JP2000296584A - Decorative sheet - Google Patents

Abstract

(57) [Summary] [PROBLEMS] Even if secondary processing such as V-cut processing and lapping processing, which is excellent in weather resistance, is performed, cracking of a decorative sheet and peeling between layers are extremely small, and waste material is also used. It is an object of the present invention to provide an inexpensive decorative sheet that does not generate toxic gas such as hydrogen chloride when using incineration as a processing means. SOLUTION: A paper base sheet layer, a picture printing layer,
An adhesive layer and a decorative sheet having a surface protective layer laminated thereon, wherein the paper-based substrate sheet layer is made of a resin-impregnated paper, and the surface protective layer is a transparent olefin-based material containing a radical scavenger and an ultraviolet absorber. The purpose is to provide a decorative sheet made of a thermoplastic resin film.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet which is adhered to various kinds of furniture and building interior materials for the purpose of decoration or surface protection, and more particularly to an inexpensive decorative sheet excellent in design and weather resistance. It is about a sheet.

[0002]

2. Description of the Related Art As a conventional decorative sheet, a decorative sheet obtained by printing a paper-based thin paper or a vinyl chloride resin film by a usual method and then laminating a transparent vinyl chloride resin film, or a three-dimensional Embossing the transparent vinyl chloride resin film surface of the decorative sheet, and filling the recesses of the emboss with ink in order to bring out the feeling and to improve the design, Is known. The reason why vinyl chloride resin film is used is that it is a general-purpose resin, has low manufacturing costs, is easy to color, has good lamination, is easy to emboss, and has vacuum forming workability.
This is because the easiness of secondary and tertiary processing such as cut workability is better or balanced as compared with other resins. However, in connection with recent environmental issues,
Because it generates hydrogen chloride gas when incinerated,
There is a need for a decorative sheet other than a vinyl chloride resin that does not contain chlorine groups because incineration cannot be used as a means for treating waste materials.

[0003] Therefore, as a decorative sheet for overcoming such drawbacks of the vinyl chloride resin film, a decorative sheet in which a paper-based thin paper is used as a base sheet and a transparent polyolefin-based resin film is laminated as a surface protective layer is proposed. However, the polyolefin-based resin film is excellent in stain resistance but has poor weather resistance, that is, the polyolefin-based resin film is deteriorated when exposed to sunlight from the outside, so that the polyolefin-based resin film is deteriorated. And the interlaminar bond strength with the adjacent layer decreases with time, and is inferior to the conventional decorative sheet using a polyvinyl chloride resin film for the surface protective layer. Etc. 2
Also in the secondary workability, cracking of the decorative sheet and peeling between layers occurred, resulting in poor quality.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to carry out secondary processing such as V-cut processing and lapping processing, which is excellent in weather resistance. However, the present invention provides an inexpensive decorative sheet free from generation of toxic gas such as hydrogen chloride when incineration is used as a means for treating waste material, with very little occurrence of cracks in the decorative sheet and peeling between layers. That is.

[0005]

To achieve the above object, the present invention provides a decorative sheet comprising a paper-based substrate sheet layer, a picture printing layer, an adhesive layer, and a surface protective layer. A decorative sheet, wherein the paper-based substrate sheet layer is made of a resin-impregnated paper, and the surface protective layer is made of a transparent olefin-based thermoplastic resin film containing a radical scavenger and an ultraviolet absorber. It is to be. With this configuration, it is excellent in surface properties such as weather resistance, solvent resistance, and stain resistance, has stable adhesion, and is excellent in secondary workability such as V cut processing and lapping processing, and is inexpensive. It can be a decorative sheet. Furthermore, since the resin does not contain chlorine atoms, it is possible to obtain a decorative sheet that does not generate toxic gas such as hydrogen chloride when subjected to incineration.

Further, the radical scavenger is a hindered amine radical scavenger. By doing so, the weather resistance can be further improved, and yellowing and deterioration can be prevented.

In the decorative sheet, since the resin-impregnated paper is impregnated with an acrylate resin, the paper-to-paper strength is increased without impairing flexibility, and V-cut processing and wrapping are performed. It becomes suitable for secondary workability such as working.

