JP2001181413A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a decorative sheet having excellent appearance, interlayer adhesivity, scratch resistance, folding whitening resistance, weather resistance, transparency, etc. SOLUTION: A sheet is formed from a polyolefin-based resin material consisting essentially of a polyolefin-based resin composition comprising an ethylene/propylene random copolymer having 0.5-30 g/10 minutes MFR at 230 deg.C and 1-6 wt.% ethylene content by NMR method, a copolymer of ethylene and a cyclic aminovinyl compound of the formula (1) (R1 and R2 are each independently a hydrogen atom or a methyl group; R3 is a hydrogen atom or a 1-4C alkyl group) and, optionally a low-density polyethylene. The sheet is subjected to decorative treatment to give a decorative sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a decorative sheet,
In particular, it relates to a decorative sheet suitable for use in interiors of buildings, surface decoration of fittings, vehicle interiors, and the like.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet used for the above-mentioned applications, a decorative sheet (for example, Japanese Patent Publication No. 58-14312, etc.) which uses a polyvinyl chloride film and which is decorated by printing, embossing or the like. In recent years, as an alternative to this, (I) a decorative sheet using a polyolefin film such as polyethylene or polypropylene has been proposed (see JP-A-2-128843), and (II) As an improved specification of I), a product obtained by mixing an olefin elastomer with a polyolefin resin obtained by graft-polymerizing a polar functional group (Japanese Unexamined Patent Publication No.
210808) or a mixture of a polyolefin resin and a polyurethane resin using a compatibilizer (Japanese Patent Application Laid-Open No. 7-26038).

[0003]

However, the proposed decorative sheet using the above-mentioned polyolefin resin sheet is not always satisfactory. That is, for the interior and exterior of buildings, for surface decoration of fittings and furniture, surface decoration sheets used for vehicle interior, etc., usually include the following
Functions such as (1) to (10) are required.

(1) Thermoformability comparable to polyvinyl chloride. In particular, the change in elongation at constant load with temperature change should be gradual and continuous, almost equivalent to that of polyvinyl chloride.
Further, deterioration of material mechanical properties such as a decrease in strength does not occur during the process from heating to cooling.

(2) Creep resistance. Exterior and interior materials are often subjected to a constant load by fittings and furniture for long periods of time, and when creep deformation occurs, the loaded parts are turned up or peeled off. Therefore, it is required that the material does not cause creep deformation as much as possible. (3) Cold bending strength. If the stress is not sufficiently relaxed by performing a bending process such as a V-cut process in cold weather, whitening, cracking, breakage, and the like are likely to occur in the bent portion.

(4) Resistance to organic solvents. The decorative sheet prevents the decorative sheet from swelling and deforming due to the solvent in the adhesive for bonding the decorative sheet and the adherend. The same applies when a decorative sheet having a multilayer structure is obtained. (5) Elongation at break, impact strength. When bending by V-cut processing or the like, this property is required in order to prevent cracks in the bent portion. (6) It has a moderate flexural modulus. This is necessary so that the followability of the decorative sheet in the bent portion is sufficient.

(7) The transparency of the topsheet is good. (8) Whitening and turbidity due to recrystallization do not occur even when heating and cooling accompanying embossing and the like are applied. (9) Easy adhesion. In particular, in the case of a base sheet, it is required that a decorative sheet can be easily adhered to various adherends using a wide range of adhesives when used. (10) Excellent weather resistance.

The decorative sheet having the above specification (I) is difficult to mass-produce industrially, and the polyolefin resin has a high degree of crystallinity. The change in physical properties is steep, and it has the disadvantage that the processable condition range is narrower than the conventional general-purpose polyvinyl chloride sheet, and among the above conditions,
The conditions (1) and (5) to (10) were not sufficiently satisfied. For (II) specifications, the conditions of (1), (5), and (6) were improved by mixing the olefin elastomer, and thermoformability and embossability were improved, but the transparency was improved. The properties, weather resistance and heat resistance were insufficient.

Recently, in order to solve the above-mentioned disadvantages of the conventional decorative sheet using an olefin resin, the same heat as a decorative sheet using a polyvinyl chloride resin while using an olefin resin is used. We succeeded in providing a decorative sheet having moldability, weather resistance, and transparency. Specifically, on a colored film whose main material is polypropylene, an elastomer, a coloring agent, and a base sheet made of an inorganic filler, molecules composed of a mixed system of isotactic polypropylene and atactic polypropylene are used as a surface sheet. It is a decorative sheet in which a colorless or colored transparent soft polypropylene resin film having a composite three-dimensional structure is laminated, and a pattern is applied to one or both of a base sheet and a surface sheet as necessary. However, even the proposed decorative sheet using a polyolefin resin sheet as described above is not completely satisfactory. That is, for the interior and exterior of buildings, for surface decoration of fittings and furniture, surface decoration sheet used for vehicle interior, etc., furthermore, the following
Functions such as (11) and (12) are required.

(11) Good productivity. Specifically, neck-in and surging phenomena are unlikely to occur. (12) The adhesion strength between the coating film and the polyolefin resin sheet does not decrease during long-term use. That is, in order to usually improve the abrasion resistance of a decorative sheet, adjust gloss, and the like, a top coat layer (OP; also referred to as Over Paint varnish) made of a resin such as a two-component curable polyurethane is formed on the surface of the decorative sheet. There are many. On the other hand, in order to impart the weather resistance of the decorative sheet, a weather stabilizer (light stabilizer) and an ultraviolet absorber are usually added to at least the outermost polyolefin resin sheet of the decorative sheet. And the like have poor compatibility with general polyolefin-based resins, and bleed to the sheet surface during long-term use, and the bleeding weather stabilizer and the like act like a release agent to form the above-mentioned top coat layer and sheet. Decreases adhesion.

An object of the present invention is to improve the performance of the conventional decorative sheet using an olefin resin with respect to the above-mentioned quality of the decorative sheet. The physical properties are such that there is little bleeding in the aging / heat resistance test, it does not hinder the adhesion to the layer (printing layer, transparent overcoat layer, substrate layer) that the resin material contacts, and it is hard to be scratch-resistant and resistant to bending whitening. It is an object to provide a decorative sheet having the following. It is another object of the present invention to provide a decorative sheet having thermoformability, weather resistance, and transparency equal to or higher than that of a decorative sheet using a polyvinyl chloride resin while using an olefin resin.

[0012]

The present inventors have conducted a number of experiments and studies to solve the above-mentioned problems, and have found that the decorative sheet may be a single-layer sheet or at least a base sheet and a decorative sheet. It has been found that a highly practical olefin resin decorative sheet can be obtained by forming a two-layer structure of a top sheet to be laminated on each sheet and sharing each condition required for the decorative sheet described above with each sheet. The present invention has been made.

[0013] That is, the present invention relates to a method for preparing M
An ethylene / propylene random copolymer having an FR of 0.5 to 30 g / 10 min and an ethylene content of 1 to 6% by weight by NMR; 90 to 98% by weight, ethylene and a cyclic compound represented by the following formula (1) A sheet formed of a polyolefin-based resin material mainly composed of a polyolefin-based resin composition containing a copolymer with an aminovinyl compound; I will provide a.

[0014]

Embedded image

(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.)

