustion. Therefore, there is a problem in waste disposal treatment that incineration cannot be performed with a general incinerator. In addition, during a fire, a person may inhale poisonous gases such as hydrogen chloride gas and cause poisoning. From this fact, the use of vinyl chloride resins tends to be avoided. It has also been pointed out that incineration of vinyl chloride-based resins with inadequate incinerators may generate toxic gases such as dioxins due to incomplete combustion.

From the above viewpoints, substitution with polyolefin resins, such as polypropylene, is performed instead of vinyl chloride resin.

The problem of vinyl chloride resin can be solved by substituting polyolefin resin, but another problem arises. That is, in resins including polyolefin resins, there is a tendency to be static electricity. Therefore, in the case of using such a material for the makeup sheet, 1) fine dust adheres to the printing disk, which causes problems such as ink leakage, and 2) air discharge caused by charging causes fire, 3) Due to the attachment of fine dust, it may interfere with secondary processing. 4) Even if you try to remove the attached fine dust, it is attached by static electricity. Problem occurs.

Therefore, adding an antistatic agent to a makeup sheet is proposed. For example, a method of applying a quaternary ammonium salt, carbon black, metal acicular crystals, or the like as an antistatic agent to a surface protective layer of a makeup sheet or the like (for example, Japanese Patent Application Laid-Open No. 2000-351182, etc.).

However, when these conventional antistatic agents are used, a) sufficient antistatic effect cannot be obtained, b) even if the effect is secured, the persistence of the effect is insufficient, and c) even if the effect is obtained, it is due to the inclusion of the antistatic agent. Any problem such as impairing the designability of the makeup sheet occurs due to haze or the like. In view of such a problem, the use of a polymer type antistatic agent is proposed. In the case of using the polymer type antistatic agent, a good and stable antistatic effect can be obtained. By the way, when using a polymeric antistatic agent, when bending a makeup sheet (for example, at the time of V-cutting process), the problem that the interface of a polymeric antistatic agent and polyolefin resin whitens arises. It is considered that this is caused by the occurrence of minute cracks at the interface between the polymer type antistatic agent and the polyolefin resin. Therefore, further improvement measures are required.

This invention is a cosmetic sheet containing a polymeric antistatic agent, Comprising: It aims at providing the cosmetic sheet by which the whitening at the time of bending was suppressed.

MEANS TO SOLVE THE PROBLEM As a result of earnest research in view of the problem of the prior art, when the polymer type antistatic agent is contained with an acid-modified polyolefin resin, the said objective was achieved and the present invention was completed.

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

1. A makeup sheet for laminating onto an adherend, wherein the makeup sheet has at least a polyolefin resin layer, and the cosmetic sheet contains a polymer antistatic agent and an acid-modified polyolefin resin in the polyolefin resin layer.

2. The cosmetic sheet according to 1 above, wherein at least a pattern layer and a polyolefin resin layer are laminated on the base sheet, and the polyolefin resin layer is composed of one layer or two or more layers, and the surface layer portion of the polyolefin resin layer. A cosmetic sheet in which a polymer type antistatic agent and an acid-modified polyolefin resin are contained.

3. The makeup sheet according to 1 above, wherein at least a pattern layer, a polyolefin resin layer and a surface protective layer are laminated on the base sheet, and the polyolefin resin layer is composed of one or two or more layers, and the polyolefin resin A cosmetic sheet containing a polymer type antistatic agent and an acid-modified polyolefin resin in the surface layer portion of the resin layer.

4. The cosmetic sheet according to any one of 1 to 3, wherein the surface layer portion is an area from the outer surface of the polyolefin resin layer to a depth of 1/2 or less of the thickness of the resin layer.

5. The cosmetic sheet according to any one of 2 to 4, wherein the polyolefin resin layer has a thickness of 30 µm or more, and the surface layer portion is an area from the outer surface of the resin layer to a depth of 15 µm or less.

6. The cosmetic sheet according to any one of 1 to 5, wherein the polymer type antistatic agent is at least one of polyether-ester-amide and polyether-polyolefin block polymer.

7. The cosmetic sheet according to any one of 1 to 6, wherein the polyolefin resin layer contains 3 to 35 wt% of a polymer type antistatic agent.

8. The cosmetic sheet according to any one of 2 to 7, wherein the surface layer portion contains 3 to 35 wt% of a polymer type antistatic agent.

9. The cosmetic sheet according to any one of 1 to 8, wherein 3 to 20% by weight of an acid-modified polyolefin resin is contained in the polyolefin resin layer.

10. The cosmetic sheet according to any one of 2 to 9, wherein 3 to 20% by weight of an acid-modified polyolefin resin is contained in the surface layer portion.

11. The cosmetic sheet according to any one of 1 to 10, wherein the polyolefin resin layer further comprises at least one of an ultraviolet absorber and a light stabilizer.

12. The makeup sheet according to 11 above, wherein the light stabilizer is a polymer light stabilizer.

13. The cosmetic sheet according to the above 12, wherein the polymer type light stabilizer is a copolymer of cyclic aminovinyl compound represented by the following formula (1) and ethylene.

