JP2000177035A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To scavenge formaldehyde to be emitted into the indoor air from a building material or the like and thereby prevent an unpleasant smell or an allergic symptom from being generated by adding a vegetable tannin to a foaming layer, in a decorative sheet consisting of a foaming layer based on a foaming agent and a thermoplastic resin, formed on a base material. SOLUTION: The decorative sheet 1 to be used for the wall, ceiling and the like of a residence or the like has a foaming layer 3 consisting mainly of a foaming agent and a thermoplastic resin, formed on a paper base material 2. The capability to scavenge formal dehyde of the foaming layer 3 is upgraded by adding a vegetable tannin, especially a larch tannin extracted from a larch tree to the foaming layer 3. The thermoplastic resin to be used for a foaming layer forming composition for forming the foaming layer 3 is desirably in the form of a liquid and is best suitably a vinyl chloride resin which can be pasted or the like. In addition, it is possible to improve surface physical properties such as design, anticontamination and wear resistance by forming a pictorial design layer and/or a protecting layer on the foaming layer 3 according to necessity, in the decorative sheet 1 as described above.

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 walls and ceilings of houses and the like, or fittings and furniture, and more particularly, to a building material and a furniture material excellent in design and used for houses and the like. The present invention relates to a decorative sheet having a function of capturing volatile substances released into room air from a room or the like.

[0002]

2. Description of the Related Art Conventionally, a foamed layer made of a vinyl chloride resin or the like is provided on a base material such as flame-retardant paper, and a decorative sheet or the like is provided on the foamed layer. And a decorative sheet or the like in which the pattern layer and the foam layer are provided with a concavo-convex pattern are widely and generally used because of their excellent design.

[0003] The reason for this is that building materials and furniture materials used for walls and ceilings of houses and the like, fittings and furniture, and the like, have a problem of natural destruction due to cutting of natural trees and mining of natural stones, natural trees and natural stones. Inexpensive, stable quality synthetic materials are becoming increasingly expensive due to problems such as depletion of natural resources, and because of the inconsistent quality of strength and design due to natural wood and natural stone. For example, wood-based materials such as wood plywood, wood fiber board, and particle board; gypsum-based materials such as gypsum board and gypsum slag board; fiber cement boards such as pulp cement board, asbestos slate board, asbestos cement board, and wood chip cement board; GRC and concrete, diallyl phthalate resin, benzoguanamine resin, phenol resin, melamine resin, unsaturated polyester resin Epoxy resins, such as resin-impregnated paper and resin impregnated and urethane resins have been used. However, while these synthetic materials are stable in terms of strength, they are inferior to natural wood and natural stone in terms of design, and decorative sheets are used as materials for applying surface makeup to the surfaces of these synthetic materials. That's why.

[0004] Among these synthetic materials, for example, wood-based materials are bonded to each other with an adhesive and formed into a plate-like material. Melamine-based and phenolic resin adhesives are often used, but these adhesives contain free formaldehyde, and the decomposition of the resin releases formaldehyde and releases it into the air. Ammonium chloride is used as a curing agent and a catalyst, and this becomes ammonia gas under the influence of moisture in the air and a water-soluble adhesive used when attaching a decorative sheet to the synthetic material. Is released into the air. In addition, plaster-based materials, fiber cement boards,
Also for synthetic materials such as GRC and concrete, alkaline gases such as ammonia may be released into the air due to a hardening accelerator added during the production of cement.

On the other hand, in recent years, heat insulation and airtightness have been improved in new houses and the like, and volatile substances such as formaldehyde and ammonia gas released from building materials, furniture materials, etc. into the indoor air have been improved. This causes problems such as giving unpleasant odors to residents and users, and problems such as sick house syndrome causing allergic symptoms, and is regarded as a part of the problem.

[0006]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above-mentioned problems, and has as its object to remove volatile substances released into the air from building materials and furniture materials, etc. In particular, it is an object of the present invention to provide a decorative sheet having a function of capturing formaldehyde and preventing an unpleasant odor and allergic symptoms and having excellent design.