Further, the present invention relates to an MFR at 230 ° C.
Is an ethylene / propylene random copolymer having an ethylene content of 1 to 6% by weight according to an NMR method at 0.5 to 30 g / 10 minutes; a low MFR at 75 to 96% by weight and 190 ° C. of 1 to 10 g / 10 minutes. Polyolefin based on polyolefin resin composition containing 2 to 15% by weight of a density polyethylene; and a copolymer of ethylene and a cyclic aminovinyl compound represented by the following formula (1); A sheet formed of a resin material,
Provided is a decorative sheet subjected to a decoration process.

[0017]

Embedded image

(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.) A multilayer sheet having at least a base sheet and a topsheet, wherein the topsheet is 23
MFR at 0 ° C of 0.5 to 30 g / 10 min, NMR
An ethylene / propylene random copolymer having an ethylene content of 1 to 6% by weight; a copolymer of 90 to 98% by weight with ethylene and a cyclic aminovinyl compound represented by the following formula (1); % By weight of a polyolefin-based resin composition containing a polyolefin-based resin composition as a main component, and subjecting one or both of the base sheet and the surface sheet to a decoration treatment as necessary. To provide a decorative sheet.

[0019]

Embedded image

(Wherein, 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 present invention is also a multilayer sheet having at least a base sheet and a topsheet, wherein the topsheet has an MFR at 230 ° C. of 0.5 to 30 g / 1.
0 minute, ethylene-propylene random copolymer having an ethylene content of 1 to 6% by weight by NMR method; 75 to 96% by weight, low-density polyethylene having an MFR at 190 ° C. of 1 to 10 g / 10 minutes; %, And a copolymer of ethylene and a cyclic aminovinyl compound represented by the following formula (1); formed from a polyolefin-based resin material mainly composed of a polyolefin-based resin composition containing 2 to 10% by weight. Provided is a decorative sheet, which is obtained by subjecting one or both of the base sheet and the surface sheet to a decoration treatment as required.

[0022]

Embedded image

(Wherein, 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 present invention also provides any one of the above decorative sheets, characterized in that an overcoat layer made of a resin having an isocyanate group is laminated on the surface of the sheet.

In the present invention, the polyolefin resin material may further comprise a triaryltriazine type ultraviolet absorber represented by the following formula (2) added to the resin composition in an amount of 0 to 100 parts by weight of the resin composition. .1 to 1 part by weight of the decorative sheet is provided.

[0026]

Embedded image

(Wherein, R _{4 to} R ₈ each independently represent an alkyl group having 1 to 10 carbon atoms)

[0028]

Embodiments of the present invention will be described below.

The decorative sheet of the present invention is a polyolefin resin material mainly composed of a polyolefin resin composition obtained by blending an ethylene / propylene random copolymer with an ethylene / cyclic aminovinyl compound copolymer and optionally a low-density polyethylene. And is subjected to a decoration process.

I. Polyolefin resin material (1) Polyolefin resin composition <Ethylene / propylene random copolymer> The ethylene / propylene random copolymer used in the present invention is N
It has an ethylene content of 1 to 6% by weight according to the MR method. If the ethylene content is less than the above range, it is not preferable because the bending whitening resistance is reduced, and if it is more than the above range, the scratch resistance is inferior.

The random copolymer has an MFR (melt flow rate; JIS-K6758 (230 ° C., 2.
The value measured according to 16 kg load) is 0.5 to 30.
g / 10 minutes. If the MFR is less than the above range, the molding processability is poor, which is not preferable. If the MFR is more than the above range, the material strength and weather resistance tend to decrease, which is not preferable.

The method for producing the ethylene / propylene random copolymer is not particularly limited, and any one produced by a conventionally known method can be used, and various commercially available ones can be used. . <Low-density polyethylene> The low-density polyethylene optionally used in the present invention is MFR (JIS-K6760).
(Measured according to (190 ° C., 2.16 kg load)) is 1 to 10 g / 10 min. If the MFR is less than the above range, the dispersibility of the low-density polyethylene deteriorates, so that it is not preferable.

The method for producing such low-density polyethylene is not particularly limited, and those produced by a conventionally known method can be used, and various commercially available ones can be used.

<Ethylene / Cyclic Aminovinyl Compound Copolymer> The resin composition includes a copolymer of ethylene and a cyclic aminovinyl compound represented by the following formula (1) (an ethylene / cyclic aminovinyl compound copolymer) ) Is compounded.

[0035]

Embedded image

In the above formula (1), 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 vinyl compound represented by the formula (1) can be synthesized by a known method. The content of the cyclic aminovinyl compound in the ethylene / cyclic aminovinyl compound copolymer is 1 to 10% by weight, preferably 2 to 8% by weight, and the MI of the copolymer is 0.1 to 500%.
g / 10 min. , Preferably 0.5 to 200 g / 10
min. Is desirable.

The ethylene / cyclic aminovinyl compound copolymer is produced by subjecting necessary monomers to copolymerization conditions, but can be produced by a high-pressure low-density polyethylene production apparatus. Usually produced by radical polymerization, the catalyst used is a free radical generating initiator such as dialkyl peroxide, diacyl peroxides, peroxyesters, ketone peroxides, peroxyketals, hydroperoxides, azo Compounds and the like are useful. As the polymerization apparatus, a continuous stirred tank reactor or a continuous tube reactor generally used in a high-pressure radical polymerization method of ethylene can be used. The polymerization pressure is 1
About 000-5000 kg / cm ² , polymerization temperature 100
About 400 ° C.

(2) Polyolefin Resin Material The polyolefin resin material used in the present invention may further contain a triaryltriazine type ultraviolet absorber in addition to the above polyolefin resin composition. <Triaryltriazine-type ultraviolet absorber> The triaryltriazine-type ultraviolet absorber is represented by the following formula (2).

[0039]

Embedded image

Here, in the formula (2), R _{4 to} R ₈ each independently represent an alkyl group having 1 to 10 carbon atoms. In the above formula (1), if R _{4 to} R ₈ are hydrogen, it is not preferable because bleeding is liable to occur, and if the number of carbons exceeds the above range, weather resistance is inferior. The method for obtaining the triaryltriazine type ultraviolet absorber represented by the above formula (2) is not particularly limited, and a commercially available product can be used.

<Other Ingredients> The polyolefin resin material of the present invention contains, in addition to the above-mentioned ultraviolet absorbent and weather stabilizer, other additional components as long as the effects of the present invention are not significantly impaired. can do. Such optional components include antioxidants, crystal nucleating agents, clarifying agents, lubricants, antiblocking agents, antistatic agents, antifogging agents, neutralizing agents, and metal inerts used in ordinary polyolefin resin materials. Agents, colorants, dispersants, peroxides, fillers, and optical brighteners.

In the present invention, in addition to the above-mentioned triaryltriazine type ultraviolet absorber, 2- (2'-
Hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2'-
(Hydroxy-3′-tert-amyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2 ′
2 ′ such as -hydroxy-3′-isobutyl-5′-methylphenyl) -5-chlorobenzotriazole and 2- (2′-hydroxy-3′-isobutyl-5′-propylphenyl) -5-chlorobenzotriazole -Hydroxyphenyl-5-chlorobenzotriazole UV absorbers, 2- (2'-hydroxy-3 ', 5'-di-
tert-butylphenyl) benzotriazole, 2-
Benzotriazole-based ultraviolet absorbers such as 2'-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as (2'-hydroxy-5'-methylphenyl) benzotriazole; 2,2'-dihydroxy-4-methoxybenzophenone; , 2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,
2,2′- such as 4′-tetrahydroxybenzophenone
Dihydroxybenzophenone ultraviolet absorbers, benzophenone ultraviolet absorbers such as 2-hydroxybenzophenone ultraviolet absorbers such as 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone, phenyl salicylate, 4-t- Butyl-phenyl-
A salicylate-based ultraviolet absorber such as salicylate is used.