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

14. The cosmetic sheet according to any one of 2 to 13, wherein 5 to 10% by weight of the polymer type light stabilizer is contained in the surface layer portion.

15. A decorative plate, wherein the decorative sheet according to any one of 1 to 14 above is laminated on the adherend.

1. Makeup Sheet

The makeup sheet of the present invention is a makeup sheet for laminating on an adherend, wherein the makeup sheet has at least a polyolefin resin layer, and the polymer antistatic agent and acid-modified polyolefin resin are contained in the polyolefin resin layer. do.

The cosmetic sheet of this invention has at least a polyolefin resin layer. The polyolefin resin layer may be one layer or two or more layers. In addition, when there are two or more layers, they may be laminated so as to be in contact with each other or may be laminated through other layers.

Resin which comprises a polyolefin resin layer is not specifically limited, For example, well-known resin, such as polyethylene, a polypropylene, a polybutene, an ethylene-vinyl acetate copolymer, an ionomer, an ethylene- ethylene acrylate copolymer, can be used. . These may be used alone or in combination of two or more.

The polyolefin-based resin layer includes a polymer type antistatic agent and an acid-modified polyolefin resin. A polymer type antistatic agent can use a well-known thing or a commercial item. For example, polyacrylic acid ester quaternary ammonium salt, polystyrene quaternary ammonium salt, polyether ester-amide, polyether polyolefin block polymer, etc. can be used.

In the present invention, at least one of polyether-ester-amide and polyether-polyolefin block polymer can be preferably used as the polymer type antistatic agent.

Examples of the polyether-ester-amide include a polymer composed of three components, an ether group-containing component, an ester group-containing component and an amide group-containing component. For example, the polyether ester amide containing a polyethylene oxide component and the nylon 12 component is mentioned. More specifically, polyethylene oxide part -H- [O-CH ₂ CH ₂ ] _n -O-, adipic acid part -OC (CH ₂ ) ₄ CO- and nylon 12 parts- [NH (CH ₂ ) ₁₁ CO] _The copolymer which consists of 3 parts of _n- O- is mentioned. For example, product names "IRGASTAT P 18" and "IRGASTAT P 22" (all are manufactured by Chiba Specialty Chemical Co., Ltd.).

The polyether-polyolefin block polymer is a block comprising a structure in which a block of polyolefin (a) and a block of hydrophilic polymer (b) having a volume intrinsic resistance of 10 ⁵ to 10 ¹¹ Ω · cm are alternately bonded to each other. A polymer (Japanese Patent Laid-Open No. 2001-278985) can be preferably used.

It is more preferable to use polyether ester amide from a viewpoint that a higher weather resistance is obtained among these polymer type antistatic agents. In other words, when polyether-ester-amide is used, desired weather resistance can be obtained with a smaller amount of ultraviolet absorber and / or light stabilizer.

Although content of a polymeric antistatic agent is not limited, The kind of polymeric antistatic agent used and desired antistatic performance within the range of 2-40 weight% (preferably 3 to 35 weight%) in a polyolefin synthetic resin layer. It can determine suitably according to these.

In the present invention, the acid-modified polyolefin resin is included in the polyolefin resin layer together with the polymer type antistatic agent. The acid-modified polyolefin resin is not particularly limited and may be selected in a wide range depending on the degree of compatibility improvement between the polymer type antistatic agent and the polyolefin resin. As a preferable acid-modified polyolefin resin, "product name" eumeric 1010 "(Sanyo Kasei Kogyo Co., Ltd. product) is mentioned, for example. The acid-modified polyolefin resin can effectively prevent the occurrence of cracks (gaps) that cause whitening at the interface between the polymeric antistatic agent and the polyolefin resin at the time of bending the makeup sheet.

Although content of acid-modified polyolefin resin is not limited, It can set suitably within the range of 3-20 weight% (preferably 4-15 weight%) in a polyolefin synthetic resin layer.

The acid-modified polyolefin resin used by this invention is a polyolefin resin in which at least one terminal was acid-modified. As for the acid value prescribed | regulated to JISK0070, about 1.0-100 mgKOH / g is preferable, and about 5-60 mgKOH / g is more preferable. If the acid value is less than 1.0 mgKOH / g, there is a fear that the improvement of compatibility will be insufficient. When it exceeds 100 mgKOH / g, there exists a possibility that the operability at the time of sheet forming may deteriorate.

As a polyolefin (raw material), the thing similar to the polyolefin which is matrix resin of the said polyolefin resin layer can be used. For example, homopolymers, copolymers or mixtures of these polymers, such as propylene, ethylene, butene-1, hexene-1, 4-methylpentene-1 and the like are exemplified. Among these, especially low molecular weight polypropylene is preferable.

The low molecular weight acid modified polypropylene is an acid modified polypropylene having a number average molecular weight of 800 to 20,000, preferably 1000 to 18000. The acid-modified polypropylene may be synthesized by a method of chemically adding the unsaturated carboxylic acid and / or anhydride thereof described below to a low molecular weight polypropylene having a terminal double bond, or a method of low molecular weight of a conventional acid-modified propylene. And at least some of the ends are acid denatured. Acid-modified polypropylenes have a softening point of generally 130 to 170 ° C, preferably 140 to 160 ° C.

