JP2001191455A - Decorative sheet and decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having sufficient flexibility or thermoforming properties suitable for bending processing or three-dimensional molding processing, excellent in heat resistance, oil resistance or solvent resistance and capable of being inexpensively produced because of its being composed mainly of paper. SOLUTION: Impregnated paper prepared by impregnating raw paper 1 with an NBR latex resin as an impregnating resin 3 is used as a base material sheet. As the NBR latex resin, a high nitrile NBR latex resin containing 35-50 weight % of an unsaturated nitrile monomer as a monomer component is desirable and/or a carboxylate NBR latex resin containing an unsaturated carboxylic acid monomer as a copolymerizable component is desirable.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to interior and exterior materials for buildings such as houses, construction materials, building materials such as fittings, furniture and fixtures, and the like.
The present invention relates to a decorative sheet and a decorative material for use as a surface decorative material for housing equipment and home appliances, an interior material for transportation equipment such as vehicles, and particularly, for example, a complicated sheet such as a sliding door or a solid plate. For surface decoration of two-dimensional or three-dimensional three-dimensional members, it is used by applying a V-cut bending process after attaching to a base material or attaching it to a three-dimensional base material by a lapping method, vacuum forming method, or the like. The present invention relates to a decorative sheet suitable for a used application.

[0002]

2. Description of the Related Art As a decorative sheet used for surface decoration of a three-dimensional member as described above, it has conventionally been provided with excellent secondary workability such as excellent flexibility and thermoformability, and surface hardness. A decorative sheet made of a polyvinyl chloride resin, which has widely well-balanced properties such as surface properties such as abrasion resistance and chemical resistance and weather resistance, has been most widely used.

However, in recent years, polyvinyl chloride resin has a problem that toxic gas such as hydrogen chloride and highly toxic substance such as dioxin may be generated during combustion such as in a fire or incineration. It has been pointed out that the market has been shunned, and there has been a strong social demand for such a problem-free alternative to chlorine-free materials.

In order to meet such a demand, a decorative sheet using, for example, a thermoplastic polyolefin resin as a resin containing no chlorine (see Japanese Patent Application Laid-Open No. 6-16832).
Have been proposed, and replacement with a decorative sheet made of polyvinyl chloride resin is gradually progressing.

[0005] This decorative sheet made of polyolefin resin has been shown to have excellent performance for the most common flat decorative boards, and is the most promising substitute for a decorative sheet made of polyvinyl chloride resin. Is assumed to be

However, the polyolefin resin is essentially a crystalline polymer, and also has a sea-island structure in which crystallized portions are scattered in an amorphous matrix. It is non-uniform when viewed, and local non-uniform deformation is likely to occur even during plastic deformation.

[0007] Due to this principle, the bent portion is whitened during bending such as V-cutting or lapping, or molding failure such as necking or embossing occurs during three-dimensional forming by vacuum forming or the like. There is a problem that pattern deterioration due to uneven elongation at the edges and corners of the part and base material, and quality deterioration such as whitening at the high elongation parts such as the edges and corners are likely to occur. It is difficult to use it for a complicated three-dimensional shape having a large difference in unevenness.

In order to solve such a problem, as a decorative sheet excellent in bending workability and three-dimensional forming workability, instead of a general-purpose thermoplastic resin such as polyethylene or polypropylene,
Various decorative sheets using a thermoplastic resin having more excellent flexibility and thermoformability have already been proposed.

For example, while the polyolefin resin is based on polyethylene or polypropylene, a copolymerization component such as butene, methylpentene, hexene or the like may be copolymerized, a soft polyolefin resin such as atactic polypropylene, or ethylene propylene rubber. There has been proposed a decorative sheet using a so-called flexible polyolefin-based resin or a polyolefin-based thermoplastic elastomer resin mixed with a rubber component such as hydrogenated styrene-butadiene rubber.

In place of the polyolefin-based resin, for example, an acrylic resin or an amorphous polyester-based resin is used as an amorphous non-chlorine-based resin having no sea-island structure between an amorphous portion and a crystal portion. Various decorative sheets and the like have already been proposed.