Further, in the decorative sheet, the resin-impregnated paper weighs 35 to 70 g / m ² . By doing so, an inexpensive decorative sheet having excellent workability can be obtained.

Further, when the adhesive layer contains a radical scavenger and an ultraviolet absorber, the weather resistance is further increased.

[0010] Further, the decorative sheet is characterized in that the adhesive layer is made of a two-component curable polyurethane resin. By doing so, the adhesion between the paper-based substrate sheet provided with the picture printing layer and the transparent olefin-based thermoplastic resin film as the surface protection layer can be improved, and the interlayer adhesion strength can be further increased.

Further, an embossed portion is formed on the upper surface of the surface protective layer to form an embossed concave portion, and the embossed concave portion is filled with a coloring ink by wiping, and thereafter, a top coat layer is provided. It is a decorative sheet. By doing so, a design closer to the real thing, in particular, a woodgrain pattern or the like can be obtained.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 shows a first embodiment of a decorative sheet according to the present invention.
FIG. 2 is a cross-sectional view showing a laminated structure of an embodiment, and FIG. 2 is a cross-sectional view showing a laminated structure of a second embodiment of the decorative sheet of the present invention.
1, 1 'is a decorative sheet, 2 is a paper base sheet, 3 is a picture print layer, 31 is a solid print layer, 32 is a pattern print layer, 4 is an adhesive layer, 5 is a surface protective layer (transparent olefin heat). 6 is an embossed concave portion, 7 is a colored ink layer, and 8 is a gloss adjusting resin layer.

FIG. 1 shows a laminated structure of a decorative sheet according to a first embodiment of the present invention.
Forms a pattern print layer 3 on a paper base sheet 2,
A surface protection layer 5 made of an olefin-based thermoplastic resin film containing a radical scavenger and an ultraviolet absorber is adhered on the pattern printing layer 3 via an adhesive layer 4.
The adhesive layer 4 is made of an adhesive for dry lamination made of a two-component curable polyurethane-based resin, and the paper-based substrate sheet 2 provided with the pattern printing layer 3 and the transparent olefin-based thermoplastic resin film 5 having excellent weather resistance are strongly bonded. And has a configuration in which no chlorine group is contained in the molecule.

The paper base sheet 2 used for the decorative sheet 1 of the present invention is a resin-impregnated paper obtained by impregnating a base paper for a base sheet with an impregnating agent mainly composed of a thermoplastic resin by an immersion impregnation method. is there. The base paper for the base sheet is based on paper made by a wet papermaking method. For example, thin paper, sheet-reinforced paper, high-quality paper, pure white roll paper, titanium paper and the like can be mentioned. Incidentally, the paper made by the wet papermaking method,
It includes not only paper in a narrow sense, but also paper made of a mixture of synthetic fibers and / or semi-synthetic fibers, and nonwoven fabrics made by wet papermaking. The composition of the impregnating agent is mainly composed of a thermoplastic resin.
Examples of the thermoplastic resin include a synthetic resin emulsion represented by an acrylic ester, an acrylic emulsion, a styrene acrylic emulsion, a vinyl acetate emulsion, a urethane dispersion, an epoxy dispersion, or a synthetic resin dispersion, styrene. Butadiene copolymers, synthetic rubber latex typified by acrylonitrile butadiene copolymer and the like, among which acrylate resins are preferred in terms of improving the inter-sheet strength without impairing the weather resistance, and flexibility. is there. Also, a thermosetting resin can be added if necessary, but the addition of the thermosetting resin is preferable for the hardness, but if the addition amount is large, the flexibility of the sheet is impaired and the paper breaks during processing. It will be easier.
As the impregnation method, the immersion impregnation method is used as described above. The ratio of the impregnating agent in the resin-impregnated paper (impregnation rate) was 1
It is at least 5% by weight, preferably at least 20% by weight. If the impregnation ratio is low, the inter-paper strength becomes insufficient, and the paper layer is easily peeled off. The weight of the resin-impregnated paper is as follows.
A pulp sheet mainly composed of pulp of 150 to 150 g / m ² , preferably 35 to 70 g / m ² is preferable. If the weight of the paper is too small, the density of the paper is usually high and the impregnating property is reduced. It is preferable that the density is relatively low so as not to impair.

