JPH11179824A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a whitening phenomenon or cracks from being generated at the time of V-cutting, in a decorative sheet using a film such as a an olefinic resin film. SOLUTION: The cross section shape patterned after a recessed cave-in figure 2 formed on the surface of a plastic film 1 is set as a curved line with a continuously changing curvature on an area excepting at least, a spot 4 near a part connected to the surface of the film 1. The plastic film 1 is such as of an acrylic resin, an olefinic resin, a thermoplastic polyester resin and an ethylene-vinylalcohol copolymer resin. In addition, an olefinic resin film may be laminated.

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, fittings, furniture, surface decoration of vehicle interiors and the like.

[0002]

2. Description of the Related Art Conventionally, decorative sheets used for the above applications can be classified into the following three types.

(1) Using a polyvinyl chloride film,
A decorative sheet decorated with printing, embossing or the like (Japanese Patent Publication No. 28-5036). (2) A decorative sheet that uses an olefin resin film such as polyethylene or polypropylene and is decorated with this by printing or embossing. (JP-A-54-62255,
Japanese Patent Publication No. 58-14312). (3) In order to improve the drawbacks of the olefin resin film, an olefin resin obtained by graft polymerization of a polar functional group may be mixed with an olefin thermoplastic elastomer (JP-A-6-210808). A decorative sheet using an olefin-based resin film obtained by mixing a polyurethane resin with a solubilizer (Japanese Patent Application Laid-Open No. 4-504384).

[0004]

However, each of the decorative sheets has the following problems. (1) The decorative sheet using the polyvinyl chloride film has insufficient heat resistance or bleeds (exudes) the plasticizer.
In addition to the fact that the surface has poor pollution resistance, there has been a problem that, in particular, from the viewpoint of global environmental problems, waste materials cannot be incinerated due to the generation of hydrogen chloride gas during incineration. The decorative sheet of (2) can be adapted to the global environment as a substitute for the polyvinyl chloride film for the decorative sheet of (1). However, if a simple polyethylene or polypropylene film is used as the olefin resin film, the polyvinyl chloride film is superior in terms of processing suitability such as V-cut and hot embossing, adhesion to printing and lamination, weather resistance, and cost. It is inferior to the performance that it has.

In the decorative sheet (3), the suitability of V-cut or hot embossing, and the adhesion to printing and lamination of an olefin resin film as a substitute for a polyvinyl chloride film are further improved.
Still, the impact resistance is weak, and crack breaks during V-cut processing. In particular, crystallization progresses due to the heat history at the time of embossing from heating softening to embossing plate pressing to cooling, the sheet becomes brittle, and this tendency is strengthened. In addition, there is a problem that embossing conditions are very narrow because of high crystallinity.

[0006]

In order to solve the above-mentioned problems, in the present invention, the cross-sectional shape of the concave pattern formed on the plastic film of the decorative sheet is determined by at least the surface of the plastic film on which the concave pattern is formed. In a portion other than the vicinity of the connection portion between the and the cross section, the shape was formed of a curve having a continuously changing curvature. With such a shape, the decorative sheet is V-cut (for example, Utility Model Application Publication No. 31122 in Taisho 15 and Japanese Patent Publication No.
In contrast to the tensile stress generated when forming and bending a V-shaped groove in a base material as disclosed in JP-A-39116, stress concentration applied to a plastic film can be reduced, and whitening and crack generation hardly occur. I can do it. Further, the plastic film is, for example, an acrylic resin, an olefin resin, a thermoplastic polyester resin, ethylene-
By using a transparent resin film selected from a vinyl alcohol copolymer resin, a decorative sheet that does not use a vinyl chloride resin film has excellent suitability for V-cut processing and embossing processing. In addition, the decorative sheet may have a configuration in which only the plastic film as described above is used as a support, but a configuration in which an olefin resin film is further laminated is effective.

[0007]

Embodiments of the present invention will be described below in further detail with reference to the drawings.

First, FIG. 1 explains that the cross-sectional shape of the concave pattern 2 of the decorative sheet 10 of the present invention on the surface of the plastic film 1 is a shape composed of a curve 3 having a continuously changing curvature. FIG. 2 and 3 are cross-sectional views illustrating various forms of the decorative sheet of the present invention. FIG. 2 shows a single-layer film, and FIG.
Is a two-layer film specification. FIG. 4 is an explanatory view in which the decorative sheet of the present invention is applied to V-cut processing, and FIG. 5 is an explanatory view in which the decorative sheet is applied to a three-dimensional article as an adherend.

