JP2556322B2 - Makeup sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a decorative sheet, more specifically, scratch resistance,
It is an object to provide a decorative sheet having excellent stain resistance and mattness.

(Prior Art) Conventionally, many decorative sheets are used as various building materials,
Among these decorative sheets, there are those with a glossy surface and those without a glossy surface, which are used for their respective suitable applications.

A conventional surface matte decorative sheet is a two-component curing type or heat-curing resin such as urethane resin or aminoalkyd resin in which a matting agent such as silica is mixed as a top coating on the surface of a base material such as printed paper. It is known that a curable resin paint is applied and finished. Since these matte decorative sheets have an insufficient cross-linking density of the surface layer, they have scratch resistance, stain resistance, and
Surface properties such as solvent resistance are insufficient. As a solution to these drawbacks, an ionizing radiation curable paint containing a matting agent is applied to the surface of a transparent plastic film and then cured to form a matte surface, which is adhered to the surface of a substrate having a printing layer. What laminated | stacked via the agent layer is known. Those using these ionizing radiation-curable coatings have a higher scratch resistance than those of the above-mentioned thermosetting resins because the cured coatings obtained from the coatings are highly crosslinked coatings. However, the presence of the matting agent makes the stain resistance insufficient, and the presence of the matting agent makes the curing of the coating non-uniform, so that the surface gloss changes with time and is unstable. There are drawbacks.

As a method for forming a matte surface, a physical method that does not use a matting agent, that is, an embossing method is also known, but when this method is applied to a decorative sheet that uses the thermosetting resin, it is formed. As a result, the surface of the fine uneven surface is returned to its original shape, and a sufficiently stable matte surface cannot be formed. On the other hand, when applied to the above-mentioned ionizing radiation-cured coating, the cured coating does not soften even by heat, so that it is not possible to form a sufficient fine uneven shape.

Therefore, there is a demand for a decorative sheet having excellent matting properties, scratch resistance, stain resistance, and the like.

(Means for Solving Problems) As a result of earnest research to meet the above-mentioned demands of the prior art, the present inventor provides a sufficient matting property even with an ionizing radiation-cured coating by a usual embossing treatment method. The present invention has been completed on the finding that it is possible.

That is, the present invention is a decorative sheet in which a base material, a pattern printing layer, an adhesive layer and a surface coating layer are laminated in this order, wherein the surface coating layer is a resin film having a large tensile strength,
It is a three-layer laminate of a low softening point resin film and an ionizing radiation-cured coating, wherein the uppermost cured coating has fine irregularities, and is a decorative sheet with excellent scratch resistance and matting properties.

(Function) By providing a resin film having a low softening point and a resin film having a large tensile strength under the ionizing radiation-cured film that forms a minute uneven shape, the above-mentioned ionizing radiation-cured film has sufficient mattness A shape can be formed, and various processability can be enhanced by a resin film having a large tensile strength.

(Preferred Embodiment) Next, the present invention will be described in more detail with reference to the accompanying drawings that schematically show preferred embodiments of the present invention.

The decorative sheet 10 of the present invention has a substrate 1, a pattern printing layer 2, an adhesive layer 3 and a surface coating layer 8 laminated in this order as shown in the cross section of FIG. The surface coating layer 8 is a three-layer laminate 8 including a resin film 4 having a large tensile strength, a resin film 5 having a low softening point, and an ionizing radiation-cured coating 6, and minute irregularities 7 are formed on the ionizing radiation-cured coating 6. It has been done.

The base material used in the decorative sheet 10 of the present invention is a base material used in conventionally known decorative sheets, for example, thin paper, kraft paper, high-quality paper, titanium paper, linter paper, paperboard, Any of gypsum board paper, latex-impregnated paper, synthetic resin mixed paper, non-woven fabric and the like can be used without any particular limitation.

The pattern print layer 2 may be provided on at least one surface of the base material 1 with a normal printing ink, and the printing method and the pattern to be formed are not particularly limited.

An adhesive layer 3 is formed in order to laminate the surface coating layer 8 on the above-mentioned pattern printing layer 2. This adhesive layer 3 is also made of any of the adhesives used in conventionally known laminate type decorative sheets. Can also be formed and is not particularly limited. Further, these adhesive layers 3 may be formed on the pattern printing layer 2 in advance, or the back surface of the surface coating layer 8 after providing the minute unevenness shape 7, that is, the resin film 4 having a large tensile strength. It may be provided on the surface.

The main feature of the present invention is the configuration of the surface coating layer 8 described above, and the lowermost layer of the surface coating layer 8 is:
A resin film having a large tensile strength such as polyethylene terephthalate film, nylon film, polypropylene film, cellophane film, acetate film, polycarbonate film, polystyrene film and the like is used. The resin film having a thickness of about 5 to 200 μm can be generally used, but the preferable thickness range is 10
To 50 μm.