In addition, a reactive ultraviolet absorber in which an acryloyl group or a methacryloyl group is introduced into a benzotriazole skeleton may be used. Alternatively, when high transparency is not required, an inorganic UV absorber can be added. As the inorganic ultraviolet absorber, titanium oxide, cerium oxide, iron oxide or the like having a particle size of 0.2 μm or less is used. The amount of these UV absorbers is usually about 0.1 to 5% by weight based on the total amount of the polyolefin resin material.

In order to further prevent deterioration due to ultraviolet rays and improve weather resistance, it is preferable to add a radical scavenger as another light stabilizer. Examples of the radical scavenger include bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (N-methyl-2,
(2,6,6-Tetramethyl-4-piperidinyl) sebacate, and a hindered amine radical scavenger such as a compound disclosed in Japanese Patent Publication No. 4-82625 and a piperidyl radical scavenger are used. The addition amount of these radical scavengers is usually about 0.1 to 5% by weight based on the total amount of the polyolefin resin material.

When a light stabilizer comprising a hindered amine radical scavenger is added to the polyolefin resin material, an ink layer, an adhesive layer, etc. adjacent to a decorative sheet (or a surface sheet in the case of a multilayer). If a resin containing no chlorine atom in the molecule, such as a urethane resin, a polyester resin, or a polyamide resin, is used for the layer (2), the weather resistance is improved. If vinyl chloride / vinyl acetate copolymer,
When resins containing chlorine atoms in molecules such as chlorinated polyolefins are used, hydrogen chloride is generated from these resins by the action of ultraviolet rays or heat in a dechlorination reaction, which reacts with a hindered amine radical scavenger to reduce the action. Due to deactivation and inhibition, the weather resistance is not sufficiently improved.

<Composition Ratio> The content ratio of the ethylene / propylene random copolymer in the polyolefin resin composition is 90 to 98% by weight, and the content ratio of the ethylene / cyclic aminovinyl compound copolymer is 2 to 2% by weight. 10% by weight. When the content ratio of the ethylene / propylene random copolymer is less than the above range and the content ratio of the ethylene / cyclic aminovinyl compound copolymer exceeds the above range, it is not preferable in terms of economy. On the other hand, when the content ratio of the ethylene / propylene random copolymer exceeds the above range and the content ratio of the ethylene / cyclic aminovinyl compound copolymer is less than the above range, it is not preferable because the weather resistance is poor.

When low-density polyethylene is blended in the composition, the content of the ethylene / propylene random copolymer in the resin composition is 75 to 96% by weight,
The content ratio of the low-density polyethylene is 2 to 15% by weight,
The content ratio of the ethylene / cyclic aminovinyl compound copolymer is 2 to 10% by weight. When the content ratio of the ethylene / propylene random copolymer is less than the above range, the scratch resistance is poor, so that it is not preferable. If the content ratio of the low-density polyethylene is less than the above range, the molding processability is inferior, so that it is not preferable. If the content of the ethylene / cyclic aminovinyl compound copolymer is less than the above range, the weather resistance is inferior, and therefore, it is not preferable.

The content ratio of the triaryltriazine type ultraviolet absorber in the polyolefin resin material is as follows:
0.1 to 1 part by weight based on 100 parts by weight of the resin composition. If the proportion of the triaryltriazine type ultraviolet absorber is less than the above range, the weather resistance is inferior, which is not preferable. If it exceeds the above range, it is not preferable in terms of hue and economy.

The polyolefin-based resin material of the present invention can be obtained by mixing the above essential components and additional components that are blended as required, and melt-kneading them. For the melt-kneading, for example, a kneading machine such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader blender, a Brabender plastograph, a small batch mixer, a continuous mixer, a mixing roll, etc. Done using The kneading temperature is generally 180 to 270 ° C.
Done in Further, the kneader may be a combination of two or more of the above-described kneaders.

II. Decorative Sheet The decorative sheet of the present invention is a sheet made of the above-mentioned polyolefin-based resin material (hereinafter, also simply referred to as a “polyolefin resin sheet”), which has been subjected to a decorative treatment.
The decorative sheet may be a single-layer sheet or a multi-layer sheet having at least a surface sheet and a base sheet made of the polyolefin resin material.

(1) Single-layer sheet <Production of sheet> The above-mentioned decorative sheet is appropriately blended with the above-mentioned polyolefin-based resin material as required, and is formed into a film by a conventional method such as a calendar production method or an extrusion molding method. It can be obtained by: As the decorative sheet, any of a stretched sheet and an unstretched sheet can be used. The thickness of the decorative sheet is 30 to 200 micrometers, preferably 40 to 100 micrometers.

<Easy Adhesive Layer> When the decorative sheet is a single-layer sheet, it is possible to directly print a pattern or apply an adhesive to the polyolefin resin sheet itself, but it is possible to use an ink or an adhesive. If it is necessary to make the adhesive force between the agent and the polyolefin resin sheet stronger, apply an easy-adhesion layer to the surface of the polyolefin resin sheet,
An easy adhesion treatment such as a corona discharge treatment, a plasma treatment, and an ozone treatment can be performed.

The easy-adhesion layer (also referred to as a primer layer or an anchor layer) includes acryl, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane (also referred to as urethane resin), chlorinated polypropylene, chlorinated polyethylene. In particular, after the surface of the polyolefin resin sheet is subjected to an easy adhesion treatment such as a corona discharge treatment to impart an active hydrogen-containing polar functional group such as a hydroxyl group or a carboxyl group, polyurethane or chlorine is applied on the surface. It is desirable to form an easily adhesive layer of functionalized polypropylene. S

Examples of acryl include poly (methyl meth) acrylate, poly (ethyl meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate / (meth) acrylic Butyl acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, styrene / methyl (meth) acrylate copolymer, (meth) Acrylic resin consisting of a homo- or copolymer containing (meth) acrylate such as methyl acrylate / butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer (here, (meth) acrylic Means acryl or methacryl, and the same applies hereinafter).

Polyurethane is mainly composed of polyol (polyhydric alcohol) and isocyanate as a crosslinking agent (curing agent).
Polyurethane.

Polyols having two or more hydroxyl groups in the molecule include, for example, polyethylene glycol, polypropylene glycol, acrylic polyol,
Polyester polyol, polyether polyol and the like are used.

As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4-diphenylmethane diisocyanate,
Alternatively, aliphatic or alicyclic isocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used. Alternatively, adducts or multimers of these isocyanates are also used.

<Decoration treatment> The decoration treatment applied to the decorative sheet of the present invention includes coloring (transparent or opaque coloring) by adding a pigment, printing of a pattern, embossing (heating press).
And shaping by hairline processing, formation of a metal thin film layer, and the like.

Examples of the pigment addition include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, Hansa Yellow A, quinacridone, and permanent red 4R. ,
Organic pigments (or dyes) such as phthalocyanine blue, Indaslen Buri RS, and aniline black; metal pigments made of foil powder such as aluminum and brass; pearls made of foil powder such as titanium dioxide-coated mica and basic lead carbonate Gloss (pearl) pigments and the like. These are added and dispersed as powder or flaky foil pieces.

As the pattern printing, a pattern is formed by ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like. Examples of the pattern include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric figure, a character, a symbol, and a solid surface. The pattern is provided on the front, back, front and back surfaces, or between layers of the sheet.