However, resins developed in this way that are satisfactory in physical properties are special resins having no versatility, and decorative sheets using them are inevitably very expensive. Problem.

[0012] This problem can be solved by reducing the thickness of the resin, but it is suitable for transporting on a printing machine, handling at the time of laminating to a substrate, unevenness of the surface of the substrate and adhesive. The decorative sheet is required to have a certain thickness or more from the viewpoint of concealing properties (function of maintaining the smoothness of the surface) against coating unevenness and the like, rupture resistance during vacuum forming and drawdown resistance. In fact, there is a limit to cost reduction due to thinning.

As a cheaper decorative sheet, there is also a decorative sheet (decorative paper) using paper as a base sheet instead of the thermoplastic resin sheet as described above. However, as is well known, ordinary paper is far inferior in flexibility, elongation, thermoformability, etc. as compared with a thermoplastic resin sheet, and is formed by bending such as V-cut or lapping or vacuum forming. It cannot withstand three-dimensional molding.

As a method of imparting strength and flexibility to the paper, there is a method of filling the voids of the paper fibers with a resin having excellent flexibility and having an action of bonding the fibers by an impregnation method or the like. It has also been conventionally used for decorative sheets as resin-impregnated paper.

Conventional resin-impregnated paper for decorative sheets, however, often uses a water-soluble acrylic resin or a mixed resin of an acrylic emulsion resin and a melamine resin as the impregnating resin. Insufficient flexibility and thermoformability for use in molding and three-dimensional molding, and can be practically used only for surface materials.

For the purpose of obtaining a resin-impregnated paper having better flexibility and thermoformability, attempts have been made to use, for example, SBR (styrene butadiene rubber) latex resin, MBR (methyl methacrylate butadiene rubber) latex resin, or the like. ing. However, these resins are inferior in heat resistance, oil resistance, solvent resistance, etc. by using a latex resin alone, so that a thermosetting resin such as a melamine resin must be used in combination, and as a result, sufficient bending workability and A decorative sheet having three-dimensional suitability has not been realized.

[0017]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and has sufficient flexibility and heat suitable for bending and three-dimensional forming. An object of the present invention is to provide a decorative sheet that has moldability, is excellent in heat resistance, oil resistance, solvent resistance, and the like, and can be manufactured at low cost because it is mainly made of paper. The present invention also aims to provide a decorative material using the decorative sheet.

[0018]

According to the present invention, there is provided a decorative sheet characterized by using paper impregnated with an NBR latex resin as a base sheet in order to solve the above-mentioned problems.

In particular, the NBR latex-based resin contains 35 to 5 unsaturated nitrile monomers as a monomer component.
Provided is a decorative sheet characterized by being a high nitrile NBR latex resin containing 0% by weight.

In addition, the present invention further provides a decorative sheet characterized in that the NBR latex resin is a carboxylated NBR latex resin containing an unsaturated carboxylic acid monomer as a copolymer component.

[0021] The present invention also provides, in combination with the above decorative sheet,
A decorative material, characterized in that any one of the decorative sheets described above is attached to the surface of a substrate.

Particularly, the present invention provides a decorative material characterized in that a groove is formed on the back surface of the base material and a bending process is performed on the groove processed portion.

In addition, the present invention provides a decorative material characterized in that the base material has a three-dimensional uneven shape on the surface.

[0024]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the decorative sheet and the decorative material of the present invention will be described below in detail with reference to the drawings. 1 to 5 are side sectional views showing an embodiment of a decorative sheet of the present invention, and FIGS. 6 to 8 are side sectional views showing an embodiment of a decorative material of the present invention.

As shown in FIG. 1, the decorative sheet of the present invention is obtained by using, as a base sheet, a paper obtained by impregnating a base paper 1 with an NBR latex resin as an impregnating resin 3.
The base paper 1 may be provided with a pattern print 2 representing an appropriate pattern.

