JPH1086314A - Stain resistant decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a decorative sheet having no aging deterioration such as without interlayer release at aging like a fluorine film-laminated product, yellowing with ultraviolet ray in natural light like an ultraviolet curable resin- coated product, craze or crack of a surface layer, or hard charging or hard adherence of dust when a three-dimensional molding is decorated by lapping by vacuum molding since excellent weather resistance, stain resistance, scuff resistance and easy glaze regulation with low cost and adhesive strength of the surface layer is high. SOLUTION: A sheet obtained by laminating a surface layer 1 coated with a paint containing an acrylic resin having a silanol group, an epoxy group and a hydroxyl group and a metal chylate of a curing catalyst and crosslinked, with a thermoplastic resin sheet is decorated. Further, a soft mat design in which a conductive and mat substance is added is provided on the surface layer of the decorative sheet 8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention can be used as a surface decorative sheet used for interior decoration of buildings, surface decoration of fittings, vehicle interiors, etc., and is excellent in both stain resistance and scratch resistance.

[0002]

2. Description of the Related Art Conventionally, decorative sheets used for such applications include polyvinyl chloride films, which are decorated with printing, embossing and the like (Japanese Patent Publication Nos. 28-5036 and 58-58). No. 14312).

[0003] In recent years, (1) a stain-resistant decorative sheet laminated with a fluorine film has appeared. For example, there has been a coating material for lamination coating in which a fluororesin film is joined and integrated on the outer surface of a thermoplastic resin thin sheet such as a polyvinyl chloride calender sheet via an adhesive layer. (JP-B-61-53228) (2) A decorative sheet coated with an ultraviolet curable paint has also appeared.

[0004]

The conventional decorative sheet as described in (1) is mass-produced industrially, and when used as an interior material for buildings, etc., since a single layer of fluororesin comes on the surface layer, it is not scratch-resistant. Poor sex. If the scratched area becomes dirty, it cannot be removed. Easily dusty due to charging. There is no painted design. That is, the image is matte without sharpness. Poor adhesion strength between fluorine film and base film,
Quality is unstable. There was a problem.

[0005] Further, the conventional decorative sheet as described in (2) is industrially mass-produced and has insufficient stain resistance when used for interior materials of buildings. (Easily penetrates hair dyes, etc.) Equipment for ultraviolet curing is required, which is expensive. Poor weather resistance. It turns yellow when irradiated with ultraviolet light. There was a problem.

[0006]

Therefore, in order to solve the above-mentioned problems, in the present invention, a paint containing an acrylic resin containing a silanol group, an epoxy group and a hydroxyl group and a metal chelate as a curing catalyst is provided. Despite being one-part, it cures at low temperature, and the cured coating film is extremely excellent in weather resistance, scratch resistance, chemical resistance, and stain resistance. And crosslinked, and used for the surface layer of the decorative sheet.

That is, the present inventors laminated a surface layer formed by applying a coating containing an acrylic resin containing a silanol group, an epoxy group, and a hydroxyl group and a metal chelate as a curing catalyst and cross-linking the thermoplastic resin sheet. A stain-resistant decorative sheet, characterized in that a decorative sheet is subjected to a decoration treatment.

[0008] A stain-resistant decorative sheet having a soft mat design, characterized in that a conductive and matting substance is added to the surface layer of the decorative sheet. Was developed.

[0009]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a sectional view showing an example of a decorative sheet according to the present invention, which is applied to a steel sheet to form a decorative steel sheet. FIG. 2 is a cross-sectional view showing an example of a decorative sheet according to the present invention, which is attached to a medium-density fiber board to form a kitchen door. FIG. 3 is a sectional view showing an example of a decorative sheet according to the present invention, which is applied to a plywood to form a decorative plywood.

1 and 2, in a decorative sheet formed by laminating a polyvinyl chloride layer 5 and a polyethylene terephthalate film 2, a silanol group, an epoxy group,
Surface layer 1 coated and crosslinked with a paint containing a hydroxyl group-containing acrylic resin and a metal chelate as a curing catalyst
The decorative sheet 8 having excellent stain resistance, scratch resistance, and weather resistance was obtained.

In FIG. 3, in a decorative sheet made of a polypropylene layer 20, silanol groups, epoxy groups,
By providing the surface layer 1 on which a paint containing a hydroxyl group-containing acrylic resin and a metal chelate as a curing catalyst was applied, a decorative sheet 18 excellent in stain resistance and scratch resistance was obtained.

Further, the surface layer was firmly adhered to polyethylene terephthalate or polypropylene, and a surface layer excellent in stain resistance could be provided.