First, the shape of the concave pattern of the decorative sheet of the present invention will be described in detail. As shown in the sectional view of FIG. 1, the decorative sheet 10 of the present invention
Has a shape composed of a curve 3 having a continuously changing curvature. The curve 3 defined by the present invention as the cross-sectional shape of the recessed pattern is arbitrary near the surface connection portion with the plastic film 1. There may be a shape in which the curvature changes discontinuously. Although the details are not clear, it is considered that stress concentration does not occur during V-cut processing in the portion near the surface connection portion 4. Of course, the section near the surface connection portion 4 may also have a cross-sectional shape consisting of a curve having a continuously changing curvature. in this case,
In all cross sections from the surface of the plastic film 1 to the inside of the concave pattern, the cross section is constituted by a curve having a continuously changing curvature. In the shape of the concave portion of the concave pattern seen in the conventional decorative sheet, if there is a portion having a discontinuous curvature at the valley bottom of the concave portion, stress concentration occurs there, and cracks and whitening easily occur therefrom.

Further, the cross-sectional shape of the concave pattern is a / W = x, where W is the thickness of the plastic film 1, a is the depth of the concave portion of the concave pattern 2, and b is 1/2 of the opening width of the concave portion. a
/ B = If set to y, it is preferably in the range of y <7x ² -0.95x + ² is established. If y exceeds the value defined by the above inequality, that is, y = a / b, and if the depth is too large with respect to the opening width, whitening and cracking during V-cutting are likely to occur, which is not preferable. The upper limit of y defined by the above inequality is a function of x, and x = a
/ W, when the depth a of the concave pattern becomes deeper with respect to the thickness W of the plastic film 1, the upper limit of y becomes larger, that is, the depth of the concave portion becomes larger with respect to the width of the concave portion. You can set patterns.

The use of a decorative sheet that defines the relationship between the thickness W of the plastic film 1 and the cross-sectional shape of the concave pattern 2 described above can be an alternative material to the vinyl chloride resin film as the plastic film used. ,
It is more effective when a film described later is used.
This is because, unlike a vinyl chloride resin film, crystallization of the film progresses due to the heat history at the time of forming the concave pattern, and the processability tends to decrease.

Therefore, if a concave pattern is formed without taking into account the above-mentioned geometrical elements, conventionally, when an external force at the time of V-cut is applied to the concave portion of the concave pattern, whitening and cracks are easily generated therefrom. . However, in the decorative sheet of the present invention, these whitening and cracking hardly occur, and the concave pattern shape defined by the present invention is of course effective for a decorative sheet using a conventional vinyl chloride resin film.

The recessed pattern 2 includes a wood grain conduit groove, a rugged surface (granite cleavage surface, etc.), a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, and the like. Also, a combination of these patterns may be used.

In order to form a concave pattern, for example,
As the method, there is an embossing method by heating and pressing. The embossing method is a method in which a plastic film is heated and softened, pressurized and shaped with an embossing plate, and solidified by cooling, and a known single-sheet or rotary embossing machine is used. In embossing, when embossing a single-layer film, a two-layer film, or a two-layer film, pressing the embossing plate on the surface of the plastic film and shaping the unevenness of the plate Will be formed. The decoration processing by printing or the like, which will be described later, is performed on the film before, after, or both of the concave pattern creation.
Further, when a transparent protective layer or the like is applied on the recessed pattern, it is of course performed after the formation of the recessed pattern.

Here, various forms of the decorative sheet of the present invention will be described. The decorative sheet of the present invention is formed by forming the concave pattern 2 having the above-mentioned specific shape on the surface of the plastic film 1, and there are various forms depending on the form of the decorative processing as the decorative sheet. Some of them are explained.

First, FIG. 2 is a cross-sectional view showing various forms of a structure in which a support of a decorative sheet is formed of a single-layer film of a plastic film 1 in which a concave pattern is formed. FIG.
(A) is a decorative sheet 10 having a concave pattern 2 in a colorless or colored transparent film as a plastic film 1. FIG. 2B shows a decorative sheet 10 in which the plastic film 1 is made a colorless or colored and opaque film by a filler such as a pigment. FIG.
(C) is a decorative sheet 10 having a configuration in which a decorative layer 5 is provided on the back side of a colorless or colored and transparent plastic film 1 by printing or the like with an easy-adhesion layer 6 interposed therebetween. further,
FIG. 2 (D) shows that a colored portion 7 is provided by a wiping process or the like inside the concave portion of the concave pattern 2 of the colorless or colored transparent or opaque plastic film 1 and the surface of the plastic film 1 is decorated by printing or the like. This is a decorative sheet having a configuration in which a layer 5 is provided.

