JP2000062128A - Decorative sheet and decorative laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To scavenge a harmful formaldehyde released indoors by laminating a decorative treatment layer and a surface protecting layer sequentially on the upper face of a base material sheet and forming the surface protecting layer of a curable resin coating containing a photocatalyst. SOLUTION: The decorative sheet 1 is structured of a decorative treatment layer 3 consisting of a solid ink layer 3a and a pictorial pattern ink layer 3b laminated on the upper face of a base material sheet 2 and further a surface protecting layer 4 formed of a curable resin coating containing a photocatalyst laminated on the decorative treatment layer 3. Therefore, formaldehyde which is generated from an adhesive or the like to be used for bonding a base material as a substrate material of ceiling material, flooring material, wall material or the like or the decorative sheet 1 to be laminated on the base material or applying a wall paper and released indoors, is decomposed by the photocatalyst contained in the surface protecting layer 4. Thus it is possible to lessen a pungent smell generated by the formaldehyde and thereby always maintain well- hygenic environments indoors.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used for various kinds of furniture and interior materials for building, or a decorative sheet using the decorative sheet, and in particular, it traps and removes formaldehyde released indoors, The present invention relates to a decorative sheet or veneer capable of maintaining a good hygienic environment.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet of this type, a printed sheet obtained by printing a paper or a synthetic resin sheet as a base material sheet is used as it is for a wood plywood,
It is used by attaching a decorative sheet to the surface of a wood base material such as a wood fiber board or particle board. However,
These wood-based base materials to which the decorative sheets are attached are bonded by an adhesive agent, and urea resins, melamine resins, phenol resins, etc., which are inexpensive and have strong adhesiveness, have been used as the adhesive agents. However, these adhesives contain free formaldehyde, and formaldehyde is released by decomposition of the resin. Therefore, if a decorative sheet is directly attached to such a wood-based base material, formaldehyde is released into the room or the like, which impairs the sanitary environment.

Therefore, many proposals have been made as a method for preventing the emission of formaldehyde from these wood-based materials. For example, measures such as using a resin that does not contain formaldehyde such as vinyl acetate-based resin, or using a urea resin adhesive that contains urea that captures formaldehyde have been taken. Since plywood is weak, there is a problem that the adhesive strength between layers becomes insufficient, and in the case of wood fiber board and particle board, there is a problem that physical properties such as strength are changed. When used by adding to the adhesive, there is a problem that the price becomes high and the physical properties of the finished product may change. Further, there is also a problem that formaldehyde may be released from the adhesive that attaches the decorative sheet to the decorative plate.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to bond a wood-based base material to be bonded with an adhesive or to a base material. Another object of the present invention is to provide a decorative sheet and a decorative plate having a function of capturing harmful formaldehyde released indoors by using an adhesive such as urea.

[0005]

Means for Solving the Problems The means for achieving the above object of the present invention is to provide a decorative sheet in which a decorative treatment layer and a surface protective layer are sequentially provided on the upper surface of a base sheet, wherein the surface protective layer is The decorative sheet is made of a curable resin paint containing a photocatalyst. By having such a configuration, a ceiling material, a flooring material, a base material that is a base material such as a wall material, or a decorative sheet to the base material,
Or, the formaldehyde released from the adhesive used to attach wallpaper and released indoors is decomposed by the photocatalyst contained in the surface protective layer, so that the odor caused by formaldehyde is less likely to occur. Therefore, it is possible to always keep the room in a good hygienic environment.

The photocatalyst added to the surface protective layer is made of titanium oxide. By doing so, a high catalytic activity can be obtained by lighting such as sunlight or indoor fluorescent lamps obtained in daily life, it can react with formaldehyde to oxidize and decompose formaldehyde, and it is chemically stable and long-term. The photocatalytic function can be exerted over the entire range.

[0007] Titanium oxide is to be anatase type titanium oxide. By doing so, it is further highly activated, and the odorous odor caused by formaldehyde due to oxidative decomposition of formaldehyde is extremely reduced.