The low molecular weight polypropylene having a preferred terminal double bond has a terminal double bond of 1 to 10, preferably 2 to 7, per 1000 carbons, and has a number average molecular weight of 800 to 20,000, preferably 1000 to 18000. When the number of terminal double bonds is less than 1, there is a fear that desired acid denaturation is unlikely to occur. When the number of terminal double bonds exceeds 10, there exists a tendency for the heat resistance of acid-modified polypropylene to fall. Moreover, when number average molecular weight exceeds 20000, there exists a tendency for bending whitening resistance to fall.

The acid modification can be carried out by a melt graft method, a solution graft method, or the like. The melt graft method can be carried out under the conditions of usually 0.5 to 30 hours, preferably 1 to 20 hours (reaction time) at a reaction temperature of usually 100 to 270 ° C, preferably 130 to 240 ° C. The solution graft method, after completely dissolving in xylene, uses a peroxide together, and the reaction with an unsaturated carboxylic acid and / or its anhydride is usually carried out at a reaction temperature of 120 to 180 캜, preferably 140 to 160 캜, It can carry out under conditions of 1 to 20 hours, preferably 3 to 15 hours (reaction time). In addition, a large amount of acetone or the like is used to obtain a precipitate.

The result obtained by the acid denaturation preferably contains an unsaturated carboxylic acid and / or anhydride thereof in a proportion of generally 0.01 to 20%, preferably 0.05 to 15%, particularly preferably 0.1 to 10% by weight. Do. Examples of the unsaturated carboxylic acid that is a modifier include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and nazi acid. Examples of the unsaturated carboxylic anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, nazi anhydride, and the like. Among these, maleic anhydride is preferable. In addition, the acid-modified polyolefin may be one obtained by diluting a directly modified one with an unmodified one.

The manufacturing method of the polyolefin resin layer containing a polymeric antistatic agent and acid-modified polyolefin resin is not specifically limited. For example, after adding and mixing a polymeric antistatic agent and an acid-modified polyolefin resin to molten polyolefin resin, the obtained mixture is sheeted by the extrusion method, laminated | stacked, and the said mixture is laminated | stacked another layer by the extrusion method. The method of laminating | stacking directly to the said, the method of laminating | stacking the said sheet-ized thing in several numbers, laminating | stacking them by another coextrusion method, etc. are mentioned.

In this invention, it is especially preferable that a polymeric antistatic agent and acid-modified polyolefin resin exist in the surface layer part of a polyolefin resin layer. By adopting such a configuration, effective antistatic performance and the like can be obtained with a smaller usage amount. Moreover, the whitening at the time of bending can be prevented or suppressed effectively.

The surface layer portion is a region near the surface (surface) of the polyolefin resin layer. That is, it is a surface on the opposite side to the side where a makeup sheet is laminated | stacked with a to-be-adhered body. For example, as shown in FIG. 1, when the polyolefin resin layer 11 is laminated | stacked on the to-be-adhered body 12, the area | region of the constant depth from the outer surface 13 turns into the surface layer part 14. As shown in FIG.

In the present invention, the surface layer portion also depends on the thickness of the polyolefin-based resin layer and the like, but in general, the surface layer portion is preferably a region up to a depth of 1/2 or less of the thickness of the resin layer. That is, it is preferable to make the depth of surface layer part 1/2 or less of the thickness of the said resin layer. In particular, in this invention, it is preferable to make the area | region of the depth of 15 micrometers or less from the outer surface of the polyolefin resin layer of 30 micrometers or more in thickness as a surface layer part. In addition, the upper limit of the thickness of a polyolefin resin layer may be about 200 micrometers normally.

In the present invention, one polyolefin resin layer may be composed of one layer (single layer) or two or more layers. In the case of two or more layers, the laminated body laminated | stacked 2 or more comprises a polyolefin type. When the laminated body which consists of two or more layers comprises one polyolefin resin layer, the thickness of the said resin layer means the thickness of the said laminated body. In addition, when two or more polyolefin resin layers exist in a makeup sheet, a surface layer part means the surface layer part of the polyolefin resin layer located in the furthest position from the to-be-adhered body to be laminated | stacked.

When a polymer type antistatic agent exists in a surface layer part, it is preferable to make the content into 2 to 40 weight%, especially 3 to 35 weight% generally in a surface layer part. By setting it in the said range, favorable weather resistance etc. can be acquired with further excellent antistatic performance. In addition, when a polymeric antistatic agent is present in a surface layer part, an acid-modified polyolefin resin is similarly present in a surface layer part. In general, the content of the acid-modified polyolefin resin is preferably 3 to 20% by weight, particularly 4 to 15% by weight, in the surface layer portion. By setting it in the said range, the whitening at the time of bending can be prevented or suppressed more effectively.