The low softening point resin film 5 laminated on the resin film 4 having a large tensile strength is, for example, a polyethylene film,
Examples thereof include polyvinyl chloride film, polyvinylidene chloride film, ethylene-vinyl acetate copolymer film, polyvinyl alcohol film, and the like, and are made of a resin that is sufficiently softened to be embossable depending on the temperature during the subsequent embossing treatment. The resin film 5 may have a thickness greater than that corresponding to the uneven surface of the embossing roll during the embossing process, and for example, a preferable thickness range is about 5 to 15 μm.

The resin film 4 having a large tensile strength and the resin film 5 having a low softening point may be formed separately and laminated by a method of laminating both, but preferably both are coextruded by the T-die method. Or resin film with high tensile strength 4
It is economical to extrude and laminate the resin film 5 having a low softening point on the upper side to integrate the both.

In the above-mentioned laminated film, the resin film 4 having a large tensile strength gives the laminated film a so-called "waist", and exhibits sufficient processability during embossing or bonding to the substrate 1. Further, these laminated films need to be substantially transparent, and may be colored as long as they are transparent.

On the other hand, the laminated low softening point resin film 5
Sufficient embossability is imparted to the ionizing radiation-cured coating 6 formed thereon.

On the surface of the low softening point resin film 5 of the laminated film as described above, a cured film 6 is formed from an ionizing radiation curable coating material such as an electron beam curable coating material or an ultraviolet curable coating material, which is embossed to form a fine surface. The uneven shape 7 is formed.

Electron beam curable paints and ultraviolet curable paints are similar in composition except that the latter contains a photopolymerization initiator or a sensitizer, and generally have a structure as a film-forming component. A polymer having a radical polymerizable double bond therein,
It contains an oligomer, a monomer and the like as main components, and optionally contains a non-reactive polymer, an organic solvent, wax and other additives.

Particularly preferred for the purposes of the present invention are those in which the film-forming component has an acrylate-based functional group, for example, a relatively low molecular weight polyester resin, a polyether resin,
Acrylic resin, epoxy resin, urethane resin, alkyd resin, spiro acetal resin, polybutadiene resin,
Polythiol polyene resin, oligomer or prepolymer such as (meth) acrylate of polyfunctional compound such as polyhydric alcohol, and ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, N-vinyl as a reactive diluent. Monofunctional and polyfunctional monomers such as pyrrolidone, for example, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, pentaerythritol triacrylate (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth)
It contains a relatively large amount of acrylate, neopentyl glycol di (meth) acrylate, and the like.

By using such a polyfunctional (meth) acrylate-based ionizing radiation curable coating material, it is possible to form a cured resin layer having excellent surface hardness, transparency, scratch resistance, stain resistance and the like. Further, when such a cured resin layer is required to have high flexibility and shrinkage resistance, an appropriate amount of a thermoplastic resin, for example, a non-reactive acrylic resin or various waxes, is added to the curable coating material. It is possible to meet those demands by adding. Further, these curable paints need to be transparent so that the printed pattern of the lower layer can be seen, and if they are transparent, they may be lightly colored, and in a range that does not hinder the purpose of the present invention. , May also contain a quenching agent.

Further, in order to make the above-mentioned curable paint an ultraviolet-curable paint, acetophenones, as a photopolymerization initiator therein,
Benzophenones, Michler benzoyl benzoate,
α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthones, and n as a photosensitizer
-Butylamine, triethylamine, tri-n-butylphosphine, etc. can be mixed and used.

Various grades of ionizing radiation curable coatings such as the above-mentioned electron beam or ultraviolet curable coatings are known, and all of them can be easily obtained from the market and used in the present invention.

Further, conventional curing methods can be used as they are, for example, in the case of electron beam curing, Cockloft-Walton type, Van de Graaff type, resonance transformation type, insulating core transformer type, linear type, dynamitron type, high frequency type. 50 to 1,000 KeV emitted from various electron beam accelerators, preferably 10
An electron beam having an energy of 0 to 300 KeV is used, and in the case of ultraviolet curing, an ultra-high pressure mercury lamp, a high pressure mercury lamp,
Ultraviolet rays emitted from a light source such as a low-pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp are used.

The ionizing radiation-curable coating material as described above is, for example, blade coating method, gravure coating method, rod coating method, knife coating method, reverse roll coating method, spray coating method, offset gravure coating method, kiss coating method, etc. A gravure coating method which is applied on the low softening point resin film 5 by a method, and which is particularly excellent in accuracy of coating thickness, smoothness of coating surface,
A reverse roll coating method, an offset gravure coating method and the like are suitable.

Further, if the coating amount of the above-mentioned curable coating is too small, sufficient surface hardness, surface strength or scratch resistance cannot be obtained, and if it is too large, fine unevenness having sufficient matteness by the subsequent embossing treatment. 1 to 10 because it is difficult to form the shape
A thickness in the range of 0 μm, particularly about 1 to 10 μm (thickness when dried) is suitable.