It is also desirable that the substrate sheet has a formaldehyde scavenger layer on one surface thereof. By doing so, not only adsorption from the surface but also formaldehyde generated from the base material or the adhesive used to attach the decorative sheet to the base material is captured and adsorbed by the formaldehyde scavenger, so Formaldehyde is less likely to be released from the side, less formaldehyde is suspended in the room, and irritating odor caused by formaldehyde is significantly reduced.

Further, the base sheet of the decorative sheet is made of a paper-based sheet. By doing so, the formaldehyde trapping layer can be easily formed, and since the formability generated from the base material side can be easily adsorbed due to its air permeability, the possibility that it will be released from the end surface of the base material is reduced, Less to the surface.

Further, according to the present invention, a decorative sheet provided with a formaldehyde-trapping layer, which is provided if necessary, and a surface protection layer made of a curable resin coating containing a decorative treatment layer and a photocatalyst, is attached to a wooden base material. To wear. With such a configuration, since the photocatalyst added to the surface protective layer oxidizes and decomposes the formaldehyde filled in the room, etc., it is possible to always maintain the room in a good sanitary environment. Formaldehyde generated from the wood-based substrate or from the adhesive used to attach the decorative sheet thereto is captured and adsorbed by the formaldehyde scavenger in the formaldehyde scavenging layer, so that formaldehyde is released to the surface. It will be less.

Further, a sheet having at least one of formaldehyde scavenging property, formaldehyde impermeability and moisture proof property is attached to the opposite side of the surface of the wood-based substrate to which the decorative sheet provided with the surface protective layer is attached. It may be used as a decorative veneer. This decorative board has formaldehyde scavenging ability on one side and formaldehyde scavenging ability or formaldehyde impermeability on the other side, so it is used for attaching a base material or a decorative sheet to a base material. Formaldehyde generated from the adhesive is trapped and adsorbed by the formaldehyde scavenger or blocked by the formaldehyde impermeable layer, so that formaldehyde is less likely to be released to the surface. Therefore, the irritating odor caused by formaldehyde is extremely reduced. Further, it is possible to prevent warping of the decorative board itself due to moisture absorption or moisture release from the back surface of the base material.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a sectional view showing a laminated structure of an embodiment of a decorative sheet of the present invention, and FIG. 2 is a sectional view showing a laminated structure of another embodiment of a decorative sheet of the present invention.
FIG. 3 is a sectional view showing a laminated structure of the first embodiment of the decorative plate of the present invention, FIG. 4 is a sectional view showing a laminated structure of the second embodiment of the decorative plate of the present invention, and FIG. It is sectional drawing which shows the laminated structure of 3rd Embodiment of a decorative board, 1 and 1'is a decorative sheet, 2 is a base material sheet, 3 is a decoration processing layer, 3a is a solid ink layer, 3b is a pattern ink layer, 4 Is a surface protective layer, 5 is a formaldehyde scavenging layer, 6 is a wood-based substrate, 7 is an adhesive layer, 10, 20, and 30 are decorative boards, respectively.

As shown in FIG. 1, the decorative sheet 1 of the present invention has a structure in which a decorative treatment layer 3 comprising a solid ink layer 3a and a pattern ink layer 3b is laminated on the upper surface of a base sheet 2 and a photocatalyst is contained on the decorative treatment layer 3. The surface protective layer 4 formed of the above curable resin coating is laminated, and has the ability to decompose and remove formaldehyde on the surface.

As shown in FIG. 2, the laminated structure of another embodiment of the decorative sheet of the present invention comprises a base sheet 2, a solid ink layer 3a and a pattern ink layer 3b of the decorative sheet 1 shown in FIG. A formaldehyde scavenging layer 5 is provided between the decorative treatment layer 3 and the decorative treatment layer 3, and the surface protection layer 4 is formed on the upper surface of the decorative treatment layer 3 by a curable resin coating containing a photocatalyst. Since the formaldehyde generated from the base material or the adhesive used for sticking the decorative sheet to the base material is captured and adsorbed, the formaldehyde emission from the surface side of the base material is extremely reduced. Although the formaldehyde trapping layer 5 is provided between the base material sheet 2 and the decorative treatment layer 3, it may be provided on the lower surface of the base material sheet 2 opposite to the decorative treatment layer 3. Is.