In the present invention, the polyolefin resin layer may contain an additive in addition to the polymer type antistatic agent and the acid-modified polyolefin resin. For example, UV absorbers, light stabilizers (radical scavengers), antioxidants, crystal nucleating agents, clearing agents, lubricants, anti blocking agents, antistatic agents, antifog agents, neutralizing agents, and metal deactivators used in conventional polyolefin resins , Colorants, dispersants, peroxides, fillers, fluorescent brighteners and the like. Among these, it is particularly preferable to further include at least one of ultraviolet absorbers (UVA) and light stabilizers (HALS).

As a ultraviolet absorber, it is a 2- (2'-hydroxy-3 ', 5'-di-tert- butylphenyl) -5- besides a triaryl triazine type ultraviolet absorber (Japanese Unexamined-Japanese-Patent No. 2001-181413, for example). Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl- 5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 2'-hydroxyphenyl-5-chlorobenzotriazole type ultraviolet absorbers, such as 3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole; 2'-hydroxy, such as 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole Benzotriazole-based ultraviolet absorbers such as phenylbenzotriazole-based ultraviolet absorbents; 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-tetra 2,2'- dihydroxy benzophenone series ultraviolet absorbers, such as hydroxy benzophenone; Benzophenone ultraviolet absorbers such as 2-hydroxybenzophenone ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone; Salicylic acid ester ultraviolet absorbers such as phenyl salicylate and 4-t-butyl-phenyl-salicylate; Reactive ultraviolet absorber which introduce | transduced the acryloyl group or the methacryloyl group into the benzotriazole skeleton; And inorganic ultraviolet absorbers such as titanium oxide, cerium oxide, and iron oxide having a particle diameter of 0.2 µm or less.

Although the addition amount of these ultraviolet absorbers can be set suitably according to the kind of ultraviolet absorber, etc., Usually, they may be about 0.1 to 3 weight% in surface layer part.

As a light stabilizer (radical scavenger), a polymeric light stabilizer or other light stabilizers can be used.

As the former polymer type light stabilizer, a copolymer (ethylene-cyclic aminovinyl compound copolymer) of a cyclic aminovinyl compound represented by the following general formula (1) and ethylene can be preferably used. For example, in the formula (1), a copolymer of ethylene and a compound in which R ₁ and R ₂ are methyl groups and R ₃ is a hydrogen atom can be preferably used.

&Lt; Formula 1 >

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

By using such a polymer type light stabilizer, weather resistance can be improved without accompanying the fall of antistatic performance. As a result, the two effects of good antistatic performance and excellent weather resistance can be more reliably achieved.

The MI (melt index) of the polymer is preferably from 0.1 to 500 g / min, in particular from 0.5 to 200 g / min.

The copolymer may be a known or commercially available one. Moreover, what was obtained by the well-known manufacturing method can also be used. For example, it is manufactured by applying a predetermined monomer to copolymerization conditions, but production in a high pressure low density polyethylene production apparatus is possible. It is usually produced by radical polymerization. As a catalyst used at this time, a free group generation initiator (for example, dialkyl peroxides, diacyl peroxides, peroxy esters, ketone peroxides, peroxy ketals, hydroperoxides, azo compounds, etc.) Is preferably used. The polymerization apparatus may use a continuous stirred tank reactor or a continuous tubular reactor generally used in high pressure radical polymerization of ethylene. Polymerization pressure is 1000 to 5000 kg / cm ² It is preferable to make the polymerization temperature into about 100-400 degreeC.

As the latter light stabilizer, for example, bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and bis- (N-methyl-2,2,6,6-tetramethyl- In addition to 4-piperidinyl) sebacate, hindered amine radical scavengers, such as a compound disclosed by Unexamined-Japanese-Patent No. 4-82625, a piperidyl radical scavenger, etc. are mentioned, for example.

The addition amount of an optical stabilizer is not specifically limited, Generally, within the range of about 0.1 to 10 weight% in surface layer part, it can set suitably according to the kind of optical stabilizer to be used, etc .. In particular, when using the said polymeric light stabilizer, about 5 to 10 weight% is preferable in a surface layer part.

The layer structure in the makeup sheet of this invention is not limited as long as it has the said predetermined polyolefin resin layer, The same structure as a well-known makeup sheet can be employ | adopted. For example, the cosmetic sheet in which a surface layer is formed at least on a base material sheet, a polyolefin resin layer, and also a surface protection layer as needed is mentioned.

The formation method of each layer is not specifically limited, For example, printing, such as gravure printing, flexographic printing, silk screen printing, offset printing, transfer printing, etc .; Application of spraying, rollers, brushes and the like; Any one such as laminating molded articles such as a sheet-like article can be employed. From these methods, it can select suitably combining according to the characteristic, raw material, etc. of each layer.

The thickness of each layer is not limited, either, and can be appropriately determined according to the use, properties, and the like of the final product. Usually, it can be in the range of about 0.1-500 micrometers.

Hereinafter, the structure of each layer is demonstrated as an example of embodiment of the said makeup sheet.

Substrate sheet

A base material sheet is laminated | stacked in order on the surface (surface) etc., and the to-be-adhered body mentioned later is laminated | stacked on the back surface.