In the paint of the present invention, the metal chelate is
If the chelating agent is added to the system in an equivalent amount or more, the catalytic activity is suppressed, and the catalyst is stably present during storage. However, once the paint is applied to the thermoplastic resin sheet and the chelating agent volatilizes, the catalyst activates and attaches to the silanol groups, generating Bronsted acids. Bronsted acid reacts with oxirane groups and silanol groups and, via oxonium salts, causes a cross-linking reaction competitively.

The molecular weight MW of the resin of the surface layer thus formed is in the range of 30,000 to 40,000.
To alicyclic epoxy and silanol groups.

[0015] In the case of coating, the titanium oxide is converted into a resin / pigment = 1 /
8 and then the pigment concentration is finally 100 PHR
The varnish was prepared so that

In the paint of the present invention, the curing reaction is initiated by the coordination of a metal chelate such as an aluminum chelate to a silanol group. However, a chelating agent for the metal chelate and an alcohol may be added. The reaction does not start during storage. For example, the addition of β-diketone which is a chelating agent for aluminum chelate and isobutanol hardly increases the viscosity even after storage at 40 ° C. for 100 days.

By adding a matting agent or a conductive and matting substance described later to this surface layer, the matting agent or the conductive and matting substance is coated with the functional layer to form a mat ( Matt) Although it is a design, it is possible to obtain a decorative sheet having a soft feeling and excellent in weather resistance, stain resistance, abrasion resistance, and conductivity.

As the conductive and matting substance added to the surface layer, there are a metal fine powder and an inorganic conductive filler. As the metal fine powder, in particular, aluminum,
Tin, chrome, iron, gold, silver, copper, nickel, antimony,
Magnesium and zinc are suitable. The metal fine powder is used alone or as a matting agent such as silica, calcium carbonate,
You may add together with powders, such as barium sulfate, titanium, clay, and talc. If necessary, about 0.1 to 10 parts by weight is added.

As the inorganic conductive filler, ZnO
A zinc oxide type such as (Al), SnO ₂ (Sb)
/ BaSO ₄ , such as BaSO ₄ , SnO ₂
/ BaSO barium sulfate-based, such as the ₄ ones _{(undoped), SnO 2 (Sb) /} 9Al 2 O 3 · 2B 2 aluminum borate systems, such as O ₃ things (needles), SnO ₂ (Sb)
/ Those of titanium oxide such as TiO _2, SnO ₂ (S
b) Tin oxide (ultra fine particles) such as TiO
Titanium black type such as (N), SnO ₂ (S
_{b) / K 2 O · nTiO} 2 and C / K ₂ potassium titanate system, such as O · nTiO ₂ (those needles) are used. Here, the material on the left side of / indicates the coating material, and the material on the right side of / indicates the core material. The substance in parentheses is a doping agent, for example, ZnO (Al) is a substance obtained by adding a small amount of aluminum to zinc oxide. In addition, SnO ₂
(Sb) / BaSO ₄ is a substance obtained by coating a core agent of barium sulfate with tin oxide to which a small amount of antimony is added.

The thickness of the surface layer is preferably about 2 to 20 μm. If the thickness is less than 2 μm, the stain resistance function cannot be said to be sufficient, which is inconvenient. On the other hand, when the thickness exceeds 20 μm, when a sheet is formed, the shrinkage stress increases during lamination, curling is likely to occur, or the cost increases, which is inconvenient.

By mixing known antibacterial agents and antifungal agents into the paint for forming the surface layer, a stain-resistant decorative sheet having excellent antibacterial and antifungal properties can be obtained.

The following antibacterial agents or fungicides are used:
Can be used. Antimicrobial ^{Ag +, Cu 2 +, Zn} 2 +, Hg +, Ni
Metal ions such as ² + and Cd ² + (especially Ag + is harmless to the human body and has a long lasting effect, and is therefore desirable from the viewpoint of safety and performance). Zeolite, apatite, glass, silica gel, phosphate, phosphoric acid An ion exchanger such as zirconium (especially, zeolite and zirconium phosphate, which have a proven track record and high reliability), are supported ion-exchangeably (JP-B-63-54013, JP-A-4-300975).
No., etc.).

In the above, an antibacterial ion obtained by further adding an ammonium ion to a metal ion (disclosed in Japanese Patent Publication No. 4-28646). Organic compounds having antibacterial properties, for example, sulfa agents such as P-aminobenzenesulfonamide, sulfathiazole, sulfpyridine, sulfadiazine, dithiocarbamates such as dimethyldithiocarbamate and ethylenebisdithiocarbamate, 2- (2- Frill) -3- (5
-Nitro-2furyl) acrylamide and the like.