A normal embossing method is used to form the fine irregularities 7 on the cured film 6 which is the uppermost layer of the three-layer laminate 8. The embossing method includes a method using a roll-shaped embossing plate and a method using a lithographic embossing plate, but either method may be used. These matte embossing plates are made of metal or the like and are provided with minute irregularities having a depth of about 1 to 15 μm by etching, electroforming, sandblasting, etc. However, considering the appearance of the embossed film, it is preferable that the embossed film has an embossing depth of 2 to 10 μm.

With such an embossing plate, the ionizing radiation curing coating 6
The cured film can be provided with fine unevenness 7 by embossing, but a preferable fine unevenness 7 is a temperature at which the low softening point resin film 5 softens the embossed plate, for example, about 80 to 150 ° C. It is preferable to perform the heating at the temperature of. The embossing process may be performed at any time, and may be performed before or after the surface coating layer 8 is attached to the substrate 1 having the printing layer 2.

The surface coating layer 8 and the substrate 1 having the printed layer 2 may be bonded by a conventional method.

(Effect) According to the present invention as described above, since the resin film layer having a low softening point is present under the ionizing radiation-cured film, the resin film having a low softening point is easily softened at the time of embossing treatment to be a cured film. Since the embossing is possible and the plasticity of the embossing plate is immediately lost after the mold is released, it is possible to effectively retain the fine concavo-convex shape imparted to the cured coating. Therefore, even though the ionizing radiation-cured coating has a high crosslink density, excellent mattness can be imparted.
Further, since the depth of the emboss can be freely adjusted by the thickness of the low softening point resin film, various matte decorative sheets can be provided. Further, since the low softening point resin film can be easily made to have a constant thickness, it is possible to form a fine uneven shape having a uniform depth in the cured film, and thus to provide a uniform matte surface. .

Further, since a resin film having a large tensile strength is present under the low softening point resin film, it is possible to provide sufficient processability during embossing or laminating with a substrate.

As described above, the decorative sheet of the present invention is an ionizing radiation-cured coating having a high cross-linking density and having a surface with uniform fine irregularities, and thus, with sufficient matting properties, sufficient scratch resistance,
Since it has stain resistance and solvent resistance, various problems of the prior art have been solved.

(Example) Next, an Example is given and this invention is demonstrated still more concretely.

A ground coat and a decorative pattern were printed on the surface of a 23 g / m ² thin paper (manufactured by Sanko Paper Co., Ltd.) by a gravure printing method using a printing ink (manufactured by Morohoshi Ink) made of a nitrocellulose vehicle.

On the other hand, polyethylene terephthalate and polyvinylidene chloride were co-extruded by a T-die method outside the die to a thickness of 20 μm and 5 μm, respectively, and the polyvinylidene chloride film side of this co-extruded film did not contain a delustering agent (Dainichi Seisei). 2 μm by the gravure coating method of Seika Beam PHC, polyester acrylate, etc.
To a thickness of 12.5 cm, and then pass it under two UV lamps with an output of 160 W / cm at a position of 12.5 cm on the coated surface at a speed of 10 m / min. Cured.

Next, the surface of the cured film of the above film was heat-embossed using an embossing roll (unevenness difference: 4 μm, 60 ° reflection gloss value: 4.7) whose surface was matt-treated by a sandblast method. The 60 ° reflection gloss value of the obtained embossed surface was 12.0.

Next, the back surface layer of the printed surface of the base material and the surface coating layer was dry laminated using a polyurethane adhesive (manufactured by Takeda Pharmaceutical Co., Ltd.) to obtain a decorative sheet of the present invention.

Even if the surface of this decorative sheet was strongly rubbed 20 times with steel wool # 0000, no scratch was given. When characters were written on the surface with an oil-based felt-tip pen, and after being dried and sufficiently rubbed with a dry cloth, the characters were wiped off sufficiently and no stain was observed on the surface.

For comparison purposes, the decorative sheet prepared in the same manner as above except that the ultraviolet curable coating material contained 10% by weight of a matting agent (silica) and the cured coating was not embossed Although it had almost the same matteness as the decorative sheet of No. 1, the surface was scratched in the same scratch resistance test, and ink was absorbed on the surface in the stain resistance test.
It couldn't be wiped out completely.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a cross section of a decorative sheet of the present invention. 1: Base material 2: Pattern print layer 3: Adhesive layer 4: Resin film with high tensile strength 5: Low softening point resin film 6: Ionizing radiation curing coating 7: Micro unevenness 8: Surface coating layer 10: Decorative sheet

Claims (2)

(57) [Claims] 1. A decorative sheet in which a substrate, a pattern printing layer, an adhesive layer and a surface coating layer are laminated in this order,
The surface coating layer is a three-layer laminate of a resin film having a large tensile strength, a resin film having a low softening point, and an ionizing radiation-cured film, and the cured film of the uppermost layer has a minute uneven shape, and has an abrasion resistance. Decorative sheet with excellent softness and mattness. 2. The decorative sheet according to claim 1, wherein the ionizing radiation-cured coating contains substantially no matting agent.