Inks (or paints) used for pattern printing include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene as binders.
Polyester, polyurethane, acrylic, vinyl acetate,
Vinyl chloride / vinyl acetate copolymer, cellulosic resin,
And the like, or one kind or a mixture of two or more kinds. A material obtained by adding known pigments as described above to this is used.

When printing directly on a sheet made of a polyolefin resin material, a chlorinated polyolefin, polyurethane or the like is preferable as a binder in terms of adhesiveness.
If an easy-adhesion primer is appropriately selected and formed into a layer, sufficient adhesiveness can be obtained even if other binders are used.

The embossing is carried out by heating and softening the polyolefin resin, pressurizing and shaping with an embossing plate, and fixing by cooling. A known sheet-fed or rotary embossing machine is used.

Examples of the concavo-convex pattern include a wood grain board conduit groove, a stone board surface irregularity (granite cleavage plane, etc.), a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, and the like.

Further, if necessary, the concave portions of the concavo-convex pattern can be filled with a coloring ink by a known wiping method (see Japanese Patent Publication No. 58-14312). As the coloring ink, the same ink as described above can be used.
However, from the viewpoint of abrasion resistance, it is preferable to use a two-component curable urethane resin as a binder.

The metal thin film is made of aluminum, chromium, gold,
A film is formed by a method such as vacuum evaporation and sputtering using a metal such as silver or copper. Alternatively, a combination of these may be used.
The metal thin film may be provided on the entire surface of the decorative sheet, or
It may be provided partially in a pattern.

FIG. 1 shows an example of the layer structure when the decorative sheet of the present invention is a single layer. In FIG. 1A, a decorative sheet 3 is formed by mixing a pigment 2 into a sheet 1 made of a polyolefin-based resin material. In FIG. 1 (B), an easy-adhesion layer (primer layer) 4 is formed on one surface of a sheet 1 made of a polyolefin-based resin material, and a pattern 5 is provided on the surface of the easy-adhesion layer. In FIG. 1 (C), an uneven pattern 7 is formed on the surface of a sheet 1 made of a polyolefin resin material. In FIG. 1D, the surface of a sheet 1 made of a polyolefin-based resin material is filled with a colored ink wiping 8 and further a pattern 5 is provided.

(2) Multilayer sheet When the decorative sheet of the present invention is a multilayer sheet, the decorative sheet is obtained by laminating a surface sheet made of the polyolefin resin material on a base sheet, It is characterized in that one or both of the sheet and the topsheet are subjected to a decoration treatment. When the decorative sheet is a multilayer, for example, the base sheet mainly fulfills the functions (1) to (6) and (9) of the functions (1) to (12) required for the decorative sheet described above. The top sheet laminated on the surface of the base sheet has
(1) to (8) and (10) to (12) can be mainly carried.

<Base Sheet> The base sheet is made of a resin material mainly composed of polyolefin. As the polyolefin, the above-mentioned polyolefin-based resin materials may be used as those having excellent basic performance, but other polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, polypropylene, propylene-butene-
1 copolymer, polybutene-1, butene-1, propylene, ethylene, terpolymer, butene-1, hexene-1
Octene-1 terpolymer, polymethylpentene,
Alternatively, an elastomer such as an olefinic elastomer described in JP-A-6-16832 is used. The thickness is about 30 to 200 μm, and any of a stretched sheet and an unstretched sheet can be used. However, the unstretched sheet is better in terms of molding suitability such as V-cut processing.

As the elastomer, diene rubber, hydrogenated diene rubber, olefin elastomer and the like are used. The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule, and suppresses the crystallization of the polyolefin resin (polypropylene in the present invention) to increase flexibility. Let it. Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene butadiene rubber, acrylonitrile butadiene rubber, acrylonitrile / isoprene rubber, and styrene butadiene rubber. The olefin elastomer is an elastic copolymer obtained by adding at least one kind of polyene copolymerizable with two or more kinds of olefins. As the olefin, ethylene, propylene, α-olefin, or the like is used. 1,4 hexadiene, cyclic dienes, norbornene and the like are used. Preferred olefin copolymer rubbers include, for example, elastic copolymers containing an olefin as a main component, such as ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene rubber, and ethylene-butadiene copolymer rubber. Incidentally, these elastomers are appropriately crosslinked as required. Known crosslinking agents such as sulfur, aliphatic organic peroxides and aromatic organic peroxides are used.

The amount of the elastomer added is 10 to 60% by weight, preferably about 30% by weight, based on the total amount of the resin material constituting the base sheet. If the amount of the elastomer is less than 10% by weight, the change in elongation at a constant load becomes too steep, and the elongation at break and the impact resistance decrease. If the amount of the elastomer is more than 60% by weight, the transparency and weather resistance are increased. And a decrease in creep resistance occurs.

The base sheet is preferably a colored film made of a resin material obtained by mixing the above-mentioned polyolefin with a coloring agent. Such a coloring agent is for giving a base sheet a necessary color as a decorative sheet, and includes titanium white, zinc white, red petals,
Inorganic pigments such as vermilion, ultramarine, cobalt blue, graphite, titanium yellow, carbon black, etc., organic pigments or dyes such as isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, and foil powders such as aluminum and brass Pigments, titanium dioxide-coated mica, pearlescent pigments made of foil powder such as basic zinc carbonate, and the like. The coloring may be either transparent coloring or opaque (concealing) coloring, but opaque coloring is generally preferred in order to cover the adherend.

In addition, an inorganic filler may be added to the resin material constituting the base sheet. Examples of such inorganic fillers include calcium carbonate, barium sulfate, alumina, silica, clay, and talc.
A powder of about μm is used. The addition amount is 1 to 6
It is about 0% by weight, more preferably 5 to 30% by weight.
If the amount is less than 1% by weight, the creep deformation resistance and the adhesion will decrease. If the amount is more than 60% by weight, the elongation at break and the impact resistance will decrease.

Further, if necessary, a heat stabilizer, a flame retardant, a radical scavenger and the like are added. The heat stabilizer is a known one such as a phenol type, a sulfite type, a phenylalkane type, a phosphite type, and an amine type, and is used for further improving the prevention of deterioration such as thermal discoloration during thermal processing. As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used, and these are added when it is necessary to impart flame retardancy.

A blend of these materials is formed into a film by a conventional method such as a calendering method to obtain an opaque colored base sheet. The obtained base sheet satisfies the conditions (required functions) of (1) to (6) and (9) required for the base sheet of the decorative sheet. The thickness of the base sheet is 50 to 2
It is about 100 μm, preferably about 100 μm.

The surface of the base sheet is preferably subjected to an easy-adhesion treatment such as application of an easy-adhesion layer, corona discharge treatment, plasma treatment, and ozone treatment. An acrylic resin, a vinyl chloride-vinyl acetate copolymer, a polyester resin, a urethane resin, a chlorinated polypropylene, or a chlorinated polyethylene is used as the easy-adhesion layer (also referred to as a primer layer or an anchor layer). Resins are preferred.

Examples of the acrylic resin include poly (methyl meth) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate / (meth) acrylate. Butyl acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, styrene / methyl (meth) acrylate copolymer, ) Acrylic resin consisting of a homo- or copolymer containing (meth) acrylic acid ester such as methyl acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (here, (meth) acrylic (Meaning acrylic or methacrylic).

The urethane resin (polyurethane) is a polyurethane having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent). The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, and polyether polyol.