The base sheet 2 used in the decorative sheet 1 of the present invention is, for example, thin paper, bleached kraft paper, titanium paper, paperboard, gypsum board paper, paper such as parchment paper, polyethylene film, polypropylene film and poly. It is composed of a single layer such as a vinyl chloride film, a polyethylene terephthalate film, a polycarbonate film or a plastic film such as a nylon film, or a plurality of layers of two or more kinds, and particularly has a weight of 20 to 80 g / m.
The thin paper of ² is preferably used because it is inexpensive, has a smooth surface, is excellent in printability, is easy to form a formaldehyde trapping layer, and is excellent in air permeability.

Further, on the base sheet 2, a solid ink layer 3a made of a colored ink by kneading a pigment or a dye, and, for example, patterns such as wood grain, stone grain, cloth grain, leather grain, letters and figures are revealed. The decorative treatment layer 3 such as the pattern ink layer 3b is formed by a normal printing method such as gravure printing, offset printing, screen printing. As the printing ink for forming the decoration treatment layer 3, a printing ink using a solvent-based binder resin such as a nitrified cotton-alkyd resin, a cellulosic resin, a vinyl resin, a polyester resin, an acrylic polyol resin, or a polyamide resin is used. In order to be able to express the "shine" of the wood grain well, it is preferable to add a bright pigment such as a pearl pigment or a metal powder. In addition, it is reasonable to add the formaldehyde scavenger to the ink forming the decorative treatment layer 3.

The curable resin coating material used to form the surface protective layer 4 is a known thermosetting resin as a vehicle, and a photocatalyst is added to the vehicle. Additives such as a mixture of a plasticizer, a stabilizer, a curing agent and a solvent can be used.
As a vehicle for forming the surface protective layer 4, stain resistance,
It is desirable to form a film having excellent surface properties such as scratch resistance and solvent resistance, and unsaturated polyester resin, epoxy resin, acrylic resin, two-component curable urethane resin and the like are preferable.

The photocatalyst referred to in the present invention generally refers to all those called "photocatalysts". Specifically, when photocatalyst is irradiated with light of a specific wavelength, a photochemical reaction occurs, whereby various organic substances are generated. An oxide that acts as a catalyst for decomposing, etc., or has an antibacterial or antifungal effect, such as titanium oxide (TiO ₂ ), zinc oxide (Zn oxide)
O), tin oxide (SnO), SrTiO ₃ (strontium titanate), cerium oxide (CeO), iron oxide (Fe)
_{20 3} ) and the like. Among these oxides, (1)
High catalytic activity is obtained even with illumination light required for daily life, no special light source is required, (2) chemically stable, long-term photocatalytic function is obtained, (3) no toxicity, (4) Titanium oxide is preferable because it is inexpensive and advantageous in terms of cost, and anatase-type titanium oxide is particularly preferable.

The layer for decomposing and removing formaldehyde in the present invention uses anatase type titanium. Anatase type titanium oxide is also called as "anatase" and the crystal system is tetragonal. This is one of the multiple crystal systems of titanium oxide, and this crystal system has a strong formaldehyde decomposition action, and anatase-type titanium oxide has a catalytic action that promotes the decomposition and alteration (oxidation, etc.) of organic substances. . That is, of the titanium oxides, the anatase type is easily activated by light, and is activated by the illumination light required for daily life such as sunlight and indoor lighting to oxidize and decompose formaldehyde. The average crystal grain size is preferably 6 to 30 nm, and the addition amount thereof is 10 to the binder.
150% by weight is preferred.

