JP2000025169A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet using a base material sheet comprising a polyolefinic resin, characterized by that a primer layer is hard to peel from the base material sheet and especially excellent in weathering adhesion, the adhesion of a pattern layer is good over a long period of time, the primer layer rapidly develops adhesion to the base material sheet, good in initial adhesion immediately after production, excellent in flexibility and has bending processability and excellent in workability at the time of production. SOLUTION: In a decorative sheet obtained by applying a primer layer 2 to the surface of a base material sheet 1 comprising a polyolefinic resin and subsequently providing a pattern layer 3 on the primer layer 2, the primer layer 2 is formed from a cured layer of a two-pack type curable acryl urethane resin based on acryl polyol containing octyl (meth)acrylate, cyclohexyl (meth) acrylate, methyl (meth)acrylate and (meth)acrylate having a hydroxyl group in its molecule as copolymer components and containing aliphatic or acyclic isocyanate as a crosslinking agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used for interior decoration of buildings, surface decoration of fittings, interior decoration of vehicles, etc., and used for the purpose of giving a design to these surfaces or protecting the surfaces.

[0002]

2. Description of the Related Art A decorative sheet in which a pattern is provided on a surface of a vinyl chloride resin base sheet by printing or the like has hitherto been used. However, in recent years, the material of the base sheet is shifting from a vinyl chloride resin to a polyolefin resin.

[0003] Polyolefin-based resins have poorer adhesion to ink on the surface than vinyl chloride-based resins. Therefore, when manufacturing a decorative sheet using a polyolefin-based resin as a base sheet, in order to improve the adhesion between the base sheet and the pattern, a pattern is printed after applying an easy-adhesion primer to the surface of the base sheet. Is being carried out.
24552, JP-A-10-71683, etc.). Conventionally, a two-part curable urethane resin comprising a main agent such as a polyester polyol or a vinyl chloride-vinyl acetate-maleic acid copolymer and an isocyanate-based curing agent has been used as this kind of primer.

Further, as a two-part curable urethane resin composition in consideration of weather resistance, acrylic polyol obtained by copolymerizing methyl methacrylate and 2-hydroxyethyl methacrylate as main components, or n-butyl acrylate and 2-hydroxyethyl It is known to use non-yellowing isocyanates composed of an aliphatic polyol or an alicyclic isocyanate and an acrylic polyol obtained by copolymerizing methacrylate as a main component ("Polyurethane resin handbook" edited by Keiji Iwata, pp. 406 to 407). 1987 9
Published by Nikkan Kogyo Shimbun on March 25).

[0005]

However, the polyolefin resin has a lower adhesion of the primer layer than the vinyl chloride resin, the primer is easily peeled from the base sheet, and the adhesion of the pattern is insufficient. There was a problem.

[0006] In addition, when the decorative sheet is used in places exposed to sunlight, such as near a window, not only when it is used outdoors, but also when it is used indoors, it has excellent weather resistance. It is required that the adhesion between the pattern and the base sheet (weather resistance) is such that the base sheet and the pattern layer are not easily peeled off even after being exposed to ultraviolet light, high temperature and high humidity for one year outdoors. Is desired.

The present inventors have also attempted to use a conventionally known two-pack curable urethane resin comprising the acrylic polyol and non-yellowing isocyanate as a primer for an olefin resin base sheet. However, sufficient weather resistance was not obtained.

When a pattern is printed on both sides of the base sheet, if the primer is applied inline on both sides of the base sheet, the initial adhesion of the primer to the base material immediately after coating is low, There is a problem that sheets are easily blocked. Furthermore, in the case of the above-mentioned two-component curable urethane resin, there is a problem that cracks easily enter the primer layer when bending processing such as V-cut processing is performed.

The present invention has been made in view of the above-mentioned drawbacks of the prior art, and in a decorative sheet using a base sheet made of a polyolefin resin, a primer layer is hardly peeled off from the base sheet, and in particular, it has poor weather adhesion. Excellent, the adhesion of the pattern layer is good over a long period of time, the primer layer quickly develops adhesion to the substrate sheet, the initial adhesion immediately after production is good, and the flexibility It is an object of the present invention to provide a decorative sheet having excellent folding workability and excellent workability in the production of a decorative sheet.