As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4-diphenylmethane diisocyanate,
Alternatively, aliphatic (or alicyclic) isocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used. Alternatively, adducts or multimers of these isocyanates can be used. For example, there are an adduct of tolylene diisocyanate, a trimer of tolylene diisocyanate, and the like.

A pattern layer may be formed on the surface subjected to the easy adhesion treatment, if necessary. The pattern layer can be formed on one or both of the base sheet and the surface sheet described below. FIG. 2A shows an example in which an easy-adhesion layer is formed, in which an easy-adhesion layer 14 is provided between a surface sheet 12 laminated on a base sheet 11 and a pattern layer 13. FIG.
As shown in (D), the easy-adhesion layer 14 may be provided on the side of the base sheet 11 facing the adherend 31. As the pattern processing, printing of a pattern 13 as shown in FIG.
An embossing (heating press) as shown in (B), a concave and convex pattern shaping 15 by a hairline processing or the like may be used.
Further, the concave portion of the concave-convex pattern 15 can be filled with the coloring ink 16 by a known wiping method. Also,
A metal thin film may be formed.

As the pattern printing, a pattern is formed by ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet. Wood patterns, stone patterns,
There are a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, a solid image, or the like.

As the ink (or) paint, chlorinated polyolefin resin such as chlorinated polyethylene, chlorinated polypropylene, polyester resin, urethane resin, acrylic resin, polyvinyl acetate, vinyl chloride / vinyl acetate copolymer, A cellulose resin or the like is used, and one kind or a mixture of one or more kinds is used. A material obtained by adding known pigments as described above to this is used. When printing directly on the base sheet, chlorinated polyolefin, urethane resin, etc. are preferable in terms of adhesiveness as a binder, but if an easy-adhesion primer is appropriately selected to form a layer,
Sufficient adhesiveness can be obtained by using other binders.

The embossing is performed by heating and softening the base material sheet, pressurizing and shaping with an embossing plate, and fixing by cooling. A known single-sheet or rotary embossing machine is used. Examples of the uneven shape include a wood grain board conduit groove, a stone board surface unevenness (granite cleavage face, etc.), a cloth surface texture, a matte finish, a grain, a hairline, a linear groove, and the like. The same thing as the above can be used for the coloring ink. However, from the viewpoint of abrasion resistance, a material using a two-component curable urethane resin as a binder is preferable.

The metal thin film is made of aluminum, chromium, gold,
A film is formed by a method such as vacuum evaporation and sputtering using a metal such as silver or copper. Alternatively, a combination of these may be used.
The metal thin film may be provided on the entire surface or partially in a pattern.

<Surface Sheet> In the decorative sheet according to the present invention, a film made of the above-mentioned polyolefin-based resin material is laminated as a surface sheet on the surface of the base material sheet which has been subjected to a decoration treatment as required as described above. As the polyolefin resin material, in the case of a single-layer sheet, the same resin material as the polyolefin resin material constituting the sheet is used.

In order to reinforce the function required as a surface layer of the decorative sheet, various additives, if necessary, may be added to the polyolefin resin material constituting the topsheet of the present invention.
Reinforcing materials and fillers, for example, heat stabilizers, antioxidants, antistatic agents, flame retardants and the like may be added. The heat retardant may be the same as in the case of the base sheet.

If a hindered amine radical scavenger is added to the topsheet, layers such as an urethane resin, a polyester resin, and a polyamide resin are added to layers such as an ink layer and an adhesive layer adjacent to the topsheet. When a resin containing no chlorine atom is used, the weather resistance is improved. If resins containing chlorine atoms in molecules such as vinyl chloride / vinyl acetate copolymers and chlorinated polyolefins are used, hydrogen chloride is generated from these resins by the action of ultraviolet light or heat, and this produces hindered amines. Since it reacts with the system radical scavenger to deactivate or inhibit its action, the weather resistance is not sufficiently improved.

The topsheet can be obtained by appropriately blending the above-mentioned topsheet resin material as required and forming a film by a conventional method such as a calendering method or an extrusion method. That is, by such film formation, a colorless or colored transparent soft polypropylene-based resin film is obtained, and the obtained film is required for the surface sheet of the decorative sheet (1) to (8), in particular, (7) , (8). The thickness of the topsheet is about 30 to 200 μm,
Preferably it is about 40 to 100 μm. The contact surface of the top sheet with the base sheet is preferably subjected to an easy-adhesion treatment such as application of an easy-adhesion layer, corona discharge treatment, plasma treatment, and ozone treatment in the same manner as in the case of the base sheet. Can be.

The above-mentioned base sheet, which is a colored film, and the above-mentioned surface sheet, which is a colorless or colored transparent polypropylene resin film, can be laminated by ordinary means. The lamination method may be melt extrusion coating (extrusion coating), fusion by hot pressing, or dry lamination using an adhesive such as a two-component curable polyurethane resin or polyester resin.

In the case of the decorative sheet of the present invention, even in the case of a multilayer sheet, a pattern layer can be formed on the surface on the top sheet side, if necessary. As the pattern processing, FIG.
And embossing (heating press), hairline processing or the like, or pattern printing. The pattern printing method, the type of pattern, the type of ink (or) paint, the binder, and the like may be the same as in the case of the base sheet. Further, if necessary, the concave portions of the concavo-convex pattern can be filled with a coloring ink by a known wiping method. At this time, if necessary, the embossed surface is subjected to an easy adhesion treatment such as the above-described corona discharge treatment, and the coloring ink is filled.

[0091] Preferably, an overcoat layer may be further formed on the topsheet for improving scratch resistance and adjusting gloss. As the binder, chlorinated polyolefin, two-component cured polyurethane resin or the like is preferable.

(3) Topcoat layer The topcoat layer of the decorative sheet of the present invention comprises a resin having an isocyanate group in the molecule on the surface side of the decorative sheet (or a topsheet in the case of a multilayer sheet). Can be formed.

As the resin having an isocyanate group in the molecule, a two-component curable urethane resin or a one-component curable urethane resin is used. As the two-component curable urethane resin, a mixture of the same polyol and isocyanate as described above as the resin system of the easy-adhesion layer can be used.

In a preferred embodiment when a two-part curable urethane resin is used, the number (mol number) of isocyanate groups (NCO groups) in the isocyanate is the number of hydroxyl groups (OH groups) of the polyol to be reacted therewith (reaction equivalent weight). In some embodiments, even after the reaction between the polyol and the isocyanate, a large number of unreacted isocyanate groups remain. In this case, the ratio of NCO groups / OH groups is set to a maximum of about 1.4.

The one-component moisture-curable urethane resin is a composition containing a prepolymer having an isocyanate group at a molecular terminal as an essential component. The prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at both molecular terminals, and is a solid thermoplastic resin at room temperature. The isocyanate groups react with each other due to moisture in the air to cause a chain extension reaction, and as a result, a reactant having a urea bond in a molecular chain is generated,
The urea bond further reacts with the isocyanate group at the molecular terminal to cause a biuret bond and branch to cause a crosslinking reaction.

The skeleton structure of the molecular chain of the prepolymer having an isocyanate group at the molecular terminal is arbitrary, and specific examples include a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, and a polybutazine skeleton. One or more of these skeletal structures are appropriately employed. When a urethane bond is present in the molecular chain, the terminal isocyanate group also reacts with the urethane bond to generate an allophanate bond, which also causes a cross-linking reaction.