A typical substance having a formaldehyde scavenging action which can be used in the present invention is an organic amino compound, which reacts easily with formaldehyde, and the product does not dissociate formaldehyde, and is a harmless and stable substance. And, for example, amides such as urea, ethylene urea,
Propylene urea, 5-hydroxypropylene urea, 5-
Methoxypropyleneurea, 5-methylpropyleneurea,
Parabanic acid (glyoxal monowillene), 4,5-
Cyclic alkylene ureas such as dimethoxyethylene urea, pyrrolidine, piperidine, saturated cyclic secondary amines such as formolin, 2-hydrazobenzothiazole or its derivatives, amines such as dicyandiamide, acid imides, and the like, among them, urea, Also, saturated cyclic secondary amines are preferred. Further, ammonium hydroxide may be added if necessary.

FIG. 3 shows a first embodiment of a decorative plate to which the decorative sheet 1'of the present invention is attached. Hereinafter, the same reference numerals as those of the components already described will be used, and a duplicate description will be omitted. The decorative board 10 has an adhesive layer 7 on the surface of the wooden base material 6.
The decorative treatment layer 3 including the solid ink layer 3a and the pattern ink layer 3b is formed on the surface of the base material sheet 2 through the above, and the surface protection layer 4 made of a curable resin containing anatase type titanium oxide is provided on the upper surface thereof. The decorative sheet 1 is laminated and has a property of capturing and decomposing formaldehyde released in a room or the like.

FIG. 4 shows a laminated structure of the decorative board 20 according to the second embodiment of the present invention. The decorative plate 20 of the present embodiment is different from the decorative plate 10 of the first embodiment in the configuration of the decorative sheet, and the decorative sheet 1 ′ of the decorative plate 20 has a space between the base sheet 2 and the surface protective layer 4. The formaldehyde trapping layer 5 is formed.

FIG. 5 shows a laminated structure of the decorative plate 30 according to the third embodiment of the present invention. The decorative plate 30 of the present embodiment has the same surface configuration as the decorative plate 20 of the second embodiment, and a similar decorative sheet 1 ′ is also formed on the lower surface (back surface) of the wood-based substrate 6 via the adhesive layer 7. The structure is such that the decorative sheet is adhered to both the front and back sides and has the ability to capture and decompose formaldehyde. Although not shown, as a decorative sheet to be attached to the lower surface of the wood-based substrate 6, a formaldehyde-impermeable or moisture-proof film such as a polyvinyl chloride resin film or a polyolefin resin film is subjected to a decorative treatment. What provided the layer may be used.

As the wood-based base material 6 to which the decorative sheets 1 and 1'of the present invention are attached, a wood plywood (including so-called laminated wood) using formaldehyde-emissive resin as an adhesive between layers, formaldehyde-emissive resin There is a particle board or a wood fiber board (MDF etc.) using as a binder, and in addition, in the present invention, a formaldehyde effusive resin simple substance or a formaldehyde effusive resin kneaded or impregnated with a fibrous material to form a composite. (FRP in a broad sense)
Etc. can also be used.

As a method for laminating these various wood-based base materials 6, for example, a method of applying pressure to a plate-shaped base material with a pressure roller and laminating it with an adhesive in between, The decorative sheet is placed facing or with an adhesive layer in between,
A so-called vacuum press laminating method in which a decorative sheet is laminated on the surface of a molded substrate by a pressure difference caused by vacuum suction from the molded substrate side, an adhesive agent is provided between the decorative sheets in the long axis direction of a columnar substrate such as a cylinder or a polygonal prism. There is a so-called lapping method in which a decorative sheet is sequentially pressure-bonded and laminated to a plurality of side faces forming a columnar body by a plurality of rollers having different directions while being supplied via a layer. The decorative sheet of the present invention is effective even if it is attached only to one surface of the wooden base material, but it is preferable to be attached to both the front and back surfaces of the wooden base material in order to obtain a greater effect.

These surface-coated adherends are used as decorative materials for building interiors such as wall surfaces, floors and ceilings, surface decorative materials for fittings such as window frames, doors and handrails, and furniture surfaces such as chests of drawers. Used as a decorative material. If necessary, an antibacterial agent, an antifungal agent or the like may be added to a layer other than the base material of the decorative sheet or the decorative plate of the present invention so as to have the required performance.