[0010]

According to the present invention, there is provided a decorative sheet comprising (1) a primer layer coated on a surface of a base sheet made of a polyolefin resin and then provided with a pattern layer, wherein the primer layer is octyl. Acrylic polyol containing (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate, and (meth) acrylate having a hydroxyl group in a molecule as a main component, and aliphatic or alicyclic isocyanate as a crosslinking agent. A decorative sheet characterized by being formed from a cured product of a two-component curable acrylic urethane resin.
(2) The decorative sheet according to the above (1), wherein a protective layer is laminated on the surface of the picture layer, and (3) bis (2,2,6,6-tetramethyl-4-piperidinyl) as the primer layer.
The decorative sheet according to the above (1) or (2) containing sebacate, or (4) a polar functional group containing an active hydrogen atom on the primer layer side of the surface of a base sheet made of a polyolefin-based resin. (1) wherein the functional group and the primer layer are formed by urethane bonding.
The gist is the decorative sheet according to (2) or (3).

[0011]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. The decorative sheet of the present invention is, as shown in FIG.
After subjecting one surface of the base sheet 1 made of a polyolefin resin to an easy adhesion treatment such as a corona discharge treatment to form a polar functional group containing an active hydrogen atom such as a hydroxyl group on the surface, the treated surface having a specific composition described later is formed on the treated surface. An easy-adhesion primer composition comprising a two-component curable acrylic urethane resin is applied and crosslinked and cured to provide an easy-adhesion primer layer 2 (hereinafter, simply referred to as a primer layer). The pattern layer 3 is formed using printing ink.
In addition, as shown in FIG. 1, the decorative sheet of the present invention
Is preferably covered with a protective layer 4.

The base sheet 1 may be any of a colored sheet, a non-colored sheet, a transparent sheet, and an opaque (concealing) sheet, and is appropriately used depending on the use of the decorative sheet. For example, in the case of the decorative sheet of the embodiment shown in FIG. 1, the protective layer is generally formed transparent (transparency in which a pattern or the like can be seen), and an arbitrary colored sheet is used as the base sheet. The base sheet may be a single layer as shown in the figure, or may be a laminate of two, three or more layers.

As shown in FIG. 2, the decorative sheet of the present invention is formed by using a transparent sheet as a base sheet, applying an easy-adhesion treatment to the back side of the transparent sheet, and applying a primer layer 2 thereon. Providing a pattern on the primer layer 2,
A decorative sheet in which the picture layer 3 is formed on the back side of the base sheet 1 can also be used. In addition to the layer configuration of the decorative sheet of the present invention, in addition to the embodiments shown in FIGS. 1 and 2, the base sheet may be composed of two sheets, and a pattern layer may be provided between the sheets. Alternatively, a primer layer may be provided on both sides of the base sheet 1, and the picture layer 3 may be formed by printing on both sides of the base sheet 1.

In the present invention, the base sheet 1 is made of a polyolefin resin. Polyolefin resins include polyethylene (low or high density), polypropylene (isotactic, syndiotactic,
Or a mixed type thereof), polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer and other high-crystalline non-elastomeric polyolefin resins, or various olefinic thermoplastic elastomers described below. Used. As the polyolefin-based resin sheet, any of a stretched sheet and an unstretched sheet can be used, and if necessary, a filler, a foaming agent, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, a light Various additives such as stabilizers are added. Also, the base sheet 1
Has a thickness of about 20 to 300 μm, although it depends on the application.

[0015] The olefinic thermoplastic elastomer is
The main raw material is made of either high-density polyethylene or polypropylene which is a hard segment, to which an elastomer and an inorganic filler as a soft segment are added, and the hard segment described in JP-B-6-23278. A mixture comprising an isotactic polypropylene and an atactic polypropylene as a soft segment;
JP, JP-A-5-77371, JP-A-7-31
Those comprising an ethylene-propylene-butene copolymer described in No. 6358 and the like are typical. If necessary, additives such as a coloring agent are added to this and used. The details are described below.