[0007]

The present inventors have conducted various studies to solve the above problems, and as a result, the decorative sheet of the present invention according to claim 1 has a foaming agent, In a decorative sheet having at least a foamed layer mainly composed of a thermoplastic resin, the foamed layer contains vegetable tannin. With this configuration, it is possible to obtain a decorative sheet having a function of trapping volatile substances released into the indoor air from building materials, furniture materials, and the like, particularly, formaldehyde. Can be prevented.

[0008] The invention described in claim 2 is the first invention.
Wherein the vegetable tannin is Karamatsu tannin extracted from Karamatsu. By using the vegetable tannin as the Karamatsu tannin in this way, the formaldehyde trapping ability can be improved.

[0009] The invention described in claim 3 is the first invention.
Wherein the foam layer-forming composition comprises a liquid material. By using such a foamed layer forming composition, a foamed layer can be easily formed on a base material layer using a well-known coating method.

[0010] The invention described in claim 4 is the first invention.
The decorative sheet according to any one of Items 1 to 3, wherein a picture layer and / or a protective layer is provided on the foam layer. With this configuration, it is possible to obtain a decorative sheet having excellent design and / or surface properties such as stain resistance and abrasion resistance.

The invention described in claim 5 is the first invention.
The decorative sheet according to any one of Items 1 to 4, wherein an uneven pattern is formed on the foam layer, the picture layer, and / or the protective layer. With such a configuration, it is possible to form uneven patterns of various shapes.

The invention according to claim 6 is the first invention.
Wherein the base material layer is a backing paper for wallpaper. With this configuration, flame retardancy and workability can be imparted to the base material layer.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail below with reference to the drawings and the like. First, FIG. 1 is a layer configuration diagram of a first embodiment of the decorative sheet of the present invention, and FIG. 2 is a layer configuration diagram of a second embodiment of the decorative sheet of the present invention. 1, 1 and 11 are decorative sheets, 2 is a paper base, 3 is a foam layer, 4
Denotes a picture layer, 5 denotes a protective layer, and 6 denotes an uneven pattern.

FIG. 1 is a diagram showing the layer structure of a first embodiment of the decorative sheet of the present invention, which is the most basic example of the layer structure of the decorative sheet of the present invention.
Is formed by forming a foaming layer 3 mainly composed of a foaming agent and a thermoplastic resin on a paper base material 2, and the foaming layer 3 contains Karamatsu tannin extracted from Karamatsu.

Examples of the paper base material 2 used in the present invention include flame-retardant paper for wallpaper (a sheet mainly composed of pulp, a sheet treated with a flame retardant such as guanidine sulfamate and guanidine phosphate), aluminum hydroxide paper, and inorganic paper. , be those normally are said backing paper for wallpaper and general paper, the basis weight can be used and the 50 to 300 g / m ^2, among them a basis weight of 70 to 150 g / m ^Two are preferred.

Next, as the thermoplastic resin used in the foam layer forming composition for forming the foam layer 3 of the present invention, the foam layer forming composition is a liquid material in that a known coating method can be used. It is desirable that a paste-formable vinyl chloride resin or an aqueous emulsion-formable vinyl chloride-vinyl acetate copolymer resin, an acrylic resin, a vinyl acetate resin, a urethane resin, an ethylene-vinyl acetate copolymer resin (EVA) or a blend or copolymer of EVA and an acrylic resin is preferred.

The foaming agent used for the foaming layer 3 may be a low-boiling-point hydrocarbon, a thermally expanding capsule foaming agent containing a volatile substance such as chlorofluorocarbon or petroleum ether, or an azodicarbonamide. Any or all decomposable foaming agents such as oxybisbenzenesulfonyl hydrazide can be used. The thermal expansion type capsule foaming agent has a substantially constant expansion temperature and a substantially constant expansion coefficient, and can easily form a foamed layer composed of uniform foamed cells. The thermal decomposition type foaming agent of azo compounds such as azobisformamide and the like, the cost of the foaming agent is inexpensive, and the foaming agent has excellent flame retardancy and self-extinguishing properties,
Either blowing agent is a suitable blowing agent because it is almost non-toxic. The mixing amount of these foaming agents with the thermoplastic resin may be appropriately determined depending on the required design properties, but is generally 0.5 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin.
Parts by weight are appropriate.

