JP3923580B2 - wallpaper - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative sheet suitably used as an interior material of a building, particularly as a wall covering material.
[0002]
[Prior art]
Conventionally, the following wallpaper is mainly known as a decorative sheet used for such a use.
[0003]
So-called vinyl chloride wallpaper in which a vinyl chloride resin is formed on a paper substrate is widely used. However, decorative sheets that do not use vinyl chloride have been considered in recent years, and decorative sheets using foamed polyolefin have been proposed.
[0004]
These are prepared by melt extrusion coating a polyolefin resin mixed with a foaming agent on a printed substrate sheet, or by sheeting separately by a T-die extrusion method. The method of sticking to the material sheet is taken.
[0005]
[Problems to be solved by the invention]
Such a decorative sheet has a problem that the foam surface is easily damaged.
[0006]
In addition, since polyolefin is a crystalline polymer, the temperature range of foamable viscosity is narrow and production is not stable.
[0007]
[Means for Solving the Problems]
In order to solve the above problems, in the present invention,
Laminate a polyolefin-based resin composition containing a foaming agent on a fibrous base sheet, and crosslink it by irradiating it with ionizing radiation such as an electron beam in order to widen the temperature range of foamable viscosity. Decided to let.
As a result, the production was stable, and the foam sheet on the surface was cross-linked with an electron beam, so the surface was hard and the surface was not damaged.
Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, and usually ultraviolet rays and electron beams are used. As an ultraviolet ray source, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, a metal halide lamp or the like is used. As the electron beam source, various electron beam accelerators such as a Cockroft Walton type, a bandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. Irradiation is performed with electrons having energy of 100 to 1000 keV, preferably 100 to 300 keV.
[0008]
And, the wallpaper of the present invention is a wallpaper in which a cross-linked foam layer of a polyolefin resin subjected to a decoration treatment is laminated on a fibrous base material sheet, wherein the foam layer is a hydrogenated diene type It consists of polyolefin resin to which rubber is added.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
FIG. 1 is a cross-sectional view showing an embodiment of wallpaper 4 according to the present invention, in which 1 is a pattern, 2 is a foam layer, 3 is a fibrous base sheet, and 4 is wallpaper.
[0010]
In Claim 1, the crosslinked foam layer of polyolefin resin is formed by irradiating an ionizing radiation such as an electron beam to a coating layer of polyolefin resin containing a foaming agent, followed by heating and foaming. It is what is done.
[0011]
There are various types of wallpaper 4 other than the one shown in FIG.
For example, the wallpaper 15 shown in FIG. 2 typified by Example 2 has an embossed foam layer 13 laminated on a fibrous base sheet 14, and the embossed recess has wiping ink 12. There is a wood grain pattern 11 in the part, and the whole is covered with a protective layer 10.
[0012]
As a method of laminating a polyolefin-based resin composition containing a foaming agent on a fibrous base material sheet, there are means such as extrusion lamination, dry lamination using an adhesive such as two-component curable polyurethane resin, polyester resin, sol coating, and the like. Can be used.
And in order to widen the temperature range of foaming suitable viscosity to the lamination surface of the polyolefin-type resin composition containing a foaming agent, it decided to heat-foam, after irradiating and ionizing radiation, such as an electron beam.
[0013]
As the fibrous base sheet, paper, non-woven fabric, or woven fabric is used. Here, as paper, flame-retardant paper and general paper are used. The flame retardant paper is a paper containing a flame retardant in the paper.
[0014]
Suitable flame retardants include nitrogen compounds such as urea and ammonium compounds, substances having crystal water such as magnesium hydroxide and aluminum hydroxide, and flame retardants containing phosphorus or halogen elements having self-extinguishing properties. In particular, by mixing a large amount of a substance having crystal water such as magnesium hydroxide, flame retardancy is achieved by the heat of vaporization of crystal water during combustion decomposition.
[0015]
Nonwoven fabrics include wet nonwoven fabrics and dry nonwoven fabrics. As the wet nonwoven fabric, there are a papermaking type and a dry nonwoven fabric include an adhesive type, a mechanical bond type (needle punch, stitch bond), and a spun bond type.
Specifically, rayon paper, a mixture of pulp, Japanese paper, glass nonwoven fabric, asbestos nonwoven fabric, polyester nonwoven fabric, or the like is used as the nonwoven fabric.
[0016]
Examples of the polyolefin resin in the present invention include polyethylene, ethylene-vinyl acetate copolymer, ethylene / propylene copolymer, ethylene / butene-1 copolymer, polypropylene, propylene / butene-1 copolymer, polybutene-1, Butene-1, propylene, ethylene, terpolymer, butene-1, hexene-1, octene-1, terpolymer, polymethylpentene, or JP-A-6-16832 or JP-B-6- Olefin-based elastomers described in Japanese Patent No. 23278 are used. These resins may be used alone or in combination of two or more.
[0017]
These polyolefin resins can be used by themselves, but various rubbers are preferably added in order to impart flexibility, impact resistance, and easy adhesion to the polyolefin resin. Examples of rubbers include diene