Trimethoxysilylpropyloctadecyl ammonium chloride having antibacterial and antifungal properties,
10.10-Oxybisphenoxyarsine, 2- (4
-Thiazolyl) -benzimidazole, bis (2-pyridylthio-1-oxide) zinc, 2-N-octyl-4
-Isothiazolin-3-one, 2,3,5,6-cytochloro-4- (methylthio) -phthalimide, N- (fluorodichloromethylthio) florimide, griseofulvin, tricomycin, amphotericin B and the like. Antibiotics, for example, penicillin such as phenoxymethyl penicillin and dicloxacillin, cephalosporins such as cephalotin and cefazolin, streptomycin sulfate such as streptomycin sulfate and paromomycin (sulfate), erythromycin such as erythromycin and josamycin, tetracycline such as tetracycline nitrate and loritetracycline nitrate Chloramphenicol, chloramphenicol, thiamphenicol, aminoacetic acid ester hydrochloride and the like.

As the thermoplastic resin sheet, in addition to polyethylene terephthalate, a film or sheet made of a known thermoplastic resin such as polyethylene, polypropylene, polyvinyl chloride, polyether ketone, and polyimide can be used. These may be colored sheets. Further, as the base sheet, other than a film or a sheet made of a thermoplastic resin, a sheet containing a resin for forming a surface layer such as paper or nonwoven fabric through a decorative layer and tightly adhered thereto can also be used.

The decorating treatment includes coloring (transparent or opaque coloring) by adding a pigment to at least one layer constituting the decorative sheet, printing of a pattern as shown in FIGS. 1, 2 and 3, embossing (heating press), This refers to shaping of the uneven pattern by hairline processing or the like.

As the pigment, titanium white, zinc white, red stalk,
Inorganic pigments such as vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, etc .; Dyes), metal pigments such as aluminum and brass, and pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate. These are added and dispersed as powder or flaky foil pieces.

As the picture (pattern) printing, a pattern is formed by ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet.

As the pattern, there are a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather drawing pattern, a geometric figure, a character, a symbol, a solid pattern, and the like. The pattern is on the front, back, both sides of the sheet,
Alternatively, it is provided between layers.

As the ink (or) paint, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyesters, polyurethanes, acrylics, vinyl acetate, vinyl chloride-vinyl acetate copolymers, cellulose resins, etc. are used as binders. And used alone or in combination of two or more. A material obtained by adding known pigments as described above to this is used.

The embossing is performed by softening a polyvinyl chloride resin by heating, pressing, shaping with an embossing plate, and fixing by cooling. A known sheet-fed or rotary embossing machine is used. Can be

Examples of the irregularities include a wood grain conduit groove, a stone surface irregularity (granite cleavage plane, etc.), a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, and the like.

Further, if necessary, the concave portions of the concavo-convex pattern can be filled with a coloring ink by a known wiping method (see Japanese Patent Publication No. 58-14312). The same thing as the above can be used for the coloring ink. However, from the viewpoint of abrasion resistance, a material using a two-component curable urethane resin as a binder is preferable.

The metal thin film is made of aluminum, chromium, gold,
A film is formed by a method such as vacuum evaporation and sputtering using a metal such as silver or copper. Alternatively, a combination of these may be used.
The metal thin film may be provided on the entire surface or partially in a pattern.

[Ultraviolet Absorber / Light Stabilizer] An ultraviolet absorber and / or a light stabilizer can be added in order to impart better weather resistance (light resistance) to the resin. Both the absorber and the light stabilizer are usually about 0.5 to 10% by weight, but it is generally preferable to use the ultraviolet absorber and the light stabilizer together.

Organic substances such as benzotriazole, benzophenone, salicylate, etc.
Alternatively, inorganic substances such as zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used. As the light stabilizer, a hindered amine radical scavenger such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and a radical scavenger such as a piperidine radical scavenger can be used.

The above-mentioned ultraviolet absorbers / light stabilizers and flame retardants described below are preferably mixed in any layer of the decorative sheet.

As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used, and these are added when it is necessary to impart flame retardancy. The amount of addition is about 0.1 to 20 parts by weight based on 100 parts by weight of each resin.

The stain-resistant decorative sheet of the present invention can be laminated on another adherend (backing material). Lamination is performed when the decorative sheet itself can be adhered to the adherend (at the heat melting point, etc.)
The adhesive layer may be omitted, and if the decorative sheet itself does not adhere to the adherend, it is laminated with an appropriate adhesive.

The adherend is the final product, and a decorative sheet may be laminated for the surface decoration. If necessary, the decorative sheet may be used to reinforce the mechanical strength of the decorative sheet or to provide concealment. An adherend may be laminated on the back surface.