The high-density polyethylene according to the present invention is preferably a polyethylene having a specific gravity of 0.94 to 0.96, which is a polymer having a high degree of crystallinity and a small number of branched structures obtained by a low-pressure method. High density polyethylene is used. Further, as the polypropylene, preferably, isotactic polypropylene is used.

As the elastomer in the present invention, a diene rubber, a hydrogenated diene rubber, an olefin elastomer or the like is 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 (high-density polyethylene or polypropylene in the present invention). Increase flexibility. 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 to which at least one polyene copolymerizable with two or three or more olefins is added, and the olefin is ethylene, propylene, α
An olefin or the like is used;
Hexadiene, cyclic diene, 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. In addition, these elastomers may be appropriately cross-linked by using a cross-linking agent such as an organic peroxide or sulfur, if necessary.

The addition amount of these elastomers is 1
It is about 0 to 60% by weight, preferably about 30% by weight. 1
If it is lower than 0% by weight, the change in elongation at a constant load with respect to the temperature becomes too steep, and the elongation at break, impact resistance and easy adhesion decrease, and if it is higher than 60% by weight, transparency and weather resistance are obtained. And a decrease in creep resistance occurs.

As the inorganic filler in the present invention, powder having an average particle size of about 0.1 to 10 μm, such as calcium carbonate, barium sulfate, clay, and talc, is used. The amount of addition is about 1 to 60% by weight, preferably about 5 to 30% by weight. If the amount is less than 1% by weight, the creep deformation resistance and the easy adhesion decrease. If the amount is more than 60% by weight, the elongation at break and the impact resistance decrease, and the film formation becomes difficult.

[0020] Japanese Patent Publication No. Hei 6-23278 describes,
(A) As a soft segment, the number average molecular weight Mn is 2
(B) 10 to 90% by weight of atactic polypropylene soluble in boiling heptane having a ratio of weight average molecular weight Mw to number average molecular weight Mn of 5,000 or more, Mw / Mn ≦ 7;
As a hard segment, the melt index is 0.1
Soft polypropylene consisting of a mixture of ４4 g / 10 min boiling heptane-insoluble isotactic polypropylene 90-10 wt%. Among this kind of olefin-based thermoplastic elastomers, so-called "necking" is unlikely to occur, and as a material having good suitability for molding or embossing using heat and pressure, isotactic polypropylene and It is made of a mixture with atactic polypropylene, and the weight ratio of the atactic polypropylene is 5% by weight or more and 50% by weight or less. The polypropylene-based olefin-based thermoplastic elastomer itself is already known, but when used in a conventionally known application such as a packaging container, the weight ratio of the atactic polypropylene as a soft segment is 5 to emphasize strength. Less than% by weight was exclusively used. However, when forming or embossing into a three-dimensional shape or uneven shape, necking occurs as described above, and good processing is impossible. On the other hand, contrary to the conventional composition design, embossing is performed by setting the weight ratio of atactic polypropylene to 5% by weight or more in a polypropylene-based thermoplastic elastomer.
It is possible to eliminate non-uniform deformation of the sheet due to necking in molding into an article having a three-dimensional or irregular shape, and the resulting defects such as wrinkles and pattern distortion. Particularly, the case where the weight ratio of the atactic polypropylene is 20% by weight or more is preferable. On the other hand, if the weight ratio of the atactic polypropylene is excessively increased, the sheet itself is deformed, a pattern is distorted, and in multicolor printing, defects such as a misregistration (register) are likely to occur. Further, it is not preferable because it is easily broken during molding. As the upper limit of the weight ratio of atactic polypropylene, the pattern layer is printed using a normal rotary printing machine such as rotary gravure printing, and embossing of a sheet, vacuum forming, V-cut processing, simultaneous lamination of injection molding, etc. When employed, it is at most 50% by weight, more preferably at most 40% by weight.