These topcoat films may further include, if necessary, an ultraviolet absorber (which can be selected from various types such as the above-mentioned triaryltriazine type), alumina (particularly, preferably spherical α-alumina), silica and the like. And an antibacterial agent such as silver zeolite. When a matting agent is added, the top coat functions as a gloss control coat.

As described above, an organic absorber having an OH group in the molecule and a resin having an isocyanate group on its surface are used as the ultraviolet absorber added to the decorative sheet (or the surface sheet). The UV absorber bleeds out (exudes) over time when the top coat layer is formed
When entering the top coat, the UV absorber O
Since the H group and the isocyanate group in the overcoat film undergo a urethane reaction and are captured in the overcoat film layer, the bleed out of the ultraviolet absorber over time is prevented. It is particularly effective in the case of a polyolefin resin in which the organic ultraviolet absorber easily bleeds out, and is also suitable in the case of the above-mentioned polyolefin resin material used in the decorative sheet (or the surface sheet in the case of a multilayer) in the present invention. is there.

Preferably, a gloss-controlling protective coating layer can be further formed on the overcoat layer. As the binder, chlorinated polyolefin, two-component cured polyurethane or the like is preferable.

III. Uses The decorative sheet of the present invention may be used as a decorative material as it is, or it may be used by laminating the sheet on another adherend (backing material). In the case of lamination, the adhesive layer may be omitted if the decorative sheet itself can be adhered to the adherend (due to thermal melting point, etc.), and if the decorative sheet itself does not adhere to the adherend, an appropriate adhesive It may be laminated with an agent.

The adherend is a final product, and a decorative sheet may be laminated for surface decoration. If necessary, the decorative sheet may be used to reinforce the mechanical strength of the decorative sheet or to provide concealment. An adherend may be laminated on the back surface.

Examples of the adherend include various materials such as plate materials such as flat plates and curved plates, three-dimensionally shaped articles (molded articles), and sheets (or films). Examples of materials used for plate materials, three-dimensional articles, and sheets (films) include wood veneers made of trees such as cedar, cypress, pine, lauan, and teak, wood plywood, particle board, and the like.
Wood board such as medium density fiber board (MDF), metal such as iron and aluminum, acrylic, polycarbonate, ethylene-vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS, phenolic resin, polyvinyl chloride, Cellulose-based resins, resins such as rubber, materials exclusively used as plate materials, or three-dimensional articles include ceramics such as glass, ceramics, and the like.
Non-cement ceramic materials such as cement such as ALC (foamed lightweight concrete), calcium silicate, gypsum, etc. Materials used exclusively as sheets (or films) include paper such as high-quality paper and Japanese paper, carbon, asbestos, and titanic acid. There is a nonwoven fabric or a woven fabric made of fibers such as potassium, glass, and synthetic resin.

As a method of laminating these various adherends,
For example, as described in Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488, etc., a decorative sheet is a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive layer therebetween. Between the male and female molds for injection molding,
The two molds are closed, the molten resin is injected and filled from the male mold gate, then cooled, and a decorative sheet is adhered and laminated on the surface of the resin molded article simultaneously with the molding. No. 45768, Japanese Patent Publication No. 60-5
No. 8014, etc., a decorative sheet is placed on the surface of a molded article facing or placed via an adhesive layer therebetween, and the decorative sheet is formed by a pressure difference due to vacuum suction from the molded article side. A so-called vacuum press laminating method for laminating on the surface, as described in JP-B-61-5895, JP-B-3-2666, etc., has a cosmetic in the longitudinal direction of a columnar substrate such as a cylinder or a polygonal pillar. While feeding the sheet through the adhesive layer between,
A so-called lapping method, in which a decorative sheet is successively pressed and laminated on a plurality of side surfaces constituting a columnar body by a plurality of rollers having different directions, a so-called lapping method, actual public university 15-31122.
As described in JP-A-48-47972 and the like, a decorative sheet is first laminated on a plate-like substrate via an adhesive layer, and then the decorative sheet on the opposite side of the plate-like substrate from the decorative sheet is laminated. On the surface,
Cut a V-shaped or U-shaped groove reaching the interface between the decorative sheet and the plate-shaped substrate, and then apply an adhesive in the groove, and then bend the groove to form a box or column. There is a so-called V-cut or U-cut processing method for molding a body.

In particular, as a method of bonding the decorative sheet of the present invention to a three-dimensional object having irregularities, of the above methods, (a) lapping method, (b) V-cut method, (c) simultaneous lamination method of injection molding, (D) A vacuum forming simultaneous lamination method or the like is preferable.

The decorative sheet of the present invention can be used for various applications by laminating on various adherends and subjecting it to a predetermined molding process. For example, interior decoration of buildings such as walls, ceilings and floors, window frames, doors, handrails, rims, skirting boards and other fittings, or surface makeup of construction members, furniture or surface makeup of cabinets for furniture or light electrical / OA equipment, automobiles , Interior of vehicles such as trains, interior of aircraft, makeup of window glass, etc.

[0106]

Embodiments of the present invention will be described below in detail. In addition, the evaluation method of each physical property in the following Examples and Comparative Examples is as follows.

(1) Heat Resistance Acceleration Test The decorative sheet having the overcoated film was treated at 40 ° C., 80 ° C.,
Placed in an oven set to each temperature of 00 ° C. and left for a predetermined period (predetermined period; 40 ° C. = 1 week, 80 ° C. = 2 days, 1 day
(00 ° C. = 2 hours), and the appearance was confirmed. Further, the adhesiveness of the overcoat layer was tested with a cellophane adhesive tape. As a specific test method, a cellophane adhesive tape (Nichiban Co., Ltd., trade name “Cellotape”, 24 mm width for industrial use) was applied to the surface of the coating film, and rubbed with a cloth at room temperature (20 ° C.). The tape surface was cooled to room temperature, and the cellophane adhesive tape was peeled off at once by hand. The presence or absence of adhesion of the coating film to the cellophane adhesive tape was visually confirmed.

(2) Weathering Acceleration Test Using a carbon arc lamp type sunshine weatherometer, a black panel temperature of 63 ° C. and a rain test for 18 minutes out of 120 minutes (hereinafter referred to as SWOM test) ),
By visually observing, the presence or absence of an abnormality such as floating or falling off between layers such as the OP layer was inspected.

(3) Weathering Acceleration Test Using an I-Super UV tester (manufactured by Iwasaki Electric Co., Ltd.), at a black panel temperature of 63 ° C. and an illuminance of 60 mW / cm.
² , distance from light source 240mm, irradiation spectrum band 2
After irradiating for 95 to 450 mm for 5 hours and testing for 1 hour dew condensation (hereinafter referred to as S-UV test), observe visually and inspect for abnormalities such as floating and falling off between layers such as OP layer. did.

(4) Bending Resistance Whitening Test The sheet was bent outward at 180 ° C. in a 10 ° C. atmosphere, and the appearance was evaluated. (5) Pencil hardness test Measured in accordance with JIS-K-5400 (500 g load).

[0111]

Example 1 Polypropylene resin (Nippon Polychem Co., Ltd.)
92% by weight of Novatec PP / FG3D manufactured by Novatec LD / Nippon Polychem Co., Ltd.
LC600A) 4% by weight, ethylene / cyclic aminovinyl compound copolymer (ethylene / cyclic aminovinyl compound copolymer in which R ₁ and R _{2 in} the above formula (1) are methyl groups and R ₃ is a hydrogen atom) 4% by weight % And a total of 100 parts by weight thereof, and 0.5 parts by weight of a triaryltriazine type ultraviolet absorber (a triaryltriazine compound in which R _{4 in the} above formula (2) is an octyl group, and R _{5 to} R ₈ are methyl groups). And 0.05 parts by weight of a phenolic stabilizer (tetrakis [methylene-3- (3′-5′-di-tert-butyl-4-hydroxyphenyl) propionate] methane) in a blender. The resin material obtained by the extrusion was formed into a film having a thickness of 80 μm on a transparent sheet by a T-die extruder, and both surfaces thereof were subjected to a corona discharge treatment.