As the adherend, flat plates of various materials (FIG. 1),
Objects of various shapes, such as a plate material (FIG. 2) such as a curved plate, a three-dimensionally shaped article (molded product), and a sheet (or film) are targeted. As a material used for any of a board material, a three-dimensionally shaped article, and a sheet (film), a wood board such as a wood veneer, a wood plywood, a particle board, a medium density fiber board (MDF) and a wood board such as a wood fiber board , Iron, aluminum, etc., acrylic, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS, phenolic resin, polyvinyl chloride, cellulose resin, rubber and other resins, exclusively board materials Or, as a material used as a three-dimensional article, ceramics such as glass, ceramics, etc., AL
Non-cement ceramic materials such as cement such as C (foamed lightweight concrete), calcium silicate, gypsum, etc. Materials used exclusively as sheets (or films) include paper such as high-quality paper and Japanese paper, carbon, asbestos, and titanate. There is a nonwoven fabric or a woven fabric made of fibers such as potassium, glass, and synthetic resin.

As a method of laminating these various adherends,
For example, as described in JP-B-50-19132, JP-B-43-27488, and the like, a decorative sheet is a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive layer therebetween. Between the male and female molds for injection molding,
The two molds are closed, the molten resin is injected and filled from the male mold gate, and then cooled, and a decorative sheet is adhered and laminated on the surface of the molded resin simultaneously with the molding of the molded resin. No. 45768, Japanese Patent Publication No. 60-
As described in Japanese Patent No. 58014, etc., a decorative sheet is opposed to or placed on the surface of a molded article with an adhesive layer interposed therebetween.
A so-called vacuum press lamination method in which a decorative sheet is laminated on the surface of a molded product by a pressure difference caused by vacuum suction from the molded product side,
As described in JP-B-61-5895, JP-B-3-2666, etc., a decorative sheet is supplied in the longitudinal direction of a columnar substrate such as a column or a polygonal column via an adhesive layer therebetween. A so-called lapping method, in which a decorative sheet is sequentially pressure-adhered and laminated on a plurality of side surfaces constituting a columnar body by a plurality of rollers having different directions, a real public university 15-31.
No. 122, JP-A-48-47972, etc., a decorative sheet is first laminated on a plate-like substrate via an adhesive layer, and then the plate-like substrate is on the side opposite to the decorative sheet. Cut a V-shaped or U-shaped groove reaching the interface between the decorative sheet and the plate-shaped substrate on the surface, and then applying an adhesive in the groove, and bending the groove There is a so-called V-cut or U-cut processing method for forming a box or a column.

In particular, the method for bonding the decorative sheet of the present invention to a three-dimensional object having irregularities includes (a) a lapping method, (b) a V-cut method, (c) a simultaneous lamination method of injection molding, d) A vacuum forming simultaneous lamination method or the like is preferable.

The stain-resistant decorative sheet of the present invention is laminated on various adherends, subjected to a predetermined forming process, and used for various purposes. For example, walls, ceilings, floors and other building interiors, window frames, doors,
Surface makeup of fittings such as handrails, surface makeup of furniture or cabinets of light electric / OA equipment, interior of vehicles such as automobiles and trains, interior of aircraft, makeup of window glass, etc.

[0045]

Embodiments of the present invention will be described below in detail.

Example 1 A coating containing an acrylic resin containing a silanol group, an epoxy group, and a hydroxyl group, a curing catalyst such as aluminum chelate, β-diketone, and isobutanol was gravure-coated on a corona-treated surface of polyethylene terephthalate to a thickness of 3 μm. And dried at a heating temperature of 130 ° C. for several seconds. A pattern layer was formed on the surface of the laminated sheet opposite to the corona-treated surface of polyethylene terephthalate with a urethane-based or vinyl chloride-vinyl acetate copolymer-based colored ink. The pattern layer was coated with a urethane-based adhesive for dry lamination, and bonded to a colored vinyl chloride sheet to obtain a stain-resistant decorative sheet of the present invention. By attaching the decorative sheet to an iron plate via a general steel sheet adhesive, it has a painted feeling, stain resistance,
A decorative steel sheet having excellent scratch resistance and weather resistance was obtained.