A thermoplastic elastomer comprising an ethylene / propylene / butene copolymer resin. Here, as the butene, any one of the three structural isomers of 1-butene, 2-butene and isobutylene can be used. The copolymer is a random copolymer and partially includes an amorphous portion. Preferred specific examples of the ethylene / propylene / butene copolymer include the following (i) to (iii). (i) Those described in JP-A-9-1111055. This is a random copolymer of a terpolymer of ethylene, propylene and butene. The weight ratio of the monomer components is 90% by weight or more of propylene. Melt flow rate is
It is preferable that the temperature is 230 ° C. and 2.16 kg for 1 to 50 g / 10 minutes. Then, based on 100 parts by weight of such a ternary random copolymer, 0.01 to 50 parts by weight of a transparent nucleating agent containing a phosphoric acid aryl ester compound as a main component, and 0.1 to 0.2 parts by weight of a fatty acid amide having 12 to 22 carbon atoms. 003 to 0.3 parts by weight are melt-kneaded. (ii) Those described in JP-A-5-77371. this is,
A terpolymer of ethylene, propylene and 1-butene, in which 20 to 100% by weight of an amorphous polymer having a propylene content of 50% by weight or more,
0 to 0% by weight is added. (iii) Those described in JP-A-7-316358. This is an ethylene-propylene / 1-butene terpolymer, in which the content of propylene and / or 1-butene is 50% by weight or more and the low crystalline polymer is 20 to 100% by weight.
A composition obtained by adding 5% by weight of an oil gelling agent such as an N-acylamino acid amine salt or an N-acylamino acid ester to 100 parts by weight of a composition mixed with 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene. It is. The ethylene / propylene / butene copolymer resin may be used alone, or may be used by mixing other polyolefin resins as required in the above (i) to (iii).

The base sheet 1 may contain a coloring agent. The coloring agent is used to give the base sheet the necessary color as a decorative sheet, and is made of inorganic materials such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, and carbon black. Pigment, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R,
Organic pigments or dyes such as phthalocyanine blue, metal pigments made of foil powder such as aluminum and brass, mica coated with titanium dioxide, and pearlescent pigments made of foil powder such as basic zinc carbonate are used. The coloring may be either transparent coloring or opaque (concealing) coloring. However, in the case of a decorative sheet having the configuration shown in FIG. 1, opaque coloring is preferable in order to cover the adherend. Further, in the case of a decorative sheet having a configuration as shown in FIG. 2, it is colorless and transparent or colored and transparent in order to see through the picture layer.

Further, if necessary, the base sheet 1
Heat stabilizers, flame retardants, radical scavengers, etc. 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 mixture of these materials is formed into a film by a conventional method such as a calendering method to obtain a substrate sheet. The thickness of the base sheet is about 50 to 200 μm, preferably about 100 μm. In addition, when using a composition to which a coloring agent, an inorganic filler, or both are added as a base sheet and forming a film by a melt extrusion method, the film forming suitability decreases when the film is formed into a thin film, and the surface of the base sheet is reduced. Does not finish smoothly.
Generally, a colorant or the like is added in an amount of about 10 parts by weight or more,
This tendency is conspicuous when the film is formed to a thickness of 0 μm or less. Therefore, in such a case, it is advisable to co-extrude three layers, add a colorant only to the center layer, and add no pigment or the like to the outermost layers on the front and back sides.

The surface of the base sheet 1 is preferably subjected to an easy adhesion treatment such as a corona discharge treatment, a plasma treatment, and an ozone treatment. For these easy adhesion treatments, a method usually used for this type of sheet can be used. By performing such an easy adhesion treatment, active hydrogen atom-containing functional groups such as a hydroxyl group and a carboxyl group can be generated on the surface of the base sheet. When the base sheet is formed by a melt extrusion method, these polar functional groups are generated to some extent on the surface during the formation of the film. Therefore, if the polar functional groups generated at the time of film formation are sufficient, the easy adhesion treatment may be omitted. After performing an easy adhesion treatment on the surface of the base material sheet, a specific primer composition is applied to the treated surface, dried and cured to provide a primer layer 2. The active hydrogen atom-containing functional group generated during the easy adhesion treatment or film formation also forms a urethane bond with the isocyanate group in the primer composition, whereby the adhesion between the base sheet and the primer layer is further improved.

In the present invention, the primer composition for forming the primer layer 2 is mainly composed of an acrylic polyol formed by using a monomer of octyl (meth) acrylate or cyclohexyl (meth) acrylate as a copolymer component, and the main component and an aliphatic or A two-component curable acrylic urethane resin composed by mixing an alicyclic isocyanate-based curing agent is used. Here, (meth) acrylate is a notation having the meaning of acrylate or methacrylate.