First, FIG. 3 shows a configuration using a multilayer film as a support for a decorative sheet. In FIG. 3, a plastic film having a multilayer, two-layer film specification, that is, a plastic film having a concave or concave pattern is formed. 1 is a cross-sectional view showing various forms of a decorative sheet 10 having a configuration including a laminate of an olefin resin film 8 and an olefin resin film 8. FIG. 3A shows a colorless or colored and transparent film having a concave pattern 2 as a plastic film 1, and a colorless or colored and transparent olefin-based resin film 8 having a decorative layer formed thereon by printing or the like. The decorative sheet 10 has a configuration in which the decorative sheets 10 are laminated through the intermediate sheet 5. FIG. 3B is a decorative sheet 10 having a configuration in which the olefin resin film 8 is made colorless or colored and opaque by a filler such as a pigment in the configuration of FIG. 3A. When printing the decorative layer 5, the plastic film 1 side, the olefin-based resin film 8 side,
Or both can be both. Next, FIG. 3 (C)
The decorative sheet 10 has a configuration in which an easy-adhesion layer 6 is provided between the decorative layer 5 and the olefin-based resin film 8 in the configuration of FIG. Further, FIG. 3 (D) corresponds to FIG.
In contrast to the above configuration, the colored portion 7 is provided inside the concave portion of the concave portion 2, and the transparent resin layer 9 is provided on the entire surface of the plastic film 1 having the concave portion 2 provided with the colored portion 7. Sheet 10. The easy-adhesion layer 6 is usually on the side on which the decorative layer 5 is printed, but any of them can be used.

Although several decorative layers of the decorative sheet having a single-layer or double-layer film as the support have been described above, the decorative sheet according to the present invention is not limited to the above-described configuration in the drawings. It is not something to be done. For example, a transparent protective layer may be formed on the entire surface of the plastic film 1 on which the concave pattern 2 is formed. Various modes (not shown) are possible by a combination of these layer configurations.

Next, each material of the decorative sheet of the present invention will be described sequentially.

First, as the plastic film 1 on which the concave pattern 2 is formed, a polyvinyl chloride film may be used, but an olefin resin such as an acrylic resin or a polypropylene resin, an ethylene-vinyl alcohol copolymer resin, Alternatively, one selected from thermoplastic polyester-based resins is preferably used. These resins are particularly preferable as resins that can be used as substitutes for polyvinyl chloride films in view of global environmental problems. The thickness of the plastic film 1 depends on the resin material, the difference between the single-layer specification and the multi-layer specification, and the depth and shape of the recessed pattern to be formed.
Usually, it is about 10 to 300 μm. In the case of a multilayer specification, if the olefin-based resin film to be laminated is used as a main support, the plastic film 1 has a thickness of 10 μm.
It is also possible to make it thinner. In the case of a single-layer specification, the thickness is preferably 20 μm or more because it is necessary to maintain the mechanical strength of the support. Further, any of stretched and unstretched may be used, but in terms of molding suitability such as V-cut processing,
Unstretched films are better.

Examples of the acrylic resin include poly (meth) acrylate, poly (ethyl) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate. −
From homo- or copolymers containing (meth) acrylates, such as butyl (meth) acrylate, ethylene-methyl (meth) acrylate, and styrene-methyl (meth) acrylate Resin. In addition, "(meth) acryl" means acryl or methacryl.

As the olefin-based resin, various resins which can be used as an olefin-based resin film described later as a film to be laminated with a plastic film can be arbitrarily selected and used.

As the ethylene-vinyl alcohol copolymer resin, the thermoplastic and water resistance of ethylene and the rigidity, oil resistance, solvent resistance, Although the magnitude of the chargeability can be arbitrarily adjusted, a film having an ethylene component of 30 to 45 mol% is preferable in order to obtain a film having both characteristics as much as possible and having excellent workability. If it is less than 30 mol%, the thermoplasticity, heat processing suitability and water resistance are poor, and if it exceeds 45%, the rigidity, oil resistance, solvent resistance and antistatic properties are poor, which is not preferable. The ethylene-vinyl alcohol copolymer resin film may be a stretched film or an unstretched film. However, in view of flexibility of the film, suitability for bending, suitability for embossing, etc. It is preferable to use
Generally, a random copolymer of ethylene and vinyl alcohol is used.

The thermoplastic polyester resin is, for example, a resin typified by polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate / isophthalate copolymer and the like, and terephthalic acid, isophthalic acid, naphthalene as an acid component. A polyester having an aromatic dicarboxylic acid such as a dicarboxylic acid and an aliphatic diol such as ethylene glycol, diethylene glycol, butanediol, and hexanediol as an alcohol component.

The film of the non-chlorine-containing resin as described above, when forming a recessed pattern on the film surface by hot pressing such as embossing, as compared with a conventional polyvinyl chloride film, heat softening to emboss plate pressing. Due to the progress of crystallization due to the heat history of cooling, the film tends to become brittle, and thus whitening and cracks were likely to occur during V-cut processing, but the cross-sectional shape of the concave pattern is described in the present invention as described above. By forming the shape, the whitening and the occurrence of cracks can be prevented.

The decorative sheet of the present invention may be a decorative sheet (FIG. 2) in which a concave pattern is formed on the plastic film by hot pressing such as embossing and one layer of the plastic film is used as a support. As shown in the cross-sectional views of the decorative sheets of various forms of No. 3, a layer structure in which the olefin-based resin films 8 are laminated may be employed.

