JP2001341273A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which does not contain vinyl chloride, has a sufficient design of unevenness, and has a good releasability from an adhesive. SOLUTION: An ultraviolet-curing type having a printing ink layer (b), an intermediate coating layer (c) which is a urethane-based clear ink, and a pattern printed with a gravure plate having a plate depth of 100 to 200 μm on a substrate sheet (a). What is claimed is: 1. A decorative sheet having an overcoat layer (d) which is an ink in this order, wherein the intermediate coat layer (c) and the overcoat layer (d) contain a silicone oil having a reactive group.

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 used for building materials and has excellent releasability and design from an adhesive and has a small environmental load.

[0002]

2. Description of the Related Art Conventionally, many decorative sheets have been used for building materials. These have not only protected the surface, but also provided a design by printing a design. In recent years, not only the design itself but also a decorative sheet using a matte ink for the surface layer has been provided for calmness (Japanese Patent Application Laid-Open No. 52-36002). or,
BACKGROUND ART In order to provide a woodgrain, a stone feeling, and a three-dimensional effect, decorative sheets for building materials having irregularities on the surface have appeared.

Japanese Patent Application Laid-Open No. 57-31573 discloses a method in which a cured resin is lyophobized on an ink layer containing a lyophobic agent to form irregularities. Patent No. 2884842
Japanese Patent Laid-Open Publication No. HEI 7-260, introduces a method of emphasizing a feeling of unevenness by thickly embedding a transparent protective layer on a pattern printing layer.

However, these methods do not have a sufficient degree of unevenness, and there is a need for a decorative sheet having a more three-dimensional effect. A method of forming unevenness by thick printing using an ink containing 80 to 90% of a vinyl chloride sol to enhance the unevenness is known. Environmental load is increasing.

[0005] Sufficient unevenness can be formed on the uppermost layer by printing the convex portion thickly with an ultraviolet curable ink, but the adhesiveness with the intermediate coating layer is required. When an adhesive label or the like is attached, there is a problem in the releasability of the surface layer from the adhesive. Therefore, there is a demand for a decorative sheet having a sufficient uneven feeling, that is, a design property, a good releasability for an adhesive, and a low environmental burden.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a decorative sheet which does not contain vinyl chloride, has a sufficient design with a sense of unevenness, and has a good releasability from an adhesive. is there.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a similar silicone oil-containing UV curable ink is used on the intermediate layer containing a specific silicone oil to form the uppermost layer. The present inventors have found that the above problem is solved by printing a pattern, and have reached the present invention.

That is, the constitution of the present invention comprises a printing ink layer (b) on a base sheet (a), an intermediate coating layer (c) which is a urethane clear ink, and a plate depth of 100 to 200 μm.
A decorative sheet having, in this order, an overcoat layer (d), which is an ultraviolet-curable ink having a pattern printed with a gravure plate, wherein the intermediate coat layer (c) and the overcoat layer (d) have a reactive group. It is a decorative sheet containing oil.

The composition of the present invention further comprises a cosmetic sheet wherein the silicone oil having a reactive group contained in the intermediate coating layer is an amino-modified silicone oil. A decorative sheet in which the silicone oil having a group is methacryl-modified silicone is included.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The constitution of the present invention is that a printing ink layer, an intermediate coating layer and a plate depth of 100 to 200 .mu.m
A decorative sheet having a top coat layer having a pattern printed with a gravure plate in this order, wherein the middle coat layer is a urethane-based clear ink containing a silicone oil having a reactive group, and the top coat layer is a silicone having a reactive group. A decorative sheet characterized by being an ultraviolet curable ink containing oil. The individual requirements are described below in detail.

Hereinafter, in order to distinguish the inks of the respective layers, the ink used for the printing ink layer is referred to as "colored ink", the ink used for the intermediate coating layer is referred to as "intermediate ink", and the ink used for the upper coating layer is referred to as "UV ink". .

As the material of the base sheet, papers such as reinforced paper and resin-impregnated paper, and plastic films such as PET and olefin are used. Among them, impregnated paper is preferably used.

As the main component of the coloring ink of the printing ink layer, nitrated cotton, alkyd resin, polyurethane resin, acrylic resin and butyral resin are preferable. Particularly preferred is an ink using nitrified cotton and a polyurethane resin.

Examples of the coloring pigment component contained in the coloring ink include inorganic pigments such as red iron oxide, titanium dioxide, vermilion, ultramarine, patina and carbon black, and organic pigments such as azo pigments, phthalocyanine pigments, quinacridone pigments and isoindoline pigments. Is preferred. As the extender, calcium carbonate, silica, alumina and barium sulfate are preferred. The solvent contained in the colored ink may be any of a water-based solvent and a solvent-based solvent, and the organic solvent is preferably an aliphatic, aromatic, ketone, or alcohol-based mixture.