Acrylic polyol is used as a monomer.
It is obtained by copolymerizing at least one or both of (A) octyl (meth) acrylate and cyclohexyl (meth) acrylate, (B) a general-purpose acrylate, and (C) a hydroxyl group-containing acrylate. As the octyl (meth) acrylate, any of n-octyl (meth) acrylate and 2-ethylhexyl (meth) acrylate can be used.
Ethylhexyl (meth) acrylate is used. Examples of the general-purpose acrylate monomer include methyl (meth) acrylate, ethyl (meth) acrylate, butyl n- (meth) acrylate, and propyl (meth) acrylate. The hydroxyl group-containing acrylate includes 2-hydroxyethyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, 1-chloro-2-hydroxyethyl (meth) acrylate, and the like.

The composition of the above monomer component in the acrylic polyol is preferably in the following range. Component (A) 30 to 65% by weight Component (B) 10 to 45% by weight Component (C) 10 to 40% by weight Among the above monomer components, (A) is a combination of octyl acrylate and cyclohexyl acrylate [usually blending ratio] Is preferably about 1: 2 to 2: 1 (weight ratio)],
(B) is preferably methyl methacrylate, and (C) is preferably 2-hydroxyethyl methacrylate.

By increasing the content of the component A, the weather resistance can be improved.
And the flexibility is improved, while the blocking resistance is reduced. Increasing component B improves blocking resistance, but decreases weather resistance and flexibility. Also, by increasing the component C, the initial adhesion and the weather resistance adhesion are increased, but the flexibility is reduced. Therefore, each component is mixed in the above ratio, and the advantages of each component are drawn out and the disadvantages are suppressed.

The production examples of the acrylic polyol are shown below. A solvent having the following component composition was charged into a reaction vessel equipped with a stirring device, a dropping device, and a reflux condenser, and N _{2 was} sealed.
The temperature was raised to 0 to 90 ° C., and a monomer having the following composition was continuously added dropwise over 3 hours, followed by heating and stirring for 2 hours. Next, 1.2 parts by weight of a polymerization initiator (azoisobutyronitrile) was dropped from the dropping device while stirring, and then the mixture was heated at 80 to 90 ° C for 3 hours.
The mixture was reacted by heating and stirring for an hour to obtain an acrylic polyol. The obtained acrylic polyol has a hydroxyl value of 10 mg.
KOH / g and average molecular weight was 12,000.

[Monomer composition] 25 parts by weight of methyl methacrylate 15 parts by weight of 2-hydroxyethyl methacrylate 15 parts by weight of octyl acrylate 20 parts by weight of cyclohexyl acrylate 22 parts by weight of styrene Solvent composition 80 parts by weight of xylene acetic acid 20 parts by weight of butyl

As the isocyanate used as the curing agent, divalent or higher valent aliphatic isocyanate, alicyclic isocyanate or aromatic isocyanate is used. Aliphatic isocyanates are preferred from the viewpoint of good weather resistance and excellent discoloration prevention. Examples of the aliphatic or alicyclic isocyanate include 1,6-hexamethylene diisocyanate (HDI), 2,2,4 (2,4,4) -trimethylhexamethylene diisocyanate (TMDI),
4,4'-dicyclohexylmethane diisocyanate (HMDI), 1,4-cyclohexyl diisocyanate (CHDI), isophorone diisocyanate (IPD
I), lysine diisocyanate (LDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and the like. As the aromatic isocyanate, toluene diisocyanate (TDI),
And diphenylmethane diisocyanate (MDI). The isocyanate may be an adduct or a multimer of the above isocyanate.

The primer composition can be formed by mixing components such as a solvent and an additive in addition to the acrylic polyol and the isocyanate.