Next, a wood pattern was prepared using a coloring ink (100 parts by weight of an acrylic polyol and 8 parts by weight of 1,6-hexamethylene diisocyanate, and a pigment composed of an acrylic urethane ink pattern, carbon black, and titanium oxide). Gravure printing, 100 parts by weight of acrylic polyol and 10 parts by weight of 1,6-hexamethylene diisocyanate on the opposite side (surface), and the matting agent is silica particles
An ink having an average particle diameter of 2 μm was formed by gravure printing to form a 2 μm-thick overcoat layer. Table 1 shows the evaluation results of the product properties and the like.

[0113]

Example 2 As a colored base sheet, 100 parts by weight of isotactic polypropylene, 60 parts by weight of hydrogenated styrene-butadiene rubber, 25 parts by weight of an inorganic filler composed of fine particles of calcium carbonate, titanium white, red iron oxide, graphite meter A 60 μm thick polyolefin-based colored base sheet colored with 5 parts by weight of a coloring pigment was produced.

After the corona discharge treatment, a grain pattern was printed on the surface of the colored base sheet by gravure printing using the same ink as in Example 1, and the opposite surface (back surface) was subjected to corona discharge treatment, followed by silica coating. A urethane-based primer coat (1,6-hexamethylene diisocyanate + acrylic polyol) containing 2% by weight (manufactured by Showa Ink Industries, Ltd.) was formed to a thickness of 2 μm by gravure printing to obtain a printed colored film. Thereafter, an adhesive layer composed of polyester polyol and 1,6-hexamethylene diisocyanate was added to 10 μm.
Then, a transparent surface sheet having a thickness of 80 μm and made of the resin material described in Example 1 and previously formed into a film was bonded to each other by dry lamination.

The multi-layer sheet composed of the colored substrate sheet having the colored pattern printed thereon and the transparent surface sheet was further subjected to a heat treatment, and embossed using an emboss (hereinafter, also referred to as “EM”) plate having a wood grain conduit pattern. The embossed surface is subjected to a corona discharge treatment to form a transparent overcoat layer having a thickness of 3 μm comprising acryl polyol, 1,6-hexamethylene diisocyanate and silica particles having an average particle diameter of 2 μm by gravure roll coating. I got Table 1 shows the evaluation results of the product properties and the like.

[0116]

Example 3 Based on 60% by weight of high density polyethylene, 30% by weight of hydrogenated styrene-butadiene rubber as a thermoplastic elastomer, 10% by weight of fine particles of calcium carbonate as an inorganic additive, and red pigment and carbon black as coloring pigments Was added and 5% by weight of a heat stabilizer and a hindered amine radical scavenger were blended to obtain an opaque colored sheet formed into a film having a thickness of 60 μm by a calendering method. This colored base sheet (colored PE)
After the corona discharge treatment, a wood grain pattern was printed by gravure printing using the same ink as in Example 1, and the opposite surface was subjected to corona discharge treatment, followed by a urethane-based primer coat (1,6- Hexamethylene diisocyanate + acrylic polyol) (manufactured by Showa Ink Industries, Ltd.)
Was formed by gravure printing to obtain a printed colored base sheet.

Thereafter, the polyester polyol and 1,6
An adhesive layer made of hexamethylene diisocyanate was formed to a thickness of 10 μm, and the resin material described in
It was melt-extruded at a resin temperature of 240 ° C. and a thickness of 60 μm from a die to obtain a multilayer sheet composed of a colored-pattern-printed substrate sheet and a transparent surface sheet. The multilayer sheet was further heated and embossed using an EM plate having a wood grain conduit pattern.
The embossed surface is subjected to a corona discharge treatment, and the concave portion formed by EM is colored ink (the binder is acrylic polyol 1).
00 parts by weight, 8 parts by weight of 1,6-hexamethylene diisocyanate, and the pigment is composed of red stalks and carbon black).
A transparent top coat layer comprising hexamethylene diisocyanate and a matting agent (silica particles) having an average particle size of 2 μm was formed to a thickness of 2 μm by gravure roll coating to obtain a decorative sheet. Table 1 shows the evaluation results of the product properties and the like.

[0118]

Comparative Example 1 80 parts of polypropylene (Softrex EL6D21 manufactured by Nippon Petrochemical Co., Ltd.) and polyurethane resin (“PANDEX T515” manufactured by Dainippon Ink and Chemicals, Inc.)
7 "), 10 parts of a compatibilizer (" Yumex 1010 "manufactured by Sanyo Chemical Co., Ltd.), and 3000 parts of ultraviolet absorber (Tinuvin234 manufactured by Ciba Specialty Chemicals)
m), light stabilizer Ciba Specialty Chemicals I
rganox1010 at 2000 ppm) and mixed with a T-die extruder.
A film was formed to a thickness of 0 μm, and corona discharge treatment was performed on both surfaces. Next, a colored ink (the binder is acrylic polyol 10)
0 parts by weight and 1,6-hexamethylene diisocyanate 8
Parts by weight, the pigment is made of acrylic urethane ink pattern, carbon black, and titanium oxide), and gravure printing of a wood grain pattern is performed. On the other side, 100 parts by weight of acrylic polyol and 10 parts by weight of 1,6-hexamethylene diisocyanate, The matting agent formed a transparent overcoat layer having a thickness of 2 μm by gravure printing of an ink composed of silica particles (average particle size: 2 μm). Table 2 shows the evaluation results of the physical properties of the product.

[0119]

Comparative Example 2 As a colored base sheet, 100 parts by weight of isotactic polypropylene, 60 parts by weight of hydrogenated styrene-butadiene rubber, 25 parts by weight of an inorganic filler composed of fine particles of calcium carbonate, titanium white, red iron oxide, and graphite meter A 60 μm thick polyolefin resin sheet colored with 5 parts by weight of a coloring pigment was produced. After the corona discharge treatment, a grain pattern is printed on the colored raw material by gravure printing. The corona discharge treatment is also performed on the opposite surface, and a urethane-based primer coat (1,6-hexamethylene diisocyanate + acryl polyol) containing 8% by weight of silica is used. ) (Manufactured by Showa Ink Industry Co., Ltd.) was formed by gravure printing to obtain a printed colored base sheet.

Thereafter, the polyester polyol and 1,6
-An adhesive layer made of hexamethylene diisocyanate is formed to a thickness of 10 μm, and an olefin-based thermoplastic elastomer (100 parts of Softlex manufactured by Nippon Polyolefin Co., Ltd., 20 parts of Admer Mitsui Chemicals, Inc. 2 parts of Tuffmer Co., Ltd., UV absorber (Tinuvin326 manufactured by Ciba Specialty Chemicals)
4,000 ppm) and a transparent surface sheet having a thickness of 80 μm and made of a resin mixed with 3000 ppm of Irganox 1010 manufactured by Ciba Specialty Chemicals. The multilayer sheet consisting of the colored pattern printed substrate sheet and the transparent surface sheet was further subjected to heat treatment, and embossed using an EM plate having a wood grain conduit pattern. The embossed surface is subjected to a corona discharge treatment, and a transparent overcoat film layer composed of an acrylic polyol, an isocyanate, and silica particles having an average particle diameter of 2 μm is gravure-coated at 3 μm.
It was formed to a thickness to obtain a decorative sheet. Table 2 shows the evaluation results of the product properties and the like.