The base paper 1 may be any fibrous sheet having a water-absorbing property that can be impregnated with a resin, such as thin paper, titanium paper, resin-mixed paper, inter-sheet reinforced paper, bleached or unbleached kraft paper. Various papers such as paper, linter paper, high quality paper, coated paper, inorganic paper, flame retardant paper, paperboard, Japanese paper, and natural fibers,
Woven or nonwoven fabrics made of recycled fibers, synthetic fibers, inorganic fibers, and the like can be used.

Further, as long as additional impregnation of the resin is possible, the resin may be already impregnated with the same or different resin, and ordinary resin-impregnated paper may be used. In addition, a material obtained by mixing, laminating, or compounding a plurality of materials selected from these materials can also be used.

The thickness of the base paper 1 is not particularly limited, but is usually used for decorative sheets having a basis weight of about ²⁰ to 200 g / m ² (before impregnation with an NBR latex resin). It is common to use those in the range of about 40 to 120 g / m ² (same), and basically the same thing can be used for the decorative sheet of the present invention.

Above all, if it is too thin, it may be broken during bending or three-dimensional molding, while if it is too thick, the flexibility of the sheet becomes insufficient, and the sharp-angle bending workability and the followability to the formed shape deteriorate. Therefore, for the purpose of the present invention, a basis weight of 6
Those having about 0 to 80 g / m ² (same) are most suitable.

On the surface of the base paper 1, a pattern print 2 representing a design pattern of a desired design is applied as necessary.

There are no particular restrictions on the type of printing ink used in the pattern printing 2 or on the printing method, etc., and a colorant such as a dye or pigment is dissolved or dispersed in a suitable solvent together with a suitable binder resin. Conventionally known using printing ink or paint, for example, gravure printing method, gravure offset printing method, planographic offset printing method, dry offset printing method, letterpress printing method, screen printing method, flexographic printing method, inkjet printing method, etc. Can be provided by printing or painting by any printing method or painting method.

The type of binder resin such as printing ink used in the pattern printing 2 is not particularly limited.
When the pattern printing 2 is performed before the impregnation, the affinity with the fibers constituting the base paper 1 is taken into consideration, and the contamination of the impregnating liquid of the impregnating resin 3 and the deterioration of the printed pattern are prevented. It is necessary to select in consideration of the water resistance of the printing ink film after printing and drying.

More specifically, for oil-based inks, cellulose derivatives such as nitrified cotton are used; for water-based inks, proteins such as milk casein or soy protein are used; and aqueous inks such as acrylic or vinyl acetate are used. Aqueous latex systems such as emulsion systems and MBR systems are suitable.

There are no particular restrictions on the type of pattern design represented by the pattern print 2, and for example, wood patterns, stone patterns, abstract patterns, geometric patterns, and the like that have been widely used in the field of conventional decorative sheets. For the purpose of letters, symbols, or combinations thereof, or simple coloring or color adjustment, it may be a single-color solid color. In short, any desired pattern is adopted according to the intended use of the decorative sheet. can do.

In the decorative sheet of the present invention, the base paper 1 is impregnated with an NBR latex resin as the impregnating resin 3. By impregnating the base paper 1 with the NBR latex resin, it is possible to improve the elongation percentage of the base paper 1 by a maximum of about 30 to 40%, such as bending workability such as V-cut processing and lapping processing, vacuum forming processing and the like. There is an advantage that a decorative sheet having excellent three-dimensional moldability can be easily obtained.

The NBR latex resin used in the present invention comprises, as is well known, an unsaturated nitrile monomer such as acrylonitrile or methacrylonitrile and a conjugated diene monomer such as butadiene or isoprene. If necessary, a desired amount of an unsaturated monomer copolymerizable therewith is blended, and various additives such as an emulsifier such as an anionic surfactant, a polymerization initiator, and a molecular weight modifier are added in required amounts. An aqueous latex obtained by copolymerizing the resulting monomer composition by an appropriate polymerization method such as an emulsion polymerization method.