Examples of the olefin resin film 8 include polyethylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, polypropylene,
Butene-1 copolymer, polybutene-1, butene-1, propylene, ethylene terpolymer, butene-1, hexene-1, octene-1, terpolymer, polymethylpentene, or JP-A-6 A resin composed of an olefin-based elastomer described in, for example, Japanese Patent No. 16832 is used.
The thickness is about 50 to 500 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.

These olefin resins are used as a film by themselves, but various rubbers can be added to impart flexibility, impact resistance and easy adhesion to the resin film. Examples of the rubber include a diene rubber, a hydrogenated diene rubber, and an olefin elastomer, and among them, a hydrogenated diene rubber is preferable. Hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of diene rubber molecule, and is used as a modifier for a resin film. There is a role to improve the nature and transparency. In addition, generally, when a diene rubber is added to an olefin resin, the double bond of the diene rubber causes the weather resistance,
Although the heat resistance is lower than that of the olefin resin containing no diene rubber, the hydrogenated diene rubber has no decrease in weather resistance and heat resistance.

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. Among them, styrene-butadiene rubber is a preferred diene rubber. The amount added is about 1 to 90 parts by weight based on 100 parts by weight of the polyolefin resin. If it is less than 1 part by weight, the elasticity due to rubber addition, elongation,
Impact resistance is insufficient, and cracks and cracks are likely to occur during bending processing such as V-cut processing and drawing processing. On the other hand, if it is 90 parts by weight or more, the elasticity and the elongation are too large, and the registration during printing becomes poor, which is not preferable.

In the two-layer film specification of the decorative sheet of the present invention, if a film made of an olefin resin is used as the plastic film having a concave pattern, both the plastic film and the film laminated therewith have an olefin resin. A configuration using a film made of the same substance (thickness is not necessarily the same), which is a base resin film, is also a form of the decorative sheet of the present invention.

When an olefin-based resin film is used, there is a correlation between the dimensional shrinkage upon heating and the crack / break resistance during bending in V-cut, and after heating in an atmosphere at 100 ° C. for 30 minutes. In the case of a long belt-shaped film, the dimensional shrinkage ratio (based on before heating) is preferably in the range of −2 to + 7% in the longitudinal direction of the film and −7 to + 2% in the width direction of the film. If the dimensional shrinkage deviates from this range, V
It is not preferable because cracks are easily generated during the cutting process. still,
The difference between the allowable value of the heating dimensional shrinkage ratio in the longitudinal direction and the width direction of the film depends on the material mechanical history of the film at the time of film production and how the impact force is applied at the time of film processing in the longitudinal direction and the width direction. It is because it is different. The dimensional shrinkage upon heating has a large correlation with the stretching of the olefin-based resin film. In the case of no stretching, the heating dimensional shrinkage ratio falls within this range, and when stretched three times or more, in most cases,
It is out of the range of the heating dimensional shrinkage. Therefore, when stretching, the stretching ratio is controlled so that the heating dimensional shrinkage ratio falls within the above range.

Next, as the decorative processing in the decorative sheet of the present invention, only the above-mentioned concave pattern may be used, but by further performing the decorative processing described below in combination with the concave pattern as appropriate, a decorative sheet having a higher design property can be obtained. Becomes

First, there is a decoration treatment in which a pigment or the like is kneaded into a plastic film used for a decorative sheet so as to be colored transparent or colored opaque, or colorless opaque or colored opaque. In the case of laminating an olefin resin film on a plastic film, the plastic film may be transparent as it is or may be colored and transparent. There is also. As the pigment to be kneaded and added, titanium white, zinc white, red petals,
Inorganic pigments such as vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black and the like, and organic pigments such as isoindolinone, Hansa yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indaslen blue RS, aniline black and the like (or Dyes), metal pigments such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica, and basic lead carbonate, and the like.

The decorative layer 5 may be provided by printing or the like.
The surface on which the decorative layer is provided is optional such as the front surface, the back surface, both the front and back surfaces of the plastic film, the front surface (between the plastic film) of the olefin resin film, the back surface, and the front and back surfaces. To form the decorative layer by printing, gravure printing, offset printing, letterpress printing, flexographic printing, silk screen printing, electrostatic printing, ink jet printing, or the like, or separately forming a decorative pattern on a release sheet once Any known printing means may be used, such as forming a transfer sheet and forming the transfer sheet by transfer printing using the obtained transfer sheet. The pattern of the decoration layer includes, for example, a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a character, a geometric figure, a symbol,
Examples include line drawings, various abstract patterns, and solid printing on the entire surface. The decoration layer formed by the entire surface may be a colored concealing layer. In the case of the entire surface, the decoration layer may be formed by a known coating method.