In order to further prevent the weather resistance deterioration of the adhesion of the primer layer, it is preferable to add a weather resistance additive such as an ultraviolet absorber or a light stabilizer to the primer layer.
The weather-resistant additive is, for example, a benzotriazole-based, hydroxybenzophenone-based, salicylate-based, acrylonitrile-based, metal complex-based, or ultraviolet absorbing agent composed of fine particles having a particle diameter of 0.2 μm or less of a metal oxide such as zinc oxide and cerium oxide. And light stabilizers such as a piberidine radical scavenger and a hindered amine radical scavenger. Among them, bis (2,2,6,6-tetramethyl-4-
Piberidinyl) sebacate is preferred. The addition amount of the above-mentioned weather resistance additive in the primer layer is preferably 0.1 to 5% by weight. Generally, it is preferable to use both an ultraviolet absorber and a light stabilizer. In that case, each 0.1 ~
Add 5% by weight.

The primer layer 2 is formed by applying a primer composition by gravure roll coating, roll coating, or the like. The coating amount of the primer layer 2 is 1 to 20 g /
m ² (when dry) is preferred, and more preferably 5 to 10
g / m ² (when dry).

The picture layer 3 may be made of a pattern layer such as a grain pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, a line drawing, various abstract patterns, or a solid layer such as a solid printing. Become. The picture layer 2 may be either a pattern layer only, a solid layer only, or a two-layer structure of a pattern layer and a solid layer.

The pattern layer 3 can be formed by printing and coating using a general pattern printing ink. The ink includes a binder and a colorant. Examples of the binder include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane (two-component curable urethane resin or thermoplastic urethane resin), and acrylic. , Polyvinyl acetate, vinyl chloride
One or a mixture of two or more kinds of vinyl acetate copolymers and cellulose resins is used. As a coloring agent,
Bright pigments consisting of pigments or dyes such as titanium white, carbon black, red iron oxide, graphite, ultramarine, phthalocyanine blue, quinacridone, isoindolinone, metal foil powders such as aluminum and brass, and foil powders of titanium dioxide coated mica. One type or a mixture of two or more types is used.

It is preferable to provide a protective layer 4 made of a transparent resin for improving the abrasion resistance and chemical resistance of the decorative sheet and adjusting the gloss of the surface. The protective layer 4 can be formed by coating on the surface of the picture layer 3 as shown in FIG. 1 or by sticking (laminating) a sheet formed in advance to cover the picture layer 3. When the picture layer 3 is provided on the back side of the base sheet 1 as shown in FIG. 2, it may be formed on the front side of the base sheet 1 (not shown).
The protective layer 4 is made of a polyolefin resin (similar to those listed as the material of the base sheet), an acrylic resin, a polyurethane resin, an epoxy resin, or an unsaturated (meth) resin.
A transparent or translucent resin such as an acrylate-based or epoxy-based ionizing radiation-curable resin is used. Protective layer 4
Is applied by gravure roll coating, roll coating, curtain flow coating, comma coating, extrusion (melt extrusion) coating, or the like. It is formed by a method such as dry lamination using an adhesive or fusion by a hot press.

The thickness of the protective layer 4 is 1 to 1 when dried.
Preferably, it is formed to have a thickness of about 00 μm. In the protective layer 4, various additives such as a matting agent (light diffusing agent) for matting, a lubricant, a weathering additive,
A lubricant or the like may be added. The matting agent is calcium carbonate,
Fine particles having a particle size of about 1 to 30 μm, such as silica, barium sulfate, urethane resin beads, and polycarbonate resin beads, are effective. As the lubricant, particles having a particle size of about 5 to 30 μm, such as spherical α-alumina, are used. The above-mentioned thing is used as a weather resistance additive. Wax or the like is used as the lubricant.

The decorative sheet of the present invention may be provided with decorations other than the pattern layer in addition to the pattern layer. For example, in addition to the method of adding a dye or a pigment to the above-described base sheet to perform transparent coloring or opaque coloring, a wood grain board conduit groove, a stone board surface unevenness (granite cleavage face, etc.), a cloth surface texture is provided on the surface of the protective layer 4. A,
A method of forming a concavo-convex pattern such as a satin finish, a grain, a hairline, a linear groove, or the like can be given. In order to form the concavo-convex pattern, for example, there are an embossing method by heating and pressing, a hairline processing method, and a shaping film method. The embossing method heats and softens the surface of the protective layer, presses the surface with an embossing plate to shape the concavo-convex pattern of the embossing plate, and cools and fixes it. Embossing machine or the like is used.