The mixing ratio of the unsaturated nitrile monomer to the conjugated diene monomer in the NBR latex resin may vary depending on the content of the unsaturated nitrile monomer in the range of about 15 to 50% by weight. NBR latex-based resins used in the decorative sheet of the present invention have excellent strength to withstand high elongation and are resistant to breakage. As obtained, a high nitrile type having a high content of unsaturated nitrile monomer is particularly suitable, and it is most preferable to use a product having an unsaturated nitrile monomer content of 35 to 50% by weight. desirable.

Particularly, among the NBR latex resins, acrylic acid, methacrylic acid,
When a carboxylated NBR latex resin obtained by copolymerizing an unsaturated carboxylic acid monomer such as maleic acid, fumaric acid, and itaconic acid and introducing a carboxyl group into the molecule is used, the carboxyl group of the introduced carboxyl group is reduced. By action
Adhesion with cellulose fiber which is the main component of paper is improved,
It is possible to obtain a decorative sheet which is more excellent in rupture resistance against elongation during bending and three-dimensional molding and also has improved surface abrasion resistance. The content of the unsaturated carboxylic acid monomer is preferably about 1 to 10% by weight.

In the decorative sheet of the present invention, the N
The impregnation rate of the BR latex-based resin is not particularly limited, but when the base paper 1 is a paper containing no resin other than the paste material, the impregnation rate (the impregnated resin content relative to the total weight after impregnation) is used. (Weight ratio) is about 20 to 80%. When the base paper 1 is a paper containing a resin such as a resin-impregnated paper or a resin-mixed paper, it generally depends on the type and content of the resin of the base paper 1. Base paper 1 selected from the range of about 5 to 50%
The design may be made appropriately in accordance with the characteristics and the degree of characteristics required for the intended decorative sheet.

By the impregnation treatment with the NBR latex resin, the elongation percentage of the base paper 1 can be improved up to about 30 to 40%.

As described above, the picture printing 2 may be performed before the impregnation with the NBR latex resin or after the impregnation with the NBR latex resin (FIG. 2). In the latter case, the ink layer of the pattern print 2 is NB
R latex resin is formed in a layer on the surface of the paper impregnated with the R latex-based resin.
Therefore, the surface protection layer 4 made of an appropriate transparent resin is practically essential.

As the surface protective layer 4, a curable resin having excellent physical properties is generally used. However, a curable resin having a high hardness generally has a large curing shrinkage. If no measures such as applying an anchor layer for stress relaxation on the pattern print 2 are used, the ink layer of the pattern print 2 will be broken by the shrinkage stress of the surface protection layer, and cracks and peeling will occur. Care must be taken in some cases.

On the other hand, when the base paper 1 is impregnated with the NBR latex resin after the pattern printing 2 is applied, at least a part of the printing ink of the pattern printing 2 penetrates into the base paper 1 and is integrated with the base paper 1. An accident that only the printing ink layer of the picture print 2 peels off from the surface of the base paper does not occur. In addition, the base paper 1 containing the picture print 2 is impregnated with the NBR latex resin to be integrally reinforced, and a coating layer made of the excess impregnated resin 3 is formed on the surface of the base paper 1 containing the picture print 2. Functions as a kind of surface protective layer, so that it is not necessary to form a separate surface protective layer 4 depending on the use.

Of course, in the case of a decorative sheet for applications requiring abrasion resistance, abrasion resistance, and weather resistance that cannot be tolerated by a coating layer made of the impregnated resin 3, a curable resin or the like is formed on the coating layer. The surface protection layer 4 can be formed (FIG. 3). Moreover, in this case, since the coating layer of the impregnated resin 3 functions as an anchor layer for stress relaxation, even if the surface protective layer 4 of the curable resin is directly formed without providing an anchor layer on the surface after impregnation, There is also an advantage that there is no fear that cracks, peeling, or the like occurs in the printing ink layer of the picture print 2 due to the curing shrinkage stress of the surface protective layer 4.