Various inks can be used as the printing ink for the decorative layer, and include a binder resin, a coloring agent, a solvent, and, if necessary, an extender pigment, a curing agent, and various additives. The added composition can be used. There is no particular limitation on the binder resin, and chlorinated polyethylene, chlorinated polypropylene, vinyl acetate, a vinyl chloride-vinyl acetate copolymer, a thermoplastic resin such as a cellulose resin, a room temperature such as polyurethane, or the like. Usual resins such as thermosetting resins and ionizing radiation-curable resins such as acrylic resins can be used. In addition, as a coloring agent, titanium white, zinc white,
Red pigment, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, inorganic pigments such as carbon black, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4
R, phthalocyanine blue, indaslen blue RS,
Organic pigments (including dyes) such as aniline black,
Pearlescent luster made from metal pigments such as aluminum and brass, titanium dioxide-coated mica, and foil powder such as basic lead carbonate
Conventionally known coloring pigments such as pigments can be used. As the extender, calcium carbonate, silica, alumina, barium sulfate and the like can be used. In addition, the printing ink may be any of a solvent system and an aqueous system, and in each system,
Either a solution system or a dispersion system may be used.

When printing directly on an olefin resin film, chlorinated polyolefin, polyurethane or the like is preferable as the binder resin from the viewpoint of adhesiveness, but an easy adhesion treatment may be performed on the printed surface. In addition, the easy adhesion treatment can improve the adhesion between the films and the like even in the form of a multilayer film in which a plastic film and an olefin-based resin film are laminated.

As the decorative layer 5, a metal thin film may be entirely or partially laminated in a pattern. The metal thin film may be formed of a metal such as aluminum, chromium, gold, silver, or copper by vacuum evaporation. The film is formed by a method such as sputtering. To form a pattern, a removal layer is formed in a desired pattern with a water-soluble ink on a unnecessary portion of the metal thin film. A known method such as removal of the metal thin film immediately above the surface is used. Of course, the entire or partial pattern of the metal thin film may be transferred and formed from the metal thin film previously formed on the transfer sheet by the transfer printing method. Also,
The decorative layer may be a combination of the layer formed by printing and the metal thin film.

The decorative treatment of the decorative sheet of the present invention includes:
The coloring portion 7 may be provided by applying a coloring agent to the recessed portion of the recessed pattern by the wiping method [FIG. 2 (D), FIG.
(D)). The wiping method is to apply colorant ink to the entire surface including the concave pattern by doctor blade coating or knife coating, and remove the colorant ink from the surface other than the concave part of the concave pattern to color the concave part. It is possible to use a method of filling a coloring agent to form a colored portion. As a colorant ink for forming a colored portion, a vehicle composed of a binder resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation-curable resin and a solvent and an organic pigment, an inorganic pigment, a glitter pigment, and the like. Or an ink containing an additive as required, or an emulsion-type water-based ink.

The easy adhesion treatment described above for the decorative layer is a corona discharge treatment, a plasma treatment, or a coating or printing of the easy adhesion layer (FIG. 2C,
3C). As the easy-adhesion layer, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, polyurethane resin, chlorinated polypropylene, chlorinated polyethylene, and the like are used. Among them, chlorinated propylene is a preferred resin. One. Incidentally, the formation of the easy-adhesion layer may be performed by a conventionally known coating method or printing method on the surface on which the corona treatment is appropriately performed.However, if necessary, various fillers may be used in consideration of coating suitability, printing suitability, and the like. Additives are appropriately contained.

Examples of the acrylic resin include polymethyl (meth) acrylate, polyethyl (meth) acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate. Meta)
Such as butyl acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, and styrene-methyl (meth) acrylate copolymer; An acrylic resin or the like comprising a homo- or copolymer containing (meth) acrylic acid ester. Here, (meth) acryl means acryl or methacryl.

The polyurethane resin is mainly composed of a polyol (polyhydric alcohol) and isocyanate compound
It is a reaction product using a crosslinking agent or the like as a curing agent. The polyol has two or more hydroxyl groups in the molecule, and is basically a polymer diol containing a monomer diol, a triol, or the like, and a chain of an alkylene repeating unit mainly contributing to the molecular weight thereof. , And triols. Typical polymer polyols consist essentially of either linear or branched chains of the above repeating units terminated with hydroxy groups, preferably monomeric polyols having 2, 3, 4 or more hydroxy groups including. For example, ethylene glycol, propylene glycol, glycerin,
Trimethylolpropane, 1,2,6-hexanetriol, butenediol, sucrose, glucose,
Sorbitol, pentaerythritol, mannitol,
Includes triethanolamine, n-methyldimethanolamine, and cyclic aromatic and aliphatic and triols. Further, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.

As the isocyanate compound, a polyvalent isocyanate compound having two or more isocyanate groups in a molecule is used. For example, 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, polyphenylmethane polyisocyanate called crude MDI, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane Aliphatic, alicyclic or aromatic di- or triisocyanate compounds such as -4,4'-diisocyanate and triphenylmethane triisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or polyisocyanate compound and low molecular weight glycol Or triols such as dipropylene glycol, 1,6-hexanediol, 1,2,6-hexanetriol, trimethyl Reacted with Rupuropan isocyanate-terminated low molecular weight adduct obtained can be used.