As the base sheet, for example, one formed of a thermoplastic resin can be preferably used. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene vinyl acetate copolymer, ethylene acrylic acid copolymer, ethylene acrylic acid Ester copolymers, ionomers, acrylic esters, methacrylic esters and the like.

The base sheet may be colored as necessary. In this case, a coloring agent (pigment or dye) can be added and colored with respect to the above thermoplastic resin. As a coloring agent, various dyes can also be used other than organic pigments, such as inorganic pigments, such as titanium dioxide, carbon black, and iron oxide, and phthalocyanine blue, for example. These can select 1 type, or 2 or more types from what is known or commercially available. Moreover, the addition amount of a coloring agent can also be set suitably according to a desired color tone.

The base sheet may contain various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers and the like, as necessary.

Although the thickness of a base material sheet can be suitably set according to the use of a final product, a usage method, etc., it is generally preferable to set it as 50-250 micrometers.

In the base material sheet, corona discharge treatment can also be performed on the surface (surface) in order to solidify adhesion | attachment of the ink which provides a pattern layer as needed. What is necessary is just to perform the method and conditions of a corona discharge process in accordance with a well-known method.

In addition, if necessary, a corona discharge treatment or a primer layer may be formed on the back side of the base sheet for lamination with an adherend described later. As a material for forming a primer layer, it is polyester resin, polyurethane resin (especially 2-component curable resin of polyacryl polyol, polyester polyol, polyether polyol, etc., and isocyanate compound), acrylic resin, polycarbo, for example. Compounds, such as alkyl titanate and ethylene imine, can also be used besides resins, such as a nate resin, a vinyl chloride / vinyl acetate copolymer, polyvinyl butyral resin, and a nitrocellulose resin. These can be used as they are or in the state dissolved or dispersed in a solvent, and a primer layer can be formed by a well-known printing method, a coating method, etc.

Pattern

The pattern layer may also represent letters, figures, and the like, in addition to patterns or shapes of natural materials such as wood grain and knots.

Formation of a pattern layer can be preferably performed by well-known printing methods, such as gravure printing, flexographic printing, silkscreen printing, offset printing, using the ink which is excellent in adhesiveness with a coloring thermoplastic resin layer. have.

As said ink, the ink containing a coloring agent and a binder can be used generally. What is necessary is just to select a binder of ink suitably from a well-known or commercial item according to the material of a base sheet, etc. For example, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins (preferably polyester urethane resins), acrylic resins, vinyl chloride / vinyl acetate copolymers, cellulose resins and the like can be used. have. These can use 1 type (s) or 2 or more types. In addition, a coloring agent is not specifically limited, A well-known coloring agent can be used. For example, Inorganic pigments, such as a titanium bag, zinc-ized, iron-oxide, pearl, ultramarine, cobalt blue, sulfur titanium, and carbon black; Organic pigments (including dyes) such as isoindolinone, kanji yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indaslene blue RS, and aniline black; Metal pigments such as aluminum and brass; And brass luster (pearl) pigments made of thin powder such as titanium dioxide coated mica and basic lead carbonate. These may be used alone or in combination of two or more.

Adhesive layer

In this invention, Preferably, an adhesive bond layer is interposed between a patterned layer and a polyolefin resin layer. The adhesive agent used as an adhesive bond layer can be suitably selected from the well-known or commercially available adhesives according to the component which comprises a pattern layer or a polyolefin resin layer. For example, various adhesive agents, such as polyurethane resin, polyacrylic resin, polycarbonate resin, and epoxy resin, can be used. In addition to the reaction curing type, the adhesive may be any one of a hot melt type, an ionizing radiation curing type, and an ultraviolet curing type.

What is necessary is just to perform according to a well-known method according to the kind of adhesive agent etc. which are used as an adhesion method. For example, thermosetting properties such as a method of coating onto a pattern layer by melt extrusion (extrusion coating method) using a polyolefin resin such as polyethylene or polypropylene, a polyester resin, a polyurethane resin, or an epoxy resin Coating the adhesive which added crosslinking agents, such as an isocyanate and an amine, polymerization initiators, such as methyl ethyl ketone peroxide, hydroperoxide, and azabisisobutyronitrile, polymerization promoters, such as cobalt naphthenate and dimethylaniline, as needed to resin. And dry lamination. Moreover, in this invention, a pattern layer and a polyolefin resin layer can also be laminated | stacked by thermocompression bonding using the adhesive which can be thermally crimped | bonded.

Moreover, in this invention, well-known adhesion | stimulation promotion processes, such as a corona discharge treatment, a plasma treatment, a degreasing treatment, and a surface roughening process, can also be given to an adhesive surface as needed.

Although the thickness of an adhesive bond layer differs according to the kind etc. of adhesive agents used, it can be about 0.1-30 micrometers generally.

Polyolefin  Resin layer

In this embodiment, a polyolefin resin layer is formed on a pattern layer (next adhesive layer). In this case, it is preferable that a polyolefin resin layer is a transparent layer. Moreover, as long as a pattern layer can be confirmed, a coloring transparent layer, a coloring semitransparent layer, etc. may be sufficient.