As the curable resin used for the surface protective layer 4, for example, urethane resin, melamine resin, epoxy resin, phenol resin, urea resin, benzoguanamine resin, diallyl phthalate resin, unsaturated polyester resin Thermosetting resins such as amino alkyd resins, acrylate resins or methacrylate resins, ionizing radiation-curable resins such as unsaturated polyester resins,
An appropriate one can be arbitrarily selected from various curable resins conventionally used for a surface protective layer of a decorative sheet.

However, in the case of three-dimensional molding, in particular, in order to prevent accidents such as cracking or peeling of the surface protective layer 4 during molding, the cured product has a high elongation after curing (preferably at least 50% elongation). It is desirable to employ a resin or a resin which is solid at room temperature in an uncured or semi-cured state and shows thermoplasticity, and is completely cured after three-dimensional molding. In addition, it is also possible to provide the surface protective layer 4 by painting or the like after the three-dimensional molding without providing the surface protective layer 4 before the three-dimensional molding. According to this method, the secondary processing step is somewhat complicated. However, there is an advantage that a resin having good physical properties after curing can be arbitrarily selected without being restricted by three-dimensional moldability.

Examples of the method of forming the surface protective layer 4 include a roll coating method, a knife coating method, an air knife coating method, a die coating method, a lip coating method, a comma coating method,
It may be arbitrarily selected from various coating methods such as a kiss coating method, a flow coating method, a dip coating method, a gravure coating method, and a microgravure coating method. The thickness of the surface protective layer 4 is not particularly limited, but generally ranges from 1 to 50.
It is designed within a range of about μm, and the most desirable range is about 5 to 20 μm.

By adding various functional substances to the surface protective layer 4, a desired desired functionality can be imparted to the intended decorative sheet. As such functionality,
For example, pollution prevention function, antibacterial function, fungicide function, insect control function,
Examples include a deodorizing function, a function of removing volatile organic substances such as formaldehyde, an aroma function, a moisture absorbing / releasing function, a photocatalytic function, a superhydrophilic function, a conductive function, and an ion generating function.

In order to further improve the abrasion resistance and abrasion resistance of the decorative sheet of the present invention, the surface protective layer 4 may contain abrasion-resistant particles. As the wear-resistant particles, for example, silica, alumina, glass, zirconium oxide, silicon nitride, silicon carbide, zeolite, shirasu balloon, diatomaceous earth and the like can be used.

The decorative sheet of the present invention is applied to the surface of the base paper 1 impregnated with the impregnating resin 3 directly or through the pattern printing 2 and / or the surface protective layer 4 so as to have a gloss different from those surfaces. By providing a gloss adjusting pattern layer 5 of a resin composition whose gloss state has been adjusted by the addition of a matting agent or the like (FIG. 4), or by embossing by a roll embossing method or the like, a three-dimensional pattern is obtained. A design feeling can also be imparted.

The surface protective layer 4 also has a function of giving a sense of depth and a sense of painting to the surface design of the decorative sheet by the presence of a layer made of a transparent material on the pattern print 2. These feelings of depth and painting are more advantageous as the thickness of the surface protective layer 4 is larger. However, since a curable resin is used as the surface protective layer 4, the thickness of the surface protective layer 4 is increased due to the demand for bending workability and three-dimensional moldability. Is naturally restricted. Therefore, in order to obtain a sufficient feeling of depth and painting while ensuring sufficient bending workability and three-dimensional moldability, it is preferable to provide the transparent thermoplastic resin layer 6 on the surface of the decorative sheet of the present invention ( (Fig. 5).

The kind of the transparent thermoplastic resin constituting the transparent thermoplastic resin layer 6 is not particularly limited. For example, a polyolefin resin, an acrylic resin, a polyester resin, a polyamide resin, an ethylene-vinyl alcohol copolymer resin Using any thermoplastic resin that has been conventionally used as a surface sheet material in a decorative sheet according to the related art, such as an ethylene-vinyl acetate copolymer resin, or a mixture, a composite or a laminate of two or more thereof. can do.
Among them, polyolefin-based resin, acrylic resin, or amorphous polyester-based resin is most suitable from the viewpoints of secondary workability, physical properties, and price.