Next, the vegetable tannin used in the present invention will be described. Vegetable tannin is a substance with a molecular weight of about 600 to 10,000 based on polyoxyphenyl, which is widely distributed in the plant kingdom.When heated with a dilute acid, it is hydrolyzed to produce gallic acid, egraic acid, etc. There are hydrolyzable tannins and condensed tannins that polymerize to produce water-insoluble flovafen, but the vegetable tannins used in the present invention have a molecular weight of 800-6000, more preferably 1
500-4500 condensed tannins are suitable.

The condensed tannin refers to tannin contained in the bark, heartwood, leaves, etc. of wood such as lark, oak, hemlock, wattle, chestnut, kepraccio, kutch, tea, radiator pine, etc., which are present in the plant kingdom. For example, extraction with hot water or an alkaline aqueous solution, filtration,
Concentration, drying, obtained through steps such as pulverization, tannins obtained from any plant can be used as the vegetable tannins used in the present invention, among them, especially extracted from Karamatsu Pinaceae tannins, such as Karamatsu tannins, can be suitably used.

The reason is that Pinaceae tannins represented by Karamatsu tannins extracted from Karamatsu are condensed tannins, such as flavan-3,4-diol and flavan-tannin.
Many have a flavonoid skeleton, such as 3-ol, phloroglucinol, and chalcone, in order to effectively capture formaldehyde as polyflavonoid-formaldehyde. The decorative sheet 1 of the present invention configured as described above captures volatile substances, particularly formaldehyde, released into the indoor air from building materials and furniture materials, and has a function of preventing unpleasant odors and allergic symptoms. It can be a sheet.

Further, an ultraviolet absorber may be appropriately added to the foam layer 3 as needed. This ultraviolet absorber is used for the purpose of preventing the foam layer 3 from being deteriorated by ultraviolet rays and improving the weather resistance of the foam layer 3. As the ultraviolet absorber, for example, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5 Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl ) -5
Chlorobenzotriazole, 2- (2'-hydroxy-3 '
-Isobutyl-5'-propylphenyl) -5-chlorobenzotriazole and other 2'-hydroxyphenyl-5-chlorobenzotriazole ultraviolet absorbers, 2- (2'-
Hydroxy-3 ', 5'-di-tert-butylphenyl)
2′-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as benzotriazole and 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2′-
Dihydroxy-4-methoxybenzophenone, 2,2'-
Dihydroxy-4,4'-dimethoxybenzophenone,
2,2'-dihydroxybenzophenone-based ultraviolet absorbers such as 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2-hydroxybenzophenone UV absorbers such as 2,4-dihydroxybenzophenone; salicylate UV absorbers such as phenyl salicylate and 4-tert-butyl-phenyl-salicylate; 2-ethyl-
Use of cyanoacrylate ultraviolet absorbers such as hexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, octyl-2-cyano-3,3-diphenylacrylate and the like. be able to. The amount of these UV absorbers added is
Usually, it is about 0.1 to 10% by weight.

The foamed resin layer 3 of the present invention may optionally contain an inorganic filler as needed. As a reason for this, when an olefin resin is used as the thermoplastic resin forming the foamed layer 3, the olefin resin is usually flammable, and in order to impart flame retardancy thereto, an inorganic filler is used. Is added. As the inorganic filler, for example, a mixture of one or more inorganic substances such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, barium carbonate, antimony trioxide, and titanium oxide can be used. The amount of the inorganic filler to be mixed with the olefin resin forming the foamed layer 3 must be at least 80 parts by weight based on 100 parts by weight of the olefin resin. By mixing the inorganic filler in this way, the foamed layer 3 made of an olefin-based resin can be provided with flame retardancy. Other examples include a flame retardant such as a phosphoric acid ester and silicone powder.

The foamed layer 3 of the present invention may be colored by adding a pigment or the like as needed. The coloring by adding the pigment may be transparent coloring or opaque (concealing) coloring.