As the polyisocyanate to be added to the coloring ink, tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylylene diisocyanate (XDI) and the like are preferably used, and among them, HDI is particularly preferable. An organic solvent is added to the colored ink mixed with the polyisocyanate to obtain a viscosity suitable for printing. The printing viscosity was determined by Zaan Cup No. 3 is preferably 15 to 20 seconds. As the diluting solvent to be added, a mixture of an aliphatic, aromatic, ketone, or alcohol organic solvent is preferable.

As a printing method, there are flexo printing and gravure printing, and a gravure printing method is preferable from the viewpoint of design.
The plate used for printing the colored ink preferably has 100 lines (corresponding to 80 μm) to 200 lines (corresponding to 15 μm), and among them, 110 lines (corresponding to 75 μm) is particularly preferable.

As the main component of the intermediate coating ink of the intermediate coating layer, polyester polyol, acrylic polyol, nitrified cotton, and cellulose are preferable. Particularly preferred are polyester polyols and nitrified cotton. As the pigment, an organic pigment or an inorganic pigment is preferable, and particularly preferably a silica-based inorganic pigment having an average particle diameter of 4 to 10 μm is used as a component. As the organic solvent contained in the intermediate coating ink, a mixture of aliphatic, aromatic, ketone, and alcohol is preferable.

As the silicone oil having a reactive group to be added to the intermediate coating ink, various modified silicone oils are used, and silicone modified by amino modification, methacryl modification, carboxyl modification, carbinol modification, epoxy modification, alcohol modification, etc. Oil is preferably used,
Particularly preferred is an amino-modified silicone oil.
The amount of addition is from 0.1 to the effective component of the silicone oil.
About 2% by weight is preferable. The addition method is preferably performed before adding the polyisocyanate, and is preferably mixed so as to be uniform.

As the polyisocyanate to be added to the intermediate ink, TDI, HDI and XDI are preferable. Particularly preferably, HDI is used as a component. An organic solvent is added to the mixed urethane clear ink in order to obtain a viscosity suitable for printing. The viscosity suitable for printing is Zaancup No. 4 is preferably 9 to 15 seconds. As the dilution solvent to be added, a mixture of an aliphatic, aromatic, or ketone organic solvent is preferable. The plate used for printing the intermediate coating ink is 100 lines (corresponding to 80 μm) to 200 lines (15 μm).
m), and among them, 120 lines (equivalent to 70 μm) are preferable.

The oligomer contained in the UV ink of the overcoat layer includes urethane acrylate, polyester acrylate, epoxy acrylate and unsaturated polyester. Monomers include polyethylene glycol diacrylate, acrylic morphine, pentaerythritol triacrylate, neopentyl glycol diacrylate hydroxypivalate, 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, styrene Are preferred as components.

Particularly preferably, urethane acrylate is used as the oligomer, and polyethylene glycol diacrylate, acrylic morphine, pentaerythritol triacrylate is used as the monomer.

As the photoinitiator contained in the UV ink,
1-hydroxy-cyclohexyl-phenyl-ketone,
Benzyldimethyl ketal and 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropanone are preferred. Particularly preferred are those containing 1-hydroxy-cyclohexyl-phenyl-ketone as a component.

As the pigment contained in the UV ink, pigments such as silica, talc, mica and the like are preferable, and particularly preferably a silica pigment having an average particle diameter of 4 to 15 μm is used as a component. As other additives, polymer-based and silicon-based auxiliaries are preferable, and particularly, polymer-based auxiliaries are preferable.

As the silicone oil having a reactive group to be added to the UV ink, various modified silicone oils are used, and silicone oils such as amino-modified, methacryl-modified, carboxyl-modified, carbinol-modified, epoxy-modified, alcohol-modified, etc. Are preferably used, and particularly preferred is methacryl-modified silicone oil. The addition amount is preferably about 0.5 to 2% by weight of the effective component of the silicone oil.

The plate used for printing UV ink is 100 μm
To 200 μm is preferable, and 150 μm is particularly preferable. To print UV ink, print speed 10m /
Min to 60 m / min. Viscosity suitable for printing is Zancup N manufactured by Rigosha at an ink temperature of 20 to 40 ° C.
o. 5 is preferably 9 to 20 seconds. In order to cure the UV ink, the irradiation amount of ultraviolet rays is preferably from 60 mJ to 160 mJ.

[0026]

The present invention will be described below in detail with reference to examples. The blending composition and other numerical values represent parts by weight. Printing was performed by the following method to prepare a decorative sheet.

(Preparation of colored ink) Urethane resin 3.0 Pigment 12.0 Nitrified cotton 6.2 Toluene 38.1 Xylene 6.5 Ethyl acetate 30.1 Butyl acetate 7.0 Isopropyl alcohol 16.6 Isobutyl alcohol 6. 5 ethylene glycol 2.0 N-propyl cellosolve 3.0 HDI 3.0 3 in 1
It was adjusted to 8 seconds to prepare a colored ink (black).