In particular, in the case of a decorative sheet for use in three-dimensional molding by a vacuum molding method, the thermoplastic resin used as a constituent material of the transparent thermoplastic resin layer 6 has abrasion resistance, solvent resistance and the like. In addition to surface properties, sufficient consideration must be given to thermal properties and suitability for thermoforming.

For example, in the case of a polypropylene resin, which is a typical example of a polyolefin resin, a high crystallinity polypropylene resin having excellent surface properties such as abrasion resistance and solvent resistance is mainly used while providing flexibility. For the purpose, for example, low crystalline polypropylene resin such as atactic polypropylene, flexible olefin resin such as low density polyethylene, ethylene-α olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer Resins containing one or more soft components selected from olefin elastomers such as coalesced rubber can be suitably used.

Examples of the amorphous polyester resin include, for example, polyethylene terephthalate resin having ethylene terephthalate unit as a main structural unit and sheeted under conditions that do not crystallize during film formation, or dicarboxylic acid or dicarboxylic acid ester. In the condensation polymerization reaction with a diol, for example, an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and / or an alicyclic dicarboxylic acid such as cyclohexanedicarboxylic acid and ethylene glycol, 1,4-butanediol And / or a rigid structural unit formed by using an aliphatic diol such as cyclohexane dimethanol and / or an alicyclic diol such as cyclohexane dimethanol. Using the ether-based diol, and /
Or (AB) n-type with a soft structural unit using an aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid such as sebacic acid, eicoic acid, dodecanedioic acid, and dimer acid as the dicarboxylic acid. A copolymerized polyester resin or the like made of a block copolymer and exhibiting the properties of a thermoplastic elastomer, having a glass transition temperature (Tg) of 60
A polyester resin having a cold crystallization temperature (Tc) of 120 ° C. or higher and a temperature of 120 ° C. or higher can be suitably used.

Examples of the method of laminating the transparent thermoplastic resin layer 6 include a dry lamination method or a wet lamination method with an appropriate adhesive, a heat lamination method with or without an adhesive, an ultrasonic lamination method, and a high frequency lamination. Method, a conventionally known arbitrary method such as an extrusion lamination method in which a thermoplastic resin is extruded into a sheet in a molten state and a laminate method in which the thermoplastic resin is laminated at the same time, a sand lamination method in which a different type of thermoplastic resin is sandwiched by a melt-extruded layer, and the like. be able to. Further, prior to lamination, the adhesive surface of the base paper 1 or the transparent thermoplastic resin layer 6 is subjected to easy adhesion such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, acid treatment, alkali treatment, primer treatment or anchor treatment. Surface treatment can be performed.

The surface of the above-mentioned transparent thermoplastic resin layer 6 is further provided with a surface protective layer 4 made of the same curable resin as described above, a gloss adjusting layer 5, or an embossed pattern. It is also possible to arbitrarily add a colored or non-colored ink by a wiping method or the like to the concave portion of the concavo-convex pattern.

Between the base paper 1 and the transparent thermoplastic resin layer 6, an intermediate layer 7 made of a transparent thermoplastic resin of the same type or different from the thermoplastic resin constituting the transparent thermoplastic resin layer 6 can be provided. As the intermediate layer 7, a layer made of a transparent adhesive resin for improving the adhesive strength between the base paper 1 impregnated with the impregnating resin 3 and the transparent thermoplastic resin layer 6 or the flexibility of the decorative sheet as a whole is improved. Such as a soft resin layer for
Various functions can be imparted to the decorative sheet by using various materials depending on the purpose.