By the way, the decorative processing of the decorative sheet is performed by wiping the concave portion of the concave pattern described above.
A coloring agent may be applied. As a wiping method, by applying a colorant ink to the entire surface including the concave pattern by a doctor blade coat method or a knife coat method, and removing the colorant ink from the surface other than the concave portion of the concave pattern,
A method of filling the concave portion with a coloring agent can be used.
As a colorant ink for forming a colorant, organic pigments, inorganic pigments, brilliant pigments, etc. are used in a vehicle comprising a binder resin such as a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin and a solvent and a solvent. Or an ink containing an additive as required, or an emulsion-type water-based ink.

As shown in the decorative sheet 10 of FIG. 3 (D), a transparent resin layer 9 is further provided on the surface of the plastic film 1 on which the concave pattern 2 is formed in order to further protect the surface and impart design. May be. In addition, when the concave portion of the concave pattern 2 is completely filled with the transparent resin layer and the concave portion disappears from the surface of the plastic film, the concentration of tensile stress at the time of the V-cut processing occurs, and the shape factor of the cross section is eliminated. Therefore, except for the case where the mechanical strength of the transparent resin layer is weaker than that of the plastic film so that its existence can be neglected (because the transparent resin layer usually has the function of a protective layer, there is almost no such case) The occurrence of whitening and cracking from the recess is less likely to occur. However, when the thickness of the transparent resin layer is thin with respect to the depth of the concave portion, and the concave portion due to the concave portion remains on the decorative sheet surface even after the transparent resin layer is formed, the cross section of the concave pattern defined by the present invention. The shape is effective. In this case, the value of the depth a of the recessed portion and the value b of １ ／ of the opening width of the recessed portion should be based on the depth and the opening width of the recessed shape after the formation of the transparent resin layer. When the thickness is thin, the sectional shape of the concave pattern before the formation of the transparent resin layer may be viewed. As the transparent resin layer, a plastic film of the same or different kind as the lower plastic film may be adhered, but a colorless transparent or colored transparent resin coating may be formed by coating or printing. As such a resin, for example, a polyurethane resin, an unsaturated polyester resin, a fluororesin, a polysiloxane resin, or an ionizing radiation curable resin made of various acrylates, polyesters, and the like are preferable. Although the thickness depends on the depth of the concave portion forming the concave pattern, it is usually 1 to 30.
It is about μm.

In the decorative sheet of the present invention, one of the above-mentioned plastic film and olefin resin film (usually a film on the front side) or both may be provided with an ultraviolet absorber or a light stabilizer for improving light resistance. A filler may be added for adjusting physical properties, a flame retardant for improving flame retardancy, and various additives such as a dye and a foaming agent, as required.

In order to impart good weather resistance (light resistance) to the decorative sheet, either one of the ultraviolet absorber and the light stabilizer to be added may be used. It is preferable to use a stabilizer in combination. The addition amount of the ultraviolet absorber and the light stabilizer is usually about 0.5 to 10% by weight. If the amount is less than this, the effect of improving the weather resistance cannot be sufficiently obtained, and if it is more than this, coloring occurs, and even if it is contained in a large amount, there is no effective change, which is not preferable.

Examples of the ultraviolet absorber include organic ultraviolet absorbers such as benzotriazole, benzophenone, and salicylic acid, and inorganic materials such as zinc oxide, cerium oxide, and titanium oxide having a particle size of 0.2 μm or less. Can be used. As the light stabilizer, bis- (2,2,2,
Hindered amine radical scavengers such as (6,6-tetramethyl-4-piperidyl) sebacate can be used.

As the filler, powders such as calcium carbonate, barium sulfate, clay and talc are used. Add an appropriate amount as needed.

As the flame retardant, powders such as aluminum hydroxide, magnesium hydroxide and antimony trioxide, or inorganic fillers such as calcium carbonate are used. The content of the flame retardant is appropriately adjusted depending on the intended flame retardant grade, but is 10 to 15 parts by weight per 100 parts by weight of the resin content of the film.
It is about 0 parts by weight. If the amount is less than this, the flame-retardant effect cannot be sufficiently obtained, and if it is more than this, the film becomes brittle, which is not preferable.

When the above-mentioned plastic film or olefin-based resin film is used as a decorative sheet using a cellular (sponge) foam, a resin film to which a foaming agent has been added is heated to form a foam. Allow the agent to foam. Examples of the foaming agent include azodicarbonamide, azobisisobutyronitrile, N-N'-dinitrosopentamethylenetetramine, oxybisbenzenesulfonylhydrazide, sodium hydrogencarbonate, potassium hydrogencarbonate, and the like, or acrylonitrile. A microcapsule type in which a heat-expandable gas such as hexane or isobutane is sealed in a resin spherical shell such as The addition amount is usually 1 to 10 parts by weight based on 100 parts by weight of the resin content of the film.