On the upper surface of the paper-based substrate sheet 2, a pattern comprising a solid printing layer 31 and a pattern printing layer 32 for displaying straight-grained, plate-grained wood-grain patterns such as oak, teak, walnut, cedar, cypress, etc. The printing layer 3 is made of a polyurethane-based, acrylic-based, polyester-based,
It is formed by gravure printing with a printing ink using a mixture of one or more kinds of cellulose-based binder resins, and in order to be able to express the "shine" of the grain, it is necessary to use pearl pigments or metal. It is preferable to add a glitter pigment such as powder.

Also, as the adhesive layer 4, a method of laminating by dry lamination using a two-component curable polyurethane resin is suitable. Among them, a polyol component having an OH group (acryl polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) is used as a main component, and tolylene diisocyanate, hexamethylene diisocyanate,
A two-pack curable polyurethane resin obtained by adding an isocyanate compound such as meta-xylene diisocyanate is preferred. The amount of adhesive to be applied is 5 to 20 g
/ M ² (dry), which is dried at a temperature of 40 to 70 ° C., laminated, and cured in an atmosphere of 35 to 40 ° C. for 48 to 72 hours to exhibit sufficient performance.

The surface protective layer 5 of the present invention is for protecting the picture print layer 3 and has various physical properties required as a decorative sheet, that is, weather resistance, solvent resistance, stain resistance, and abrasion resistance. It is provided in order to make a decorative sheet excellent in such properties as the like, and what is important is that a chlorine group is not contained in the molecule, so that the cost is low and the embossing is good. Such a polyolefin-based resin is a polyethylene-based homopolymer of polyethylene, ethylene-
Propylene copolymers, ethylene-based resins such as ethylene-butene-1 copolymer, as a polypropylene-based resin,
A propylene-based resin such as a homopolymer of polypropylene, a propylene-ethylene copolymer, a propylene-butene copolymer, and among others, a soft polypropylene film produced by copolymerization of an amorphous polypropylene and a crystalline polypropylene. However, with a wide range of rigidity, rich flexibility, moderate surface hardness and excellent post-processing suitability,
The embossability is good, the cost is low, and no toxic gas is generated during combustion. In addition, the surface of the transparent olefin-based thermoplastic resin film can be printed ink, paint,
In order to improve the adhesiveness with the adhesive, the surface of the film may be activated by performing a treatment such as a corona treatment and an ozone treatment. The thickness of the surface protective layer 5 is 50 to 100 μm.
It is preferable that

The radical scavenger used in the surface protective layer 5 of the present invention is used for the purpose of improving the weather resistance of the surface protective layer 5, particularly when the surface protective layer 5 is made of an olefin-based thermoplastic resin. Is added in order to prevent the thermoplastic resin from deteriorating with time due to sunlight (ultraviolet rays). As this radical scavenger, bis- (2,
2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (1,2,2
2,6,6-pentamethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidyl-tridecyl-1,2,3,4-butanetetracarboxylate, tetragis- (2, In addition to 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like, for example, Japanese Patent Publication No. 4-82
Hindered amine radical scavengers such as the compounds disclosed in Japanese Patent No. 625 are preferred. The reason for this is that hindered amine radical scavengers have a tetraalkylpiperidine as a mother nucleus, have a radical scavenging action of scavenging radicals generated by ultraviolet rays, and have various actions such as an inactive action of hydroperoxide (ROOH). It is presumed that the effect is exhibited by the mechanism, and excellent performance can be obtained as a multifunctional stabilizer. It is appropriate to add 0.01 to 3.0 parts by weight of the radical scavenger to 100 parts by weight of the olefinic thermoplastic resin.