What is necessary is just to have comprised the structure and formation method of polyolefin resin as mentioned above. For example, as shown in FIG. 2, it can also be set as the two-layered constitution of surface layer part (extrusion resin layer 2) and lower layer (extrusion resin layer 1). In this case, for example, the surface layer portion may be formed of a polyolefin resin composition containing a polymer type antistatic agent and an acid-modified polyolefin resin, and the lower layer may be formed of a polyolefin resin composition not containing a polymer type antistatic agent. The surface layer portion and the lower layer may be formed in a sheet form by co-extrusion, or may bond two sheets extruded separately. Thereby, a polyolefin resin layer can be formed.

Surface protective layer

In the present invention, the surface protective layer (so-called OP layer: overprint layer, transparency protective layer) is provided as the outermost surface layer. The surface protective layer is preferably transparent (transparent protective layer), and may be colored within the limits. Moreover, it can also be translucent in the range which can confirm a pattern layer. By forming a surface protective layer, it is possible to cover the thing which is easy to generate | occur | produce the flaw of the makeup sheet surface, and to improve scratch resistance.

Although it does not specifically limit as a material used for a surface protection layer, Although the thing similar to a well-known makeup sheet can be used, In this invention, it is preferable to use two-component curable urethane type resin. The two-component curable urethane-based resin is not particularly limited as long as it has a polyol as its main ingredient and an isocyanate is a crosslinking agent (curing agent), and commercially available products may be used. As polyol and isocyanate, what was enumerated by the said adhesive bond layer can be used preferably.

In this invention, it is preferable to use an ionizing radiation curable resin as a surface protective layer. When the ionizing radiation curable resin is used, more excellent scratch resistance, weather resistance and the like can be obtained.

As the ionizing radiation curable resin, a known or commercially available product can be used. Specifically, a composition containing at least one of prepolymers, oligomers and monomers having a polymerizable unsaturated bond or an epoxy group in a molecule is used.

Examples of the prepolymer or oligomer include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols. For example, methacrylates, such as polyester methacrylate, polyether methacrylate, polyol methacrylate, melamine methacrylate, urethane acrylates, polyester acrylate, polyether acrylate, urethane acrylate And acrylates such as polyol acrylate and melamine acrylate.

As a monomer, Styrene-type monomers, such as styrene and (alpha) -methylstyrene, Acrylic acid esters, such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, and phenyl acrylate, methyl methacrylate, Methacrylic acid esters, such as ethyl methacrylate, propyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, and lauryl methacrylate.

Substituted aminoalcohol esters of unsaturated acids include acrylic acid-2- (N, N-diethylamino) ethyl, methacrylic acid-2- (N, N-diethylamino) ethyl and acrylic acid-2- (N, N-di Benzylamino) methyl, acrylic acid-2- (N, N-diethylamino) propyl, and the like.

In addition, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neobenzyl glycol diacrylate, 1,6-hexanediol diacrylate and ethyl carbitol acrylate , Polyfunctional compounds such as diethylene glycol diacrylate, triethylene glycol diacrylate, dipropylene glycol diacrylate, ethylene glycol acrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, and ( Or) polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropioate, dipentaerythritol tetrathioglycol, and the like. Moreover, trimethylolpropane triacrylate, pentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are mentioned as an acrylate-type monomer more than trifunctional.

The formation method of the surface protection layer (transparent protective layer) by an ionizing radiation curable resin can also be followed by a well-known method, For example, the composition (paint) containing an ionizing radiation curable resin is manufactured, and a coating film is formed using this. In addition, the coating film may be cross-cured by irradiating electron beams under known use conditions (175 keV and 5 Mrad (50 kGy)). When using ionizing radiation hardening type resin, it is preferable to provide a primer layer (especially the primer layer by urethane system resin) on a 2nd polyolefin resin layer as a base.

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

Embossing is performed to give the makeup sheet a desired texture such as a wooden board surface. For example, after softening the polyolefin-based resin by heating on a heating drum, it is further heated to 160 to 180 DEG C with an infrared radiation heater, pressurized, shaped and cooled by an embossing plate provided with a concave-convex shape of a desired shape. Can be. This can be done using a known sheet or roto embossing machine. As an uneven | corrugated shape, a wood grain conduit groove | channel, a relief shape (rich uneven | corrugated shape of a rich ring), a hairline, sand grain, a checkered pattern, etc. are mentioned, for example, A desired shape can be suitably selected from these.

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

Although the thickness of a surface protection layer is not limited, Usually, it is preferable to set it as 0.1-50 micrometers, especially 1-20 micrometers.

2. Vanity

In the decorative plate of the present invention, the decorative sheet of the present invention is laminated on the adherend. More specifically, the sheet is laminated on the adherend such that the transparent protective layer of the makeup sheet is the outermost surface layer.