[0121]

Comparative Example 3 Based on 60% by weight of high-density polyethylene, 30% by weight of hydrogenated styrene-butadiene rubber as a thermoplastic elastomer, 10% by weight of fine particles of calcium carbonate as an inorganic additive, and red pigment and carbon black as coloring pigments Was added at 5% by weight, and a blend of a heat stabilizer and a hindered amine-based radical scavenger at 5% by weight was produced into a 60 μm thick opaque colored sheet by a calendering method.

After the corona discharge treatment, a grain pattern was printed on the colored substrate sheet (colored PE) by gravure printing. The corona discharge treatment was also performed on the opposite surface, and a urethane primer coat (1, 1) containing 8% by weight of silica was used. 6-Hexamethylene diisocyanate + acrylic polyol) (manufactured by Showa Ink Industries, Ltd.) was formed by gravure printing to obtain a printed colored sheet.

Thereafter, the polyester polyol and 1,6
-An adhesive layer made of hexamethylene diisocyanate was formed to a thickness of 10 μm, and the resin used in Comparative Example 2 was
The resin was melt-extruded at a resin temperature of 240 ° C. and a thickness of 60 μm from a die to obtain a multilayer sheet composed of a substrate sheet with a printed color pattern and a transparent surface sheet. The multilayer sheet was further heated and embossed using an EM plate having a wood grain conduit pattern.
The embossed surface is subjected to a corona discharge treatment, and the concave portion formed by EM is colored ink (the binder is acrylic polyol 1).
00 parts by weight, 8 parts by weight of 1,6-hexamethylene diisocyanate, the pigment is composed of red petroleum and carbon black), acrylic polyol, 1,6-hexamethylene diisocyanate, and a matting agent (silica having an average particle size of 2 μm). Particles) was formed to a thickness of 2 μm by gravure roll coating to obtain a decorative sheet. Table 2 shows the evaluation results of the product properties and the like.

[0124]

[Table 1]

[0125]

[Table 2]

[0126]

According to the decorative sheet of the present invention, various quality performances of the conventional decorative sheet using an olefin-based resin are improved. The advantage is that there is little bleeding in the aging and heat resistance test, it does not hinder the adhesion with the layer (printing layer, transparent overcoat layer, substrate layer) that the resin material contacts, and it is hard to be scratch-resistant and resistant to bending whitening. Have. In addition, it has thermoformability, weather resistance, and transparency equal to or higher than those of a decorative sheet using a polyvinyl chloride resin while using an olefin resin. Therefore, it can be suitably used particularly for interiors of buildings, surface decoration of fittings, vehicle interiors, and the like.

[Brief description of the drawings]

FIG. 1 is a diagram showing an example of a layer configuration when a decorative sheet of the present invention is a single-layer sheet.

FIG. 2 is a diagram showing an example of a layer configuration when the decorative sheet of the present invention is a multilayer sheet.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Sheet made of polyolefin resin material 2 ... Pigment 3 ... Decorative sheet 4 ... Easy adhesion layer (primer layer) 5 ... Pattern 7 ... Uneven pattern 8 ... Colored ink DESCRIPTION OF SYMBOLS 11 ... Base sheet 12 ... Top sheet 13 ... Pattern layer 14 ... Easy adhesion layer 15 ... Concavo-convex pattern 16 ... Colored ink 31 ... Adherend

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Seiji Kuroda 1-1-1, Ichigaya Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Masayuki Shibata 1-1-1, Ichigaga-cho, Shinjuku-ku, Tokyo No. 1 Inside Dai Nippon Printing Co., Ltd. (72) Inventor Toshihisa Ishihara No. 1 Tohocho, Yokkaichi-shi, Mie Japan F-term in the Materials Development Center, Japan 4F071 AA15 AA15X AA20X AA37X AA76X AA88 AA88X AC19 AE05 AH03 BC01 BC09 4F100 AA20H AA21H AA37H AH03J AK03A AK04A AK06A AK07 AK25A AK51C AK64A AL03A AL05A AT00B BA02 BA03 BA07 BA10B BA10C CA07 CA30 EH17 EH172 EJ55 EJ552 GB08 GB33 JA06A JJ03J00

Claims (6)

[Claims] An MFR at 230 ° C. of 0.5 to 30.
g / 10 minutes, ethylene / propylene random copolymer having an ethylene content of 1 to 6% by weight according to NMR method;
A polyolefin-based resin material mainly comprising a polyolefin-based resin composition containing 98% by weight, a copolymer of ethylene and a cyclic aminovinyl compound represented by the following formula (1); A decorative sheet which is a sheet to be formed and which has been subjected to a decoration process. Embedded image (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.) 2. An MFR at 230 ° C. of 0.5 to 30.
g / 10 minutes, ethylene / propylene random copolymer having an ethylene content of 1 to 6% by weight according to NMR method;
96% by weight, MFR at 190 ° C. is 1 to 10 g / 1
0% low density polyethylene; 2 to 15% by weight; and a copolymer of ethylene and a cyclic aminovinyl compound represented by the following formula (1): 2 to 10% by weight of a polyolefin resin composition. A decorative sheet, which is a sheet formed of a polyolefin resin material as a main component and which has been subjected to a decoration treatment. Embedded image (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.) 3. A multilayer sheet having at least a base sheet and a top sheet, wherein the top sheet has 230
An ethylene / propylene random copolymer having an MFR at 0.5 ° C. of 0.5 to 30 g / 10 min and an ethylene content of 1 to 6% by weight by NMR; 90 to 98% by weight, ethylene and the following formula (1) And a base material sheet formed of a polyolefin resin material mainly composed of a polyolefin resin composition containing 2 to 10% by weight of a copolymer with a cyclic aminovinyl compound to be used. And a decorative sheet obtained by subjecting one or both of the surface sheets to a decoration treatment. Embedded image (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.) 4. A multilayer sheet having at least a base sheet and a top sheet, wherein the top sheet has 230
Ethylene-propylene random copolymer having an MFR at 0.5 ° C. of 0.5 to 30 g / 10 min and an ethylene content of 1 to 6% by weight by NMR; 75 to 96% by weight, 190 ° C.
Low-density polyethylene having an MFR of 1 to 10 g / 10 min; 2 to 15% by weight, and a copolymer of ethylene and a cyclic aminovinyl compound represented by the following formula (1);
It is formed of a polyolefin-based resin material mainly containing a polyolefin-based resin composition containing 0% by weight, and is subjected to a decoration treatment on one or both of the base sheet and the surface sheet as necessary. Become a decorative sheet. Embedded image (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.) 5. The decorative sheet according to claim 1, wherein a top coat layer made of a resin having an isocyanate group is laminated on the surface of the sheet. 6. The polyolefin-based resin material further comprises a triaryltriazine type ultraviolet absorber represented by the following formula (2) added to the resin composition in an amount of 0.1 to 1 part by weight based on 100 parts by weight of the resin composition. Parts by weight.
The decorative sheet according to claim 1. Embedded image (Wherein, R _{4 to} R ₈ each independently represent a carbon number of 1 to 1)
Represents an alkyl group of 0. )