Example 1 Thin paper weighing 30 g / m ² (HP-
30) is used, and a colored solid ink layer and a wood grain pattern layer are printed on the upper surface by gravure printing using a nitrocellulose ink (Showa Ink Mfg. Co., Ltd. SAM), and urethane is further formed on the wood grain pattern layer surface. 20% by weight of titanium oxide for photocatalyst (Taika Co., Ltd., ST157) in a resin solution (KR 92 Clear, manufactured by The Inktech Co., Ltd.)
(Solid content ratio) The added transparent coating material was applied by a roll coater so as to be 12 g / m ² (wet) to form a surface protective layer, and a decorative sheet excellent in formaldehyde trapping property was produced. Next, a 2.7 mm thick E ₂ standard (JIS) MDF plate was prepared as a base material, and the decorative sheets obtained above were attached to both sides of the MDF plate using a vinyl acetate adhesive to improve formaldehyde trapping property. An excellent decorative board was obtained.

Example 2 Thin paper (weighing 30 g / m ² manufactured by Tenma Special Paper Co., Ltd., HP-
30) was used, and an aqueous solution containing a formaldehyde scavenger (FC-18-6, manufactured by Miki Riken Co., Ltd.) was applied on the upper surface thereof by a roll coater so as to be ² g / m ² (dry). A formaldehyde scavenging layer is formed, and a colored solid ink layer and a wood grain pattern layer are printed on the upper surface by gravure printing using a nitrocellulose ink (Showa Ink Mfg. Co., Ltd. SAM), and the wood grain pattern layer surface is further printed. Urethane resin liquid (manufactured by The Inktech Co., Ltd.,
KR92 clear) with titanium oxide for photocatalyst (Taika Co., Ltd., ST157) added at 20% by weight (solid content ratio) of a transparent coating material by a roll coater so as to be 12 g / m ² (wet). To form a decorative sheet excellent in formaldehyde scavenging property. Next, a 2.7 mm thick E ₂ standard (JIS) MDF plate was prepared as a base material, and the decorative sheets obtained above were attached to both sides of the MDF plate using a vinyl acetate adhesive to improve formaldehyde trapping property. An excellent decorative board was obtained.

Comparative Example 1 A decorative board was obtained in the same manner as in Example 2 except that titanium oxide for photocatalyst was not added to the transparent coating material forming the surface protective layer.

Comparative Example 2 Thin paper with a basis weight of 30 g / m ² (HP-
30) is used, and a colored solid ink layer and a wood grain pattern layer are printed on the upper surface by gravure printing using a nitrocellulose ink (Showa Ink Mfg. Co., Ltd. SAM), and urethane is further formed on the wood grain pattern layer surface. 12g / m ^{2 of} resin solution (KR92 clear, manufactured by The Inktech Co., Ltd.)
It was applied by a roll coater so as to be (wet) to form a surface protective layer to prepare a decorative sheet. Next, an E ₂ standard (JIS) MDF plate having a thickness of 2.7 mm was prepared as a base material, and the decorative sheets obtained above were attached to both surfaces thereof using a vinyl acetate adhesive to obtain a decorative plate. .

The decorative boards prepared in the above Examples and Comparative Examples were tested by the following method to measure the formaldehyde emission amount, and the results are shown in Table 1.

(Test method) 50 × 15 from the above decorative plate
10 test pieces of 0 mm are cut out to prepare test pieces.
Then, the test piece was placed in a glass desiccator having a volume of 10 liters according to JIS-A5905 formaldehyde emission test, and allowed to stand for 24 hours at a position 2 m below the illumination (fluorescent lamp, 110 w / 2 pieces), Formaldehyde emission was measured.

[0033]

[Table 1] As can be seen from the above results, in Examples 1 and 2, good results were obtained in formaldehyde trapping / decomposing performance.
E ₀ standard while using _two substrates standards (JIS) (JI
S) level formaldehyde emissions were achieved.

[0034]

As described above, the decorative sheet of the present invention is provided with the decorative treatment layer and the surface protective layer on the upper surface of the base sheet, and the surface protective layer is formed by the curable resin paint containing the photocatalyst. Formaldehyde, which is toxic to the human body, emitted from ceiling materials, floor materials, wall materials, etc., is oxidized and decomposed by a photocatalyst, and the odor caused by formaldehyde is extremely reduced. Can always be kept in a good sanitary environment.