Adherend

As a to-be-adhered body, the goods of various shapes, such as the board | plate material of various materials, a curved board, etc., a three-dimensional article [molded article], a sheet (or film), are object. As a material used for these, wooden boards, such as a timber veneer which consists of trees, such as a cedar, a cypress, a pine tree, a king, teak, a wooden board, a particle board, and a medium density fiber board (MDF); Metals or alloys such as iron, aluminum, titanium, stainless steel, brass, and Al-Mg alloys; Organic polymers (resins) such as acrylic resins, polycarbonates, ethylene / vinyl acetate copolymers, ethylene vinyl acetates, polyesters, polystyrenes, polyolefins, ABS resins, phenol resins, polyvinyl chloride, cellulose resins, and rubbers Can be mentioned. Moreover, as a raw material used only as a board | plate material or a three-dimensional article, Ceramic, such as glass, ceramics, alumina; Cement hardening bodies such as ALC (foamed lightweight concrete); Non-cement ceramic materials such as calcium silicate and gypsum can also be applied. Moreover, as a raw material used only as a sheet (or film), papers, such as a high quality paper and a Japanese paper; The present invention can also be applied to nonwoven fabrics or woven fabrics containing fibers such as carbon, asbestos, potassium titanate, glass, and synthetic resins.

To the adherend  Lamination

Lamination | stacking of a makeup sheet to a to-be-adhered body can be made similar to lamination | stacking of a well-known makeup sheet. For example, a cosmetic sheet can be preferably laminated by adhesion on a to-be-adhered body using an adhesive agent.

As an adhesive which can be used, adhesives of any form, such as a thermoplastic resin type, a thermosetting resin type, and a rubber type, can be used, for example. These can use a well-known thing or a commercial item.

As the thermoplastic resin adhesive, polyvinyl acetate resin, polyvinyl alcohol, polyvinyl acetal (polyvinyl formal, polyvinyl butyral, etc.), cyanoacrylate, polyvinyl alkyl ether, polyvinyl chloride, polyamide, polymethacrylic acid Methyl, nitrocellulose, cellulose acetate, thermoplastic epoxy, polystyrene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and the like.

Thermosetting resin adhesives include urea resin, melamine resin, phenol resin, resorcinol resin, furan resin, epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide, polyamideimide, polybenzimidazole, polybenzothiazole, and the like. This is illustrated.

Rubber (elastomer) adhesives include natural rubber, recycled rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, stereo rubber (synthetic natural rubber), Ethylene propylene rubber, block copolymer rubber (SBS, SIS, SEBS etc.) etc. are illustrated.

The cosmetic sheet of the present invention can exhibit a good antistatic performance for a long time by simultaneously containing a polymer type antistatic agent in the polyolefin resin layer with an acid-modified polyolefin resin, and further, whitening during bending is suppressed. This is based on the acid-modified polyolefin resin improving the compatibility of the polymer type antistatic agent and the polyolefin resin.

The cosmetic sheet of this invention which has such a characteristic can be used suitably for a bending process (for example, V cutting process). The cosmetic sheet can be used as a cosmetic sheet for indoor building materials, exterior and semi-exterior building materials, and can also be widely used as a cosmetic sheet for home appliances, office equipment, and instruments. In particular, it can be used suitably for the use which bend | folds a makeup sheet and laminate | stacks according to the shape of an adherend.

BEST MODE FOR CARRYING OUT THE INVENTION [

Hereinafter, the features of the present invention will be further clarified by way of examples and comparative examples. However, the scope of the present invention is not limited to the Example.

&Lt; Example 1 >

A cosmetic sheet having a structure shown in FIG. 2 was prepared.

(1) Production of Sheet Having Polyolefin Resin Layer

By adding 10 weight% of coloring agents (titanium oxide), the colored polypropylene resin film 1 (thickness: 80 micrometers) was prepared, and the corona discharge process was given to the outer surface and the back surface. Gravure printing of the coloring ink which used the two-component curable urethane type-resin as a binder was carried out on this surface (solid pattern), and the patterned layer 2 of a grain-pattern was formed with the ink which used acrylic resin as a binder on it. Further, on the back side, a primer layer 6 made of a urethane resin as a binder was formed by gravure printing to obtain a printing sheet.

Subsequently, an adhesive layer 3 containing a two-liquid curable urethane resin was formed to a thickness of 15 μm on the pattern layer 2 of the printing sheet, and then the surface layer 5 (0.01) was formed as a polyolefin resin layer on the coating film. The polypropylene resin layer which consists of two layers of mm) and lower layer 4 (0.07 mm) was laminated | stacked, and the sheet | seat in which the polyolefin resin layer was laminated | stacked was obtained.

At this time, 12.5% by weight of the polymer type antistatic agent (product name "Peresart 303" Sanyo Kasei Kogyo Co., Ltd.), acid-modified polyolefin resin (product name "Emerix 1010" Sanyo Kasei Kogyo Co., Ltd.) 5% by weight on the surface layer 5 And 4375 weight ppm of an ultraviolet absorber (product name "LA-63" manufactured by Asahi Denka Kogyo Co., Ltd.). On the other hand, the lower layer 4 contained 5000 ppm by weight of the same ultraviolet absorber as described above.

(2) Formation of Surface Protective Layer

Surface protective layers 7 and 8 were formed on the polyolefin resin layer of the sheet | seat obtained by said (1).