As the ultraviolet absorber, for example, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3′-tert-butyl-5′-
Methylphenyl) -5-chlorobenzotriazole, 2
-(2'-hydroxy-3'-tert-amyl-5 '
-Isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5 '
-Methylphenyl) -5-chlorobenzotriazole,
2'-hydroxyphenyl-5-chlorobenzotriazole-based ultraviolet absorbers such as 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-
2′-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as 3 ′, 5′-di-tert-butylphenyl) benzotriazole and 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2 '-
Dihydroxy-4-metroxybenzophenone, 2,
2,2'-dihydroxybenzophenone-based ultraviolet absorbers such as 2'-dihydroxy-4,4'-dimetoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-metro 2-hydroxybenzophenone UV absorbers such as xylbenzophenone and 2,4-dihydroxybenzophenone; salicylate UV absorbers such as phenyl salicylate and 4-tert-butyl-phenyl-salicylate;
Cyanoacrylate ultraviolet absorbers such as 2-ethyl-hexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, octyl-2-cyano-3,3-diphenylacrylate Or the like can be used. However, as the ultraviolet absorber used in the present invention, a chlorine-free benzotriazole-based, benzophenone-based, or cyanoacrylate-based is suitable, and in particular, a chlorine-free benzotriazole-based is preferred. The addition amount of these ultraviolet absorbers is usually about 0.1 to 10% by weight. here,
The above radical scavenger and ultraviolet absorber may be added to the adhesive layer in an appropriate amount, if necessary, to further improve the weather resistance.

As a second embodiment of the decorative sheet of the present invention, as shown in FIG. 2, a colored ink 7 is applied to the embossed concave portions 6 provided on the surface of the surface protective layer 5 made of the transparent olefin-based thermoplastic resin film. There is a configuration in which the gloss adjusting resin layer 8 is provided after filling, and the concave portion of the uneven pattern provided on the surface is filled with the coloring ink 7 to further enhance the design effect of the decorative sheet 1.

The embossing is performed by dry laminating the surface of the pattern printing layer 3 of the paper-based substrate sheet layer 2 and the transparent olefin-based thermoplastic resin film 5 with the adhesive layer 4, and after hot curing, the transparent olefin-based By embossing from the thermoplastic resin film 5 side with the embossed plate and then cooling,
It is formed. For processing the embossed concave portion 6, a well-known sheet-fed or rotary embossing machine is used.

Transparent olefinic thermoplastic resin film 5
As the colored ink 7 to be filled in the embossed concave portion 6,
Paints or inks are used. For example, a paint or ink obtained by using a synthetic resin such as a polyester-based resin or a polyurethane-based resin as a constituent material of a vehicle and adding a coloring pigment, an extender pigment, a plasticizer, and the like to the vehicle is used. As the vehicle to be used, a two-component curable polyurethane resin is preferably used. As a wiping method,
Any of conventional wiping methods such as a doctor blade method and a roll coating method may be used.

Even if the gloss adjusting resin layer 8 is colorless and transparent,
Alternatively, it may be colored and transparent, or may be matte and transparent, and is provided to adjust the glossiness of the surface of the decorative sheet, but also has a role of surface protection. The gloss adjusting resin layer 8 is formed by applying a paint using an appropriate vehicle, and as the vehicle, one or two or more thermosetting resins such as a polyurethane resin, an unsaturated polyester resin, and an epoxy resin are used. Can be used. The paint (ink) for forming the gloss adjusting resin layer 8 includes:
Usually, an appropriate amount of matting agent is dispersed to give a desired matting degree, but a gloss type ink containing no matting agent may be used. The matting agent used includes inorganic hollow bodies such as mica, silica, calcium aluminate, silica sand, or resins such as acrylic resins, polyamide resins, polyurethane resins, polyethylene resins, and melamine resins, and modified products of these resins. Elastic spherical organic resin beads or the like formed. As a method of applying the paint, a method such as gravure coating, roll coating, and air knife coating is used.

In the decorative sheets 1 and 1 'of the present invention, since the paper base sheet layer 2 is made of paper resin impregnated paper, a general-purpose polyvinyl acetate emulsion adhesive is used for a substrate such as plywood. It can be firmly bonded and laminated, and the finished veneer has excellent properties such as weather resistance, solvent resistance, stain resistance, and abrasion resistance, so it can be used for building interior materials, wall materials, partitions, doors and other surface materials. It can be used for various purposes, and can also be used for forming a V-cut groove in plywood and bending it, and for wrapping of irregularly shaped wood and irregularly shaped products.