The decorative sheet 81 of the present invention described in detail above
For example, wood base materials such as wood veneer, plywood, laminated wood, medium density fiber board, hard fiber board, particle board, gypsum board, slate board, calcium silicate board, slag gypsum board, slag cement board, wood Inorganic base material such as wool cement plate, lightweight cellular concrete plate, glass fiber reinforced concrete plate, etc., metal base material such as steel plate, copper plate, brass plate, aluminum plate, duralumin plate, stainless steel plate, acrylic resin plate, styrene resin plate As a cosmetic material bonded to the surface of various base materials 82 such as a synthetic resin base material such as an ABS resin plate, a polycarbonate resin plate, and a fiber reinforced plastic resin plate through an appropriate adhesive as necessary. Used for various applications (FIG. 6).

Since the decorative sheet 81 of the present invention is excellent in bending workability and three-dimensional forming workability, the decorative sheet 81 of the present invention is adhered to the surface of a plate-like base material 82. Is subjected to groove processing such as V-cut processing, and the groove processing section is bent as the bending processing section 9 (FIG. 7), or the decorative sheet 81 of the present invention is formed into a base material 82 previously formed into a desired three-dimensional shape. By forming and bonding along the surface of the base material by a method such as a lapping method or a vacuum forming method (FIG. 8), a decorative material having a desired three-dimensional shape can be obtained.

[0061]

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

Example 1 An image of an abstract pattern was first formed on a surface of a titanium paper for building material having a basis weight of 80 g / m ² by a gravure printing method using a nitrocellulose-based printing ink. A high nitrile carboxylated NBR latex (Nipol LX511, manufactured by Nippon Zeon Co., Ltd., solid content: 40%) was impregnated by a dipping method at an impregnation amount of 94 g / m ² and dried to prepare a decorative sheet of the present invention.

The elongation percentage of the obtained decorative sheet was 5
% And a grain width of 40%.

The decorative sheet was previously coated with a two-component urethane resin-based adhesive on the surface to a coating amount of 10 g / m ² after drying, and dried. The radius of curvature of the edge portion as shown in FIG. 8 was 5R.
When three-dimensionally formed and laminated on the surface of a wooden base material having a three-dimensional three-dimensional shape by vacuum forming, no forming defects such as necking, breakage, pattern elongation, whitening, etc. occurred, and the base material surface was uneven. A good cosmetic material product excellent in stain resistance, solvent resistance, and oil resistance was obtained without picking up unevenness in application of the adhesive or the adhesive.

Instead of the above-mentioned vacuum forming method, processing of a decorative material by a soft wrapping method or a V-cut bending method was attempted. In any case, molding defects such as pattern elongation, breakage, and whitening occurred. And a good cosmetic material product could be obtained.

Example 2 A wood-grain pattern was first formed on the surface of a resin-impregnated paper having a basis weight of 80 g / m ² by a gravure printing method using a nitrifying cotton-based printing ink. Was impregnated with the same impregnating resin as used in the above at an impregnation amount of 5.3 g / m ² and dried.

Next, an isocyanate-curable two-component urethane resin containing a reactive silicone compound containing a hydroxyl group was applied to the impregnated paper by a gravure coating method to a coating amount of 7 g / m ² after drying. After drying to the touch by heat drying, isocyanate-curable two-liquid urethane resin blended with a silica-based matting agent and a reactive silicone compound containing a hydroxyl group, and a conduit tuned with the wood pattern by gravure printing. The decorative sheet was printed in a pattern and cured at room temperature to prepare a decorative sheet of the present invention.

The elongation percentage of the obtained decorative sheet was 3
%, And 25% grain width.

Using the above decorative sheet, Example 1
Under the same conditions as in the case above, vacuum molding, soft wrapping and V-cut bending were used to produce a decorative material, and in each case, there were no molding defects such as necking, breakage, pattern elongation, and whitening. Without picking up irregularities on the surface of the base material and uneven application of the adhesive, stain resistance and solvent resistance,
A good cosmetic material product excellent in oil resistance was obtained.

Example 3 A wood-grain pattern was first formed on a surface of a resin-impregnated paper having a basis weight of 75 g / m ² by gravure printing using a nitrifying cotton-based printing ink. Was impregnated with the same impregnating resin as used in the above at an impregnation amount of 10 g / m ² and dried.