Further, when the photocatalyst added to the surface protective layer is titanium oxide, particularly anatase type titanium oxide, it is activated by ordinary sunlight and indoor lighting without special light source, and formaldehyde is oxidatively decomposed. Therefore, a cheap and cost-effective decorative sheet can be obtained.

Further, by providing a formaldehyde scavenging layer on one surface of the base material sheet, scavenging and adsorbing formaldehyde, which is toxic to the human body, emanating from the base material or the adhesive used for attaching the decorative sheet to the base material is adsorbed. As a result, the amount released to the surface can be suppressed, and further high trapping efficiency can be obtained.

Further, a formaldehyde scavenging layer is provided on the upper surface of the base material sheet via an adhesive agent on one surface of the base material,
Further, a decorative sheet provided with a surface protective layer containing anatase type titanium oxide is laminated, and a sheet having at least one of formaldehyde scavenging property, formaldehyde impermeable property and moisture proof property is laminated on the other surface. Since the decorative sheet has formaldehyde trapping property on one side and formaldehyde trapping property or formaldehyde impermeable property on the other side, it is necessary to attach the decorative sheet to the base material or the base material. The formaldehyde generated from the adhesive used is trapped and adsorbed by the formaldehyde scavenger, or blocked by the formaldehyde impermeable layer, so that formaldehyde is released to the surface very little, and the surface protective layer is further protected. The anatase-type titanium oxide contained in the In order to oxidize and decompose formaldehyde,
It is possible to obtain a decorative plate that can always keep the interior of the room in a good hygienic environment.

[Brief description of drawings]

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

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

FIG. 3 is a cross-sectional view showing a laminated structure of the first embodiment of the decorative board of the present invention.

FIG. 4 is a cross-sectional view showing a laminated structure of a second embodiment of a decorative board of the present invention.

FIG. 5 is a cross-sectional view showing a laminated structure of a third embodiment of a decorative board of the present invention.

[Explanation of symbols]

1, 1'decorative sheet 2 Base sheet 3 decoration processing layer 3a Solid ink layer 3b Design ink layer 4 Surface protection layer 5 Formaldehyde trapping layer 6 Wood-based materials 7 Adhesive layer 10, 20, 30 Veneer

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 25, 1998 (1998.8.2)
5)

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

[0033]

[Table 1] As can be seen from the above results, in Examples 1 and 2, good results were obtained in formaldehyde trapping / decomposing performance.
E ₀ standard while using _two substrates standards (JIS) (JI
S) level formaldehyde emissions were achieved.

Continued front page    F term (reference) 4F100 AA21C AJ06B AK22 AK22G                       AK51C AP00A AP03A AR00B                       AR00C AR00D AT00A BA03                       BA04 BA07 CB00 CC00C                       DG10A GB08 HB00B HB31B                       JB12C JD01D JD04D JD14                       JD14D JL00C

Claims (7)

[Claims] 1. A decorative sheet in which a decorative treatment layer and a surface protective layer are sequentially provided on the upper surface of a base sheet, wherein the surface protective layer is formed of a curable resin paint containing a photocatalyst. Makeup sheet. 2. The decorative sheet according to claim 1, wherein the photocatalyst is made of titanium oxide. 3. The decorative sheet according to claim 2, wherein the titanium oxide is anatase type titanium oxide. 4. The decorative sheet according to claim 1, wherein a formaldehyde scavenging layer is provided on one surface of the base sheet. 5. The decorative sheet according to claim 4, wherein the base material sheet of the decorative sheet is a paper-based sheet. 6. A decorative board, wherein the decorative sheet according to claim 1 is attached to a wood-based substrate. 7. A sheet having at least one of formaldehyde scavenging property, formaldehyde impermeable property, and moisture proof property on the surface opposite to the surface of a wood-based substrate having a decorative sheet provided with the surface protective layer attached thereto. 7. The decorative board according to claim 6, wherein the decorative board is attached.