As described above, the layer structure of the decorative sheet of the present invention is, for example, a single-layer film specification in which a plastic film is used as a support, and a concave pattern is formed on the support, and if necessary, decoration processing such as printing is performed. Or a multilayer film specification in which an olefin-based resin film is laminated on a plastic film having a concave pattern formed thereon or simultaneously with the formation of the concave pattern, and further subjected to a decoration treatment by printing or the like as necessary. there were.

In order to obtain a decorative sheet of a two-layer film type as shown in FIG. 3, for example, after printing a decorative layer 5 by printing on an olefin-based resin film 8, the plastic film 1 is wrapped over the decorative layer 5 by doubling embossing. The concave pattern 2 may be embossed on the surface simultaneously with the thermal lamination. Alternatively, the plastic film 1 after the concave pattern 2 is formed on the surface may be laminated on the olefin-based resin film 8 by dry lamination. The decorative layer 5 by printing that is interposed between these films may be formed on one or both films. In addition, as appropriate,
The surface on which the improvement in adhesiveness is desired is subjected to an easy-adhesion treatment such as an easy-adhesion layer.

The decorative sheet according to the present invention as described above is used for laminating on the surface of various members to apply surface decoration. As an adherend, a metal plate of iron, aluminum, etc., a veneer of wood,
Wood board such as wood plywood, wood fiber board, ceramics such as glass and ceramics, board material such as cement board such as ALC, board material of resin board such as polypropylene and phenolic resin, or resin molding made of these various materials Three-dimensionally shaped articles are included. In particular, the decorative sheet of the present invention has improved V-cut suitability, and is suitable for adherends conventionally used for V-cuts such as wooden boards, but adherends made of other materials However, it is also suitable for applications in which a decorative sheet is folded as in the case of V-cut. The decorative member laminated with a decorative sheet by these methods and surface-decorated is used for interior decoration of a building such as a wall surface, a ceiling, a floor, a surface decoration of fittings such as a window frame, a door, a handrail, furniture and light electric appliances / OA. It can also be used for surface makeup of equipment cabinets, vehicle interiors such as automobiles, trains, and aircraft, and window crows.

A method of laminating a decorative sheet on these various adherends is, for example, a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive, Japanese Patent Publication No. Sho 50-1.
No. 9132, JP-B-43-27488, etc., after a decorative sheet is placed between both male and female molds for injection molding, a molten resin is injected and filled into the mold to form a resin molded product. At the same time, a so-called injection molding simultaneous lamination method in which a decorative sheet is adhesively laminated on the surface,
No. 45768, Japanese Patent Publication No. 60-58014, etc., a decorative sheet is opposed to or placed on the surface of a three-dimensional article such as a molded article with an adhesive therebetween, and the three-dimensional article side So-called vacuum press lamination method in which a decorative sheet is laminated on the surface of a three-dimensional article by a pressure difference caused by vacuum suction from the Japanese Patent Publication No. 61-5895, Japanese Patent Publication No. 3-2
As described in JP-A-666, etc., in the major axis direction of a columnar substrate such as a cylinder and a polygonal pillar, while supplying a decorative sheet via an adhesive layer therebetween, by a plurality of rollers having different directions,
A so-called lapping method in which decorative sheets are sequentially pressure-bonded and laminated on a plurality of side surfaces constituting a columnar base material, Japanese Utility Model Publication No. 15-31122, and Japanese Patent Application Laid-Open No. 48-47972.
As described in the publication, first, a decorative sheet is laminated on a plate-shaped substrate via an adhesive layer, and then, on the surface of the plate-shaped substrate opposite to the decorative sheet, a decorative sheet and a plate-shaped Cut the V-shaped or U-shaped groove to reach the interface with the substrate,
Next, there is a so-called V-cut or U-cut processing method in which an adhesive layer is applied in the groove and the groove is bent to form a box or a column.

In particular, the method of bonding the decorative sheet of the present invention to a three-dimensional object having irregularities includes the following method:
In addition to being suitable for the cutting method and the lapping method, it shows its true value in the laminating method for extending the decorative sheet, such as the injection molding simultaneous laminating method and the vacuum press laminating method. FIG. 4 is an explanatory diagram when the decorative sheet of the present invention is applied to V-cut processing. In FIG. 1A, the back surface of the flat adherend 30 is cut into a right-angled triangle as a V-cut portion 31, and a plastic film having a concave pattern 2 formed on the front surface of the adherend 30. 1 shows a state in which the decorative sheet 10 in which the decorative sheet 1 and the olefin-based resin film 8 are laminated with the decoration layer 5 interposed therebetween is laminated with the adhesive layer 20 made of an appropriate adhesive interposed therebetween. FIG. 7B shows the state after the 90 ° bending process is performed at the V-cut portion. Also, FIG.
As the adherend 32, the decorative sheet 10 of the present invention is formed on the surface of a three-dimensional article made into a three-dimensional object by a molded product or other methods.
Are laminated. Note that the adhesive layer may be omitted in the injection molding simultaneous lamination method or the like.