Further, a colored layer may be formed in the concave portion of the above-mentioned uneven pattern by a wiping method. As a wiping method, after applying the colorant ink to the entire surface including the concave portion by the doctor blade coating method or the knife coat method, the colorant ink is removed from the surface other than the concave portion, so that only the concave portion is colored. Form a layer. The colorant ink forming the colored layer is composed of a colorant such as a dye, a pigment, and a bright pigment as described above, a thermoplastic resin, a thermosetting resin, a binder resin such as an ionizing radiation-curable resin, and a vehicle. Inks and emulsion type water-based inks can be used.

Further, in order to impart flame retardancy to the decorative sheet, a powder such as aluminum hydroxide or magnesium hydroxide may be added as a flame retardant to the base sheet 1, the protective layer 3, or the like.

Further, in order to impart antibacterial properties to the decorative sheet, antibacterial agents such as zeolite powder carrying silver ions and antioxidants such as 10,10′-oxybisphenoxyarsine are applied to the base sheet 1 and the protective layer 3. A fungicide may be added.

The decorative sheet 1 of the present invention can be laminated on various adherends, subjected to a predetermined molding process and the like, and used for various decorative purposes. For example, interior decoration of buildings such as walls, ceilings and floors, surface decoration of fittings such as window frames, doors, handrails, furniture such as wardrobes or surface decoration of cabinets for light electric / OA equipment such as television receivers, automobiles, trains And other applications such as vehicle interiors, aircraft interiors, window glass cosmetics, and the like.

[0045]

Example 1 A 100 μm-thick polypropylene resin sheet (crystalline polypropylene 100 mainly composed of isotactic polypropylene) having both surfaces subjected to corona discharge treatment to form active hydrogen atom-containing functional groups on the surface as a base sheet. 25 parts by weight of hydrogenated styrene-butadiene rubber, 10 parts by weight of calcium carbonate, and a total of 5 parts by weight of a pigment mainly composed of titanium white, red iron oxide, and graphite), and corona discharge treatment of the sheet was performed. After applying a two-component curable acrylic urethane resin primer having the following composition to the surface of the surface under the following coating conditions to form a primer layer having a thickness of 2 μm, the acrylic resin and vinyl chloride-vinyl acetate copolymer Using a mixture of 8: 2 weight ratio of the coalesced as a binder, a red wood pattern and a wood grain pattern using a pigment-based ink composed mainly of carbon black. To obtain a decorative sheet printed with the via a rotary printing press. The decorative sheet after printing was wound around a paper tube having a diameter of 3 inches with a winding number of 100 m and cured in an atmosphere of 40 ° C. for 3 days to completely crosslink and cure the primer layer.

[Two-component curable urethane resin primer composition] 100 parts by weight of acrylic polyol (* 1) 8 parts by weight of hexamethylediisocyanate 10 parts by weight of solvent (ethyl acetate: toluene = 1: 1 weight ratio) * 1 : The acrylic polyol used was the one shown in the above Production Example.

[Primer coating conditions] Coat with a gravure roll coater.

Comparative Example 1 A decorative sheet was obtained in the same manner as in Example 1 except that a polyester polyol urethane resin primer having the following composition was used for comparison. [Polyester polyol-based urethane resin primer composition] 100 parts by weight of polyester polyol (* 2) 8 parts by weight of hexamethylene diisocyanate 10 parts by weight of solvent (ethyl acetate: toluene = 1: 1 weight ratio) * 2 [polyester polyol composition] -Neopentyl glycol 150 parts by weight-TMP 22 parts by weight-Adipic acid 72 parts by weight-Isophthalic acid 123 parts by weight An average molecular weight of 1,000 obtained by reacting the above components.