The elongation percentage of the obtained printed impregnated paper was 3
%, And 30% grain width.

A two-component urethane-based topcoat agent was applied to the surface of a transparent polypropylene resin film having a thickness of 50 μm to a coating amount of 6 g / m ² after drying, and cured by drying and curing.
On the other hand, on the back surface, a polyvinyl chloride-urethane-based thermal adhesive anchor was applied at a coating amount of 6 g / m ² after drying to prepare a surface film.

The printed impregnated paper has a thickness of 50 μm on the printing surface.
m, a transparent amorphous polyester-based resin film is placed thereon, and the transparent polypropylene-based resin film is further placed with the surface of the transparent polypropylene-based resin film coated with the thermal adhesive anchor agent facing the surface, and three layers are laminated by a doubling embossing method. At the same time as bonding
An embossed concave portion of a conduit pattern was formed on the surface of the transparent polypropylene resin film to prepare a decorative sheet of the present invention.

Using the obtained decorative sheet, an attempt was made to produce a decorative material by vacuum forming, soft lapping, and V-cut bending under the same conditions as in Example 1 above. No molding defects such as necking, breakage, pattern elongation, whitening, etc., no irregularities on the substrate surface and no uneven application of adhesive, and excellent resistance to contamination, solvent and oil. A good cosmetic product was obtained.

[0075]

As described in detail above, the decorative sheet of the present invention has excellent extensibility due to impregnation with an NBR latex resin, despite the use of inexpensive paper as the base material. Since elasticity is imparted, even if bending processing such as V-cut processing or lapping processing, or three-dimensional forming processing such as vacuum forming processing, molding defects such as breakage, necking, whitening, and pattern elongation may occur. In addition, it is possible to stably and inexpensively manufacture a cosmetic material product which is excellent in various physical properties and appearance quality, such as excellent in oil resistance, stain resistance, and solvent resistance.

[Brief description of the drawings]

FIG. 1 is a side sectional view showing an embodiment of a decorative sheet of the present invention.

FIG. 2 is a side sectional view showing an embodiment of the decorative sheet of the present invention.

FIG. 3 is a side sectional view showing an embodiment of the decorative sheet of the present invention.

FIG. 4 is a side sectional view showing an embodiment of the decorative sheet of the present invention.

FIG. 5 is a side sectional view showing an embodiment of the decorative sheet of the present invention.

FIG. 6 is a side sectional view showing an embodiment of the decorative material of the present invention.

FIG. 7 is a side sectional view showing an embodiment of the decorative material of the present invention.

FIG. 8 is a side sectional view showing an embodiment of the decorative material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base paper 2 ... Picture printing 3 ... Impregnating resin 4 ... Surface protective layer 5 ... Gloss adjustment picture layer 6 ... Intermediate layer 7 ... Transparent thermoplastic resin layer 81 ... Decorative sheet 82 ... Base material 83 ... bending part

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AB21H AK07 AK27A AK28A AK51G AL01A AT00B BA02 DB14B DD01B DG10 EH46 EH462 EJ82 EJ822 GB08 GB31 GB48 HB31 JB07 JJ03 JK13 YY00A 4L055 AG70 AG74 AGA10 AG17 AG97

Claims (6)

[Claims] 1. A decorative sheet comprising a base sheet made of paper impregnated with an NBR latex resin. 2. The NBR latex resin according to claim 1, wherein the NBR latex resin is a high nitrile NBR latex resin containing 35 to 50% by weight of an unsaturated nitrile monomer as a monomer component. Makeup sheet. 3. The decorative sheet according to claim 1, wherein the NBR latex-based resin is a carboxylated NBR latex-based resin containing an unsaturated carboxylic acid monomer as a copolymer component. 4. A decorative material comprising the decorative sheet according to claim 1 attached to a surface of a substrate. 5. The decorative material according to claim 4, wherein a groove is formed on a back surface of the base material, and a bending process is performed on the groove processed portion. 6. The decorative material according to claim 4, wherein the base material has a three-dimensional uneven shape on a surface.