[0056]

EXAMPLES Hereinafter, the decorative sheet of the present invention will be described more specifically with reference to examples.

First, a corona-treated one side of a 100 μm-thick polyethylene resin film having a beige hiding power as an olefin resin film having the following composition,
A primer ink (NH media, manufactured by The Inktec Co., Ltd.) is gravure coated to form an easily adhesive layer, and then a pattern ink (Chemical X, manufactured by The Inktec Co., Ltd.) is formed thereon.
1) was gravure printed to print a wood grain decorative layer.

Polyethylene resin film composition High density polyethylene 60 parts by weight Styrene-butadiene rubber (thermoplastic elastomer) 30 parts by weight Calcium carbonate 10 parts by weight

On the other hand, as a transparent plastic film, an acrylic resin film (Acribrene HBS-027, manufactured by Mitsubishi Rayon Co., Ltd.) having a thickness of 30 μm was thermally laminated on the film on which the decorative layer had been formed, and at the same time, the surface of the plastic film was Then, a concave pattern of the wood grain conduit was formed. Furthermore, in the concave portion of the formed concave pattern,
Urethane resin ink (manufactured by Showa Ink Industries, Ltd., GM
-A12), a colored portion was formed by a wiping process. Furthermore, transparent ink (Showa Ink Industry Co., Ltd.)
And OP-A12) were gravure coated to form a transparent resin layer as a protective layer to obtain a decorative sheet of the present invention.

The cross-sectional shape of the concave pattern of the decorative sheet is determined by the thickness W = 13 of the film on which the concave pattern is formed.
For 0 μm (30 μm + 100 μm), the depth a of the recess a = 60 μm, x = a / W = 0.46, b of 1/2 of the opening width of the recess is 60 μm, and y = a / b = 1 2.0. 7x ² -0.95x + 2 = 3.0 and y =
a / b = 1.0 is a shape less than 3.0. Further, as shown in FIG. 1, the cross-sectional shape of the concave pattern was a curve having a continuously changing curvature including the vicinity of the connection with the surface.

When the V-cut portion of the obtained decorative sheet was adhered to a right-angled triangular flat plate-like wooden plywood using an adhesive and then bent at 90 °, the portion corresponding to the V-cut portion was removed from the portion corresponding to the V-cut portion. No whitening or cracking occurred.

[0062]

According to the decorative sheet of the present invention, even if the decorative sheet has a concave pattern, whitening or cracking occurs at the time of the V-cut because the sectional shape is a curve having a curvature that changes continuously. Hateful. Furthermore, the plastic film used for the decorative sheet can be used as a substitute for the conventional polyvinyl chloride film as a polyvinyl chloride resin, such as acrylic resin, olefin resin, polyester resin, and ethylene-vinyl alcohol copolymer resin. In the case of using a resin film made as described above, it is effective in preventing whitening and cracking at the time of V cutting, and further, in a decorative sheet in which the plastic film and the olefin resin film are laminated, whitening and cracking occur. It is difficult to obtain excellent V-cut processing aptitude.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a cross-sectional shape of a concave pattern of a decorative sheet of the present invention.

FIG. 2 is a cross-sectional view showing various forms (single-layer film specification) of the decorative sheet of the present invention.

FIG. 3 is a sectional view showing various forms (two-layer film specification) of the decorative sheet of the present invention.

FIG. 4 is a cross-sectional view illustrating application of the decorative sheet of the present invention to V-cut processing.

FIG. 5 is an explanatory view applied to a three-dimensional article as an adherend of the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Plastic film 2 Depressed pattern 3 Curve 4 Near surface connection part 5 Decorative layer 6 Easy adhesion layer 7 Colored part 8 Olefin-based resin film 9 Transparent resin layer 10 Decorative sheet 20 Adhesive layer 30 Adherend (flat plate) 31 V cut part 32 adherend (three-dimensional shaped article)

Claims (4)

[Claims] 1. A decorative sheet, characterized in that the cross-sectional shape of the concave pattern formed on the surface of the plastic film is a curve having a continuously changing curvature at least except for the vicinity of the connection with the surface. 2. The cosmetic according to claim 1, wherein the plastic film is a resin film selected from an acrylic resin, an olefin resin, a thermoplastic polyester resin, and an ethylene-vinyl alcohol copolymer resin. Sheet. 3. The decorative sheet according to claim 2, wherein the plastic film is a transparent film. 4. A decorative sheet comprising the plastic film according to claim 1, 2 or 3 and an olefin-based resin film laminated.