FIG. 2 is a diagram showing a layer structure of a decorative sheet according to a second embodiment of the present invention. The decorative sheet of the present invention is an example of a layer having the best design and physical properties. The decorative sheet 11 of the present invention has a pattern layer 4 formed on the foam layer 3 of the decorative sheet 1 having the most basic layer configuration of the present invention shown in FIG. To form
The uneven pattern 6 is provided from the protective layer 5 side to the foam layer 3.

The picture layer 4 of the present invention can be generally formed with ink by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, and the like. Examples of the print pattern include a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and a print pattern such as a solid image. As the vehicle, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, acrylic, vinyl acetate, vinyl chloride-vinyl acetate copolymer, cellulose resin, polyamide resin And the like, and one or more kinds thereof may be used as a mixture, to which a pigment, a solvent, various auxiliaries and the like are added to form an ink.
May be appropriately selected from the above-mentioned vehicles according to the type of thermoplastic resin used for the formation or the required physical properties. Also, if necessary, a corona discharge treatment or / and an anchor coating agent is applied to the surface of the foam layer 3 on which the picture layer 4 is provided for the purpose of improving the adhesion between the foam layer 3 and the picture layer 4. And the like.

The protective layer 5 is provided for imparting scratch resistance, chemical resistance, stain resistance and the like to the decorative sheet of the present invention, and includes an epoxy resin, an acrylic resin, a urethane resin. A thermosetting resin such as a resin is suitable.
A liquid-curable urethane resin or a one-liquid moisture-curable urethane resin is preferred. The reason for this is that an organic compound having an OH group in a molecule is used as an ultraviolet absorber, and the protective layer 5 is formed of a resin having an isocyanate group, whereby the ultraviolet absorber exudes to the surface. Also, since the isocyanate group in the protective layer and the OH group of the ultraviolet absorber are urethane-bonded and trapped in the protective layer, it is possible to prevent the ultraviolet absorber from exuding to the surface over time. That's why.

The two-component curable urethane resin is a urethane resin containing polyol as a main component and isocyanate as a crosslinking agent (curing agent). The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, and polycarbonate polyol. Further, as the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule can be used. For example, aromatic isocyanates such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate,
Alternatively, aliphatic (or alicyclic) isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate can be used. Alternatively, adducts or multimers of the above various isocyanates can also be used. For example,
Adducts of tolylene diisocyanate, trimers of tolylene diisocyanate (trimers) and the like.

The one-component moisture-curable urethane resin is a composition containing a prepolymer having an isocyanate group at a molecular terminal as an essential component. The prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at both molecular terminals, and is a solid thermoplastic resin at room temperature. Isocyanate groups react with each other due to moisture in the air to cause a chain extension reaction, and as a result, a reactant having a urea bond in a molecular chain is generated,
The urea bond further reacts with the isocyanate group at the molecular terminal to cause a biuret bond and branch to cause a crosslinking reaction.

The skeleton structure of the molecular chain of the prepolymer having an isocyanate group at the molecular terminal is arbitrary, and specific examples include a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, and a polybutadiene skeleton. One or more of these skeletal structures are appropriately employed. If there is a urethane bond in the molecular chain,
The terminal isocyanate group also reacts with the urethane bond to form an allophanate bond, and a cross-linking reaction is also caused by the allophanate bond.

The protective layer 5 may be formed by applying a solution of a two-component curable urethane resin or a one-component moisture-curable urethane resin to a known coating method such as a gravure printing method or a roll coating method. In the case of a one-component moisture-curable urethane resin, the one-component moisture can be formed by coating the foam layer 3 provided with the pattern layer 4 on the surface of the pattern layer 4. It can be formed by applying a curable urethane resin in the same manner by a known coating method such as a roll coating method or an extrusion coating method. The thickness of the protective layer 5 is suitably 0.5 to 100 μm, usually 1 to 10 μm.

Next, as a method of forming the concavo-convex pattern 6 on the decorative sheet of the present invention, a well-known sheet-fed or a rotary embossing machine is used when the decorative sheet is heated. The outermost layer (in FIG. 2, the protective layer 5), which is located on the opposite side of the material layer, is made uneven by an embossing plate, and then cooled to form the outermost layer (FIG. 2).
In the above, an uneven pattern can be formed from the protective layer 5) to the foamed layer 3. Examples of the shape of the uneven pattern 6 include a wood grain board conduit groove, a stone board surface unevenness, a cloth surface texture, a satin finish, a grain, a hairline, and a linear groove.