Example 2 An acrylic resin containing a silanol group, an epoxy group and a hydroxyl group, titanium oxide, an aluminum chelate as a curing catalyst,
3 parts of silica having a particle diameter of 4 μm is dispersed in a paint containing β-diketone, isobutanol, silicon and silica, and gravure-coated on a corona-treated surface of polyethylene terephthalate to form a layer having a thickness of 5 μm. Dried for seconds. A pattern layer was formed on the surface of the laminated sheet opposite to the corona-treated surface of polyethylene terephthalate with a urethane-based or vinyl chloride-vinyl acetate copolymer-based colored ink. The pattern layer was coated with a urethane-based adhesive for dry lamination, and bonded to a colored vinyl chloride sheet to obtain a stain-resistant decorative sheet of the present invention. The decorative sheet was coated on a kitchen door made of a medium-density fiberboard by a vacuum press to obtain a natural mat-like kitchen decorative door. This kitchen decorative door had surface properties excellent in stain resistance, scratch resistance, and weather resistance.

Example 3 A paint, which is a mixture of an acrylic resin containing a silanol group, an epoxy group and a hydroxyl group, a curing catalyst such as aluminum chelate, β-diketone, isobutanol, silicon and aluminum powder, was subjected to corona treatment with polyethylene terephthalate. The surface was gravure coated and laminated at a thickness of 5 μm, and dried at a heating temperature of 130 ° C. for several seconds. A pattern layer was formed on the surface of the laminated sheet opposite to the corona-treated surface of polyethylene terephthalate with a urethane-based or vinyl chloride-vinyl acetate copolymer-based colored ink. The pattern layer was coated with a urethane-based adhesive for dry lamination, and bonded to a colored vinyl chloride sheet to obtain a stain-resistant decorative sheet of the present invention. The decorative sheet was coated on a kitchen door made of a medium-density fiberboard by a vacuum press to obtain a natural mat-like kitchen decorative door. This kitchen decorative door was not easily dusted and had surface properties excellent in stain resistance, scratch resistance and weather resistance.

Example 4 A pattern layer (wood pattern) was formed on one side of a 100 μm white polypropylene film mixed with titanium using a urethane-based or vinyl chloride-vinyl acetate copolymer-based colored ink. An acrylic resin containing a silanol group, an epoxy group, and a hydroxyl group, a curing catalyst such as aluminum chelate, β-diketone, isobutanol, and a paint made of zeolite supported on a zeolite in an ion-exchangeable manner, on a printing surface of a white polypropylene film. And then dried at a heating temperature of 90 ° C. for several seconds. A white polypropylene film is pressed from the pattern layer side with an embossing plate adjusted to 50 ° C having a duct-like uneven shape while being softened along a drum heated to 150 ° C, and has an embossed shape. A stain-resistant decorative sheet of the present invention was obtained. The decorative sheet was coated on a plywood via a urethane-based adhesive to obtain a decorative plywood having a natural matte-like wooden skin. This decorative plywood had surface properties excellent in stain resistance, scratch resistance, weather resistance and antibacterial properties.

[0050]

Industrial Applicability The stain-resistant decorative sheet of the present invention has an effect of being excellent in weather resistance, stain resistance and scratch resistance while being low in cost. The effect that gloss adjustment is easy is produced. Due to the strong adhesive strength of the surface layer, when wrapped and decorated on a three-dimensional molded product by vacuum molding, it does not delaminate over time like a fluorine film laminated product, and also like an ultraviolet curable resin coated product In addition, there is an effect that there is no deterioration with time such as yellowing due to ultraviolet rays in natural light, cracks in the surface layer, and cracks. As it is hard to be charged, it is hard to get dust.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing an example of a decorative sheet according to the present invention, which is applied to a steel sheet to form a decorative steel sheet.

FIG. 2 is a cross-sectional view showing an example of a decorative sheet according to the present invention, which is attached to a medium density fiber board to form a kitchen door.

FIG. 3 is a cross-sectional view showing an example of a decorative sheet according to the present invention, which is applied to a plywood to form a decorative plywood.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Surface layer 2 Polyethylene terephthalate film 3 Picture layer 4 Adhesive layer 5 Polyvinyl chloride layer 6 Adhesive layer 7 Steel plate 8 Decorative sheet 9 Decorative steel sheet 10 Medium density fiber board 11 Kitchen door 18 Decorative sheet 20 Polypropylene layer 21 Plywood 22 Decorative plywood

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B32B 27/00 B32B 27/00 E 27/30 27/30 A B41M 3/06 B41M 3/06

Claims (2)

[Claims] 1. A decorative sheet is formed by laminating a thermoplastic resin sheet and a surface layer formed by applying and cross-linking a coating containing an acrylic resin containing a silanol group, an epoxy group and a hydroxyl group and a metal chelate as a curing catalyst. A stain-resistant decorative sheet characterized by being treated. 2. The surface layer of the decorative sheet according to claim 1,
A stain-resistant decorative sheet having a soft mat design, characterized by adding a conductive and matting substance.