Comparative Example 2 A decorative sheet was obtained in the same manner as in Example 1 except that a vinyl chloride-vinyl acetate-maleic acid copolymer / isocyanate primer having the following composition was used. [Primer composition] ・ 100 parts by weight of vinyl chloride-vinyl acetate-maleic acid copolymer ・ 8 parts by weight of hexamethylene diisocyanate ・ 10 parts by weight of solvent (ethyl acetate: toluene = 1: 1 weight ratio)

For the decorative sheets of the examples and comparative examples,
After printing, the wound-up after curing was unwound, and the adhesion of the primer layer and the picture layer to the back surface of the base material sheet, that is, the presence or absence of blocking was visually confirmed. In addition, the initial adhesion immediately after pattern printing and the weather adhesion after 100 hours of the super UV weather resistance tester were measured from the printing surface with a cellophane adhesive tape (Nichiban Co., Ltd., trade name cellotape, width 24 mm. (For industrial use), peeled and tested. Table 1 shows the test results.
Shown in Super UV weathering tester, using Iwasaki Electric Co., Ltd. SUV-W13 type, UV intensity 60 mW / cm ² of the band of the 295～450Nm, test temperature (black panel temperature) 63 ° C., 70% humidity, ultraviolet radiation 20 hours and 4 hours of dew condensation were alternated. 10 under these conditions
Zero hour exposure is roughly equivalent to one year of outdoor exposure in Florida, USA.

In addition, both the decorative sheets of Examples and Comparative Examples were bonded to a 10 mm-thick Rawan plywood surface using an adhesive of a vinyl acetate emulsion in a state where the weathering tester was not irradiated. A groove having a V-shaped cross section reaching the adhesive layer was cut on the non-adhesive surface side of the decorative sheet, and the plywood was bent in an atmosphere of 150 ° C. so that the groove was closed, and V-cut.

[0052]

[Table 1] * 1: Whether the primer cracks at the bent part

[0053]

As described above, the decorative sheet of the present invention comprises, as a primer layer, octyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl (meth) acrylate, and (meth) acrylate containing a hydroxyl group in the molecule. Is used as a main component, and a two-component curable acrylic urethane resin having an aliphatic or alicyclic isocyanate as a crosslinking agent is used as a polyester polyol or vinyl chloride-vinyl acetate-maleic acid as a polyol. Compared with a conventional decorative sheet using a primer made of a two-component curable urethane resin using a copolymer, the adhesion of the primer layer to the base sheet made of the polyolefin resin is not limited to the initial adhesion. Good after weathering test, used outdoors Decorative sheet having no good design property of danger such as the release of the design layer for a long time can be obtained even if the total.

Even immediately after the application of the primer layer to the substrate sheet, the primer layer quickly develops adhesion and has good initial adhesion. Also, there is no risk of blocking, and the workability when producing a decorative sheet is excellent. Further, the flexibility of the primer layer is good, and the primer layer is less likely to be broken or peeled off during bending such as V-cutting.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing an example of the decorative sheet of the present invention.

FIG. 2 is a longitudinal sectional view showing another embodiment of the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base sheet made of polyolefin resin 2 Primer layer 3 Picture layer

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toru Sakamoto 1-1-1, Ichigaya-Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (72) Inventor Kazuho Kawano 1-chome, Ichigaya-cho, Shinjuku-ku, Tokyo No. 1-1 F-term in Dai Nippon Printing Co., Ltd. (reference) 4F100 AH02H AH03H AH07H AK03A AK07 AK25B AK51B AK73 AL01B BA02 BA41 CA02B EJ62 EJ65B GB08 GB33 HB00 HB00B JB13B JK06 JL01 JL11

Claims (4)

[Claims] 1. A decorative sheet having a pattern layer provided after a primer layer is applied to the surface of a base sheet made of a polyolefin-based resin, wherein the primer layer comprises octyl (meth) acrylate, cyclohexyl (meth) acrylate, Cured product of a two-part curable acrylic urethane resin containing methyl (meth) acrylate and acrylic polyol containing (meth) acrylate having a hydroxyl group in its molecule as a copolymer component and aliphatic or alicyclic isocyanate as a crosslinking agent A decorative sheet characterized by being formed from: 2. The decorative sheet according to claim 1, wherein a protective layer is laminated on the surface of the picture layer. 3. The method according to claim 1, wherein a bis (2,2,6,6-
The decorative sheet according to claim 1 or 2, further comprising (tetramethyl-4-piperidinyl) sebacate. 4. An active hydrogen atom-containing polar functional group is provided on the surface of a base sheet made of a polyolefin resin on the primer layer side, and the polar functional group and the primer layer are bonded by urethane. The decorative sheet according to claim 1, 2, or 3.