(Preparation of Intermediate Ink A) Polyester polyol 10.4 Nitrified cotton 11.8 Toluene 51.5 Ethyl acetate 44.3 Methyl isobutyl ketone 5.7 Amino-modified silicone oil 0.5 HDI 11.3 or more At room temperature, Zahn Cup No. 4 in 1
It was adjusted to 0 seconds to prepare an intermediate coating ink A.

(Preparation of Intermediate Ink B) Polyester polyol 9.8 Nitrified cotton 11.1 Toluene 54.3 Ethyl acetate 47.7 Methyl isobutyl ketone 5.3 Silica pigment 5.5 Amino-modified silicone oil 0.5 HDI 11.3 With the above composition, the viscosity is normal temperature, and Zahn Cup No. 4 in 1
It was adjusted to 0 seconds to prepare an intermediate coating ink B.

(Adjustment of UV ink) Urethane acrylate 32.2 Polyethylene glycol diacrylate 35.2 Acrylic morphine 16.0 Pentaerythritol triacrylate 9.2 1-Hydroxy-cyclohexyl-phenyl-ketone 4.2 Polymer additive 0.2 Silica-based pigment 3.0 Methacryl-modified silicone oil 1.0 With a blend of not less than 30 and a viscosity of 30 ° C. 5 was adjusted to 11 seconds to prepare a UV ink.

Example 1 A colored ink was prepared under the following conditions.
The intermediate coating ink A and the UV ink were successively subjected to gravure printing to prepare a decorative sheet 1. (1) Base sheet 60 g resin impregnated paper (2) Colored ink Gravure plate depth 110 lines (corresponding to 75 μm) (3) Intermediate coating ink A Gravure plate depth 120 lines (corresponding to 70 μm) (4) UV ink Gravure plate depth (corresponding to 150 μm) (5) Printing speed 30m / min (6) UV irradiation 60mJ

Example 2 A decorative sheet 2 was prepared by printing in the same manner as in Example 1 except that the intermediate ink B was used instead of the intermediate ink A.

Example 3 In Example 1, the amount of the amino-modified silicone oil added to the intermediate ink A was 2.5.
The printing was performed in the same manner as in Example 1 except that the decorative sheet 3 was formed.

Comparative Example 1 In the preparation of the ink of Example 1, an alkyl-modified silicone oil having no reactive group was used instead of the amino-modified silicone oil in the intermediate coating ink.
5 parts, instead of the methacryl-modified silicone oil of the UV ink, 1.0 part of a polyether-modified silicone oil having no reactive group was added, and printing was performed under the same conditions as in Example 1 except that the comparative decorative sheet 1 was used. Created.

Comparative Example 2 A comparative decorative sheet 2 was prepared by printing under the same conditions as in Example 1 except that the amino-modified silicone oil of the intermediate coating ink A was omitted.

With respect to the decorative sheets described above, the design property representing the feeling of unevenness was visually evaluated by a four-level (、, △, Δ, ×) sensory test. Regarding the adhesive release property, a new cellophane tape was stuck to a certain coating part according to the Cellotape (registered trademark) peel test, and then the operation of peeling was repeated until a part of the coating film was released. The number was evaluated.
20 times or more (回), 10-19 times (○),
In the case of 5 to 9 times (△), in the case of 4 times or less (×).
Table 1 shows the results.

[Table 1]

[0037]

Industrial Applicability The decorative sheet according to the present invention does not contain vinyl chloride, has a light environmental load, has a sufficient design of unevenness, and has good releasability from an adhesive such as an adhesive label.

 ────────────────────────────────────────────────── ─── Continued on the front page F term (reference) 2H113 AA03 AA06 BA03 BA27 BB07 BC00 BC13 CA46 DA15 DA43 DA53 DA57 DA62 DA64 EA10 4F100 AH06C AH06D AK41 AK51C AK52C AK52D AL06D AT00A BA04 BA07 BA10A BA10D CA13B10B31B10B31B10BCAB

Claims (4)

[Claims] 1. An ultraviolet curing method comprising a printing ink layer (b), an intermediate coating layer (c) which is a urethane-based clear ink, and a pattern printed with a gravure plate having a plate depth of 100 to 200 μm on a substrate sheet (a). A decorative sheet having a top coat (d), which is a mold ink, in this order, wherein the intermediate coat (c) and the top coat (d) contain a silicone oil having a reactive group. 2. The decorative sheet according to claim 1, wherein the silicone oil contained in the intermediate coating layer (c) is an amino-modified silicone oil having a reactive group. 3. The decorative sheet according to claim 1, wherein the silicone oil contained in the overcoat layer (d) is a methacryl-modified silicone oil having a reactive group. 4. The silicone oil having a reactive group in the intermediate coating layer (c) has a content of 0.1 to 2% by weight,
The decorative sheet according to any one of claims 1 to 3, wherein the content of the silicone oil having a reactive group in the overcoat layer (d) is 0.5 to 2% by weight.