Although the embodiment has been described so far in which vegetable tannin is contained in the foamed layer, the present invention is not limited to this. For example, vegetable tannin may be contained in at least one of the base layer, the picture layer and the protective layer. They can also be included to increase the effect of trapping volatile substances, especially formaldehyde.

[0033]

The present invention will be described in more detail with reference to the following examples. Example 1 An inorganic backing paper having a thickness of 130 μm [Ceraform W-120A manufactured by Lintec Co., Ltd.] was used as a base material layer, and a foam layer forming composition having the composition shown in Table 1 was dried on the surface thereof by a sol coating method. Sometimes after coating and drying to a thickness of 70μm,
The foaming layer forming composition is heated in a foaming furnace (at 170 ° C. for 1 minute).
At the same time as forming a foamed layer, the surface of the foamed layer was embossed with a cloth-shaped embossing plate, and then cooled to obtain a decorative sheet having an embossed pattern.

[0034]

[Table 1]

Example 2 An inorganic backing paper having a thickness of 130 μm [Ceraform W-120A manufactured by Lintec Co., Ltd.] was used as a base material layer, and the foamed layer forming composition having the composition shown in Table 2 was sol-coated on the surface thereof. After coating and drying to a thickness of 70 μm when dry by the method,
The foaming layer forming composition is heated in a foaming furnace (at 160 ° C. for 1 minute).
At the same time as forming a foamed layer, the surface of the foamed layer was embossed with a cloth-shaped embossing plate, and then cooled to obtain a decorative sheet having an embossed pattern.

[0036]

[Table 2]

The decorative sheet of the present invention obtained in the above Examples 1 and 2 was applied to the entire 6 surfaces forming 8 m ³ of a closed formaldehyde space having an air concentration of 1 ppm, and the air concentration of formaldehyde after 3 hours was measured. It was measured. The formaldehyde concentration in the closed space provided with the decorative sheets of Examples 1 and 2 was
In each case, it was recognized that the content was reduced to 0.08 ppm or less, and the effectiveness of the decorative sheet of the present invention was confirmed.

[0038]

The decorative sheet of the present invention has been described in detail so far. However, by forming the foamed layer as a layer containing tannin, volatile substances released into the air from building materials and furniture materials, etc. In particular, it effectively captures formaldehyde,
The cosmetic sheet has an effect of preventing unpleasant odors and allergic symptoms, and is also excellent in design.

[Brief description of the drawings]

FIG. 1 is a layer configuration diagram of a first embodiment of a decorative sheet according to the present invention.

FIG. 2 is a layer configuration diagram of a second embodiment of the decorative sheet according to the present invention.

[Explanation of symbols]

 1,11 decorative sheet 2 paper base material 3 foam layer 4 picture layer 5 protective layer 6 uneven pattern

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AJ00B AK01B AT00A BA02 CA01B DG10A DJ01B DJ04B EH46 EJ02 EJ42 GB08 GB81 HB00 HB21B JB16B

Claims (6)

[Claims] 1. A decorative sheet having at least a foaming layer formed from a foaming agent and a foaming layer-forming composition mainly composed of a thermoplastic resin on a base material layer, wherein the foaming layer contains vegetable tannins. A decorative sheet characterized by becoming. 2. The decorative sheet according to claim 1, wherein the vegetable tannin is Karamatsu tannin extracted from Karamatsu. 3. The decorative sheet according to claim 1, wherein the foam layer-forming composition comprises a liquid material. 4. A picture layer and / or a protective layer is provided on the foam layer.
The decorative sheet according to any one of items 1 to 3, wherein 5. The decorative sheet according to claim 1, wherein an uneven pattern is formed on the foam layer, the picture layer, and / or the protective layer. 6. The decorative sheet according to claim 1, wherein the base material layer is a backing paper for wallpaper.