Example 1 A concealed solid ink layer and a wood pattern of an oak pattern were formed on a surface of a resin-impregnated paper weighing 50 g / m ² using an ink obtained by adding an isocyanate curing agent to an acrylic-polyol resin using a gravure printing machine. Layers. On the other hand, an adhesive made of a two-component curable polyurethane resin is applied to a transparent polypropylene film containing an ultraviolet absorber and a radical scavenger having a thickness of 80 μm with a gravure roll coater so as to be 15 g / m ² (dry), and dried. Then, the decorative sheet was prepared by dry laminating the surface of the printed resin-impregnated paper with the grain pattern layer.

Example 2 The decorative sheet obtained in Example 1 was heated at a drum temperature of 110
° C, Teflon roll temperature 120 ° C, emboss cylinder temperature 50 ° C, nip pressure 25kg / cm ² , speed 10m
/ Min. To produce a decorative sheet having embossed concave portions. Furthermore, after applying the two-component curable urethane-based coloring ink on the polypropylene film surface on which the recesses due to the embossing are formed on the surface by a roll coating method, the coloring ink adhering to portions other than the recesses with a doctor blade is removed. After removal, the colored ink was filled into the embossed concave portions formed on the surface of the laminated sheet and solidified. Further, a two-part curable urethane-based topcoat ink was coated on the sheet with a gravure roll having a plate depth of 60 μm to prepare a decorative sheet excellent in design and workability.

[0027]

As described above, the present invention provides a transparent olefin-based thermoplastic resin film containing a radical scavenger and an ultraviolet absorber as a surface protective layer on the surface of a paper-based resin-impregnated paper as a base sheet. By adopting a configuration laminated by dry lamination, a decorative sheet having excellent weather resistance, small variation in adhesive strength, stable adhesiveness, and excellent secondary workability such as V-cut and wrapping can be obtained. In addition, since the resin does not contain chlorine atoms, the gas generated during incineration does not contain toxic gases such as hydrogen chloride, so there is no problem of polluting the environment. Incineration means can be used as a means.

Further, embossed concave portions are formed on the upper surface of a transparent olefin-based thermoplastic resin film as a surface protective layer, and the embossed concave portions are colored by wiping. The resulting decorative sheet is obtained.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing a laminated structure of a decorative sheet according to a first embodiment of the present invention.

FIG. 2 is a cross-sectional view showing a laminated structure of a decorative sheet according to a second embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 1 'Cosmetic sheet 2 Paper base sheet 3 Picture printing layer 31 Solid printing layer 32 Pattern printing layer 4 Adhesive layer 5 Surface protective layer 6 Embossed concave part 7 Colored ink layer 8 Gloss adjustment resin layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) B32B 27/40 B32B 27/40 33/00 33/00 F term (Reference) 4F100 AH03C AH03G AH03H AK01A AK01D AK03C AK07 AK25A AK51 AK51G AR00B BA03 BA04 BA07 BA10A BA10C BA10D CA07C CA07G CA30C CA30G CB00 CB00C CB02 DD09C DG10A EJ82A GB08 GB81 HB01 HB21C HB31B JA13A JB16C JK06 JL00 JL01 JLN JN01JLN

Claims (7)

[Claims] 1. A paper base sheet layer, a picture printing layer,
An adhesive layer and a decorative sheet having a surface protective layer laminated thereon, wherein the paper-based substrate sheet layer is made of a resin-impregnated paper, and the surface protective layer is a transparent olefin-based material containing a radical scavenger and an ultraviolet absorber. A decorative sheet comprising a thermoplastic resin film. 2. The decorative sheet according to claim 1, wherein in the decorative sheet, the radical scavenger is a hindered amine radical scavenger. 3. The decorative sheet according to claim 1, wherein in the decorative sheet, the resin-impregnated paper is impregnated with an acrylate resin. 4. The decorative sheet according to claim 1, wherein the resin-impregnated paper has a basis weight of 35 to 70 g / m ² . 5. The decorative sheet according to claim 1, wherein in the decorative sheet, the adhesive layer contains a radical scavenger and an ultraviolet absorber. 6. The decorative sheet according to claim 1, wherein in the decorative sheet, the adhesive layer is made of a two-component curable polyurethane resin. 7. In the decorative sheet, an embossing process is performed on an upper surface of the surface protective layer to form an embossed concave portion, and the embossed concave portion is filled with a coloring ink by wiping, and then a gloss adjusting resin layer is provided. The decorative sheet according to any one of claims 1 to 6, wherein