First, corona discharge treatment was performed on the polyolefin resin layer. Subsequently, a coating film containing a transparent top coat, which is a mixture of acryl polyol, 1,6-hexamethylene diisocyanate, and silica particles having an average particle diameter of 2 μm, was formed by gravure roll coating on the corona discharge treated surface. The thickness of the surface protective layer was 4 micrometers.

<Example 2>

A cosmetic sheet was produced in the same manner as in Example 1 except that the content of the compatibilizer was 10% by weight.

<Example 3>

A cosmetic sheet was produced in the same manner as in Example 1 except that the polymer type antistatic agent was used as a polyether ester-amide type polymer type antistatic agent (product name "IRGASTAT P 18" manufactured by Chiba Specialty Chemical Co., Ltd.).

<Example 4>

A cosmetic sheet was produced in the same manner as in Example 3 except that the content of the compatibilizer was 10% by weight.

&Lt; Comparative Example 1 &

A cosmetic sheet was produced in the same manner as in Example 1 except that no compatibilizer was used.

Comparative Example 2

A cosmetic sheet was produced in the same manner as in Example 3 except that no compatibilizer was used.

&Lt; Reference Example 1 &

A cosmetic sheet was produced in the same manner as in Example 1 except that neither the polymer type antistatic agent nor the compatibilizer was used.

&Lt; Test Example 1 >

<Bending test of the cosmetic sheet>

After the cosmetic sheet prepared in Examples, Comparative Examples and Reference Examples was bent by 180 °, the presence or absence of whitening of the surface of the cosmetic sheet was checked.

The state of the outer surface of each makeup sheet after a test is shown in FIG.

&Lt; Reference Example 1 &

On the basis of the whitening state of the one (which does not include both the polymer type antistatic agent and the compatibilizing agent), the whitening state of Comparative Example 1 and Comparative Example 2 (both of which contain the polymer type antistatic agent and does not include the compatibilizing agent) In evaluation, it turns out that a whitening degree is large. On the other hand, when the whitening state of Examples 1 and 3 containing 5 weight% of compatibilizers is evaluated, whitening is suppressed. In addition, when the whitening state of Examples 2 and 4 containing 10 wt% of a compatibilizer was evaluated, the whitening state was about the same as that of Reference Example 1 containing no polymeric antistatic agent, and the whitening by the addition of the polymeric antistatic agent. It can be seen that is sufficiently suppressed.

According to this invention, the cosmetic sheet containing a polymeric antistatic agent can provide the cosmetic sheet by which the whitening at the time of bending was suppressed.

Claims (15)

A makeup sheet for laminating onto an adherend, wherein the makeup sheet has at least a polyolefin resin layer, and the cosmetic sheet contains a polymer type antistatic agent and an acid-modified polyolefin resin in the polyolefin resin layer. The cosmetic sheet according to claim 1, wherein at least the pattern layer and the polyolefin resin layer are laminated on the base sheet, and the polyolefin resin layer is composed of one layer or two or more layers, and the surface layer portion of the polyolefin resin layer is formed. A cosmetic sheet containing a polymer type antistatic agent and an acid-modified polyolefin resin. The cosmetic sheet is a laminate of at least a pattern layer, a polyolefin-based resin layer and a surface protective layer on a base sheet, and the polyolefin-based resin layer is composed of one or two or more layers, and the polyolefin-based number. A cosmetic sheet containing a polymer type antistatic agent and an acid-modified polyolefin resin at the surface layer portion of the stratum layer. The cosmetic sheet according to claim 2 or 3, wherein the surface layer portion is an area from the outer surface of the polyolefin resin layer to a depth of 1/2 or less of the thickness of the resin layer. The cosmetic sheet according to claim 2, wherein the polyolefin-based resin layer has a thickness of 30 µm or more, and the surface layer portion is an area from the outer surface of the resin layer to a depth of 15 µm or less. The cosmetic sheet according to claim 1, wherein the polymer type antistatic agent is at least one of polyether-ester-amide and polyether-polyolefin block polymer. The cosmetic sheet according to claim 1, wherein the polyolefin resin layer contains 3 to 35% by weight of a polymer type antistatic agent. The cosmetic sheet according to claim 2, wherein the surface layer portion contains 3 to 35 wt% of a polymer type antistatic agent. The cosmetic sheet according to claim 1, wherein 3 to 20% by weight of the acid-modified polyolefin resin is contained in the polyolefin resin layer. The cosmetic sheet according to claim 2, wherein 3 to 20% by weight of the acid-modified polyolefin resin is contained in the surface layer portion. The cosmetic sheet according to claim 1, wherein the polyolefin resin layer further comprises at least one of an ultraviolet absorber and a light stabilizer. The cosmetic sheet according to claim 11, wherein the light stabilizer is a polymer light stabilizer. The cosmetic sheet according to claim 12, wherein the polymer type light stabilizer is a copolymer of cyclic aminovinyl compound represented by the following formula (1) and ethylene. &Lt; Formula 1 >

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The cosmetic sheet according to claim 2, wherein 5 to 10% by weight of the polymer type light stabilizer is contained in the surface layer portion. The decorative sheet of Claim 1 by which the makeup sheet of Claim 1 is laminated | stacked on a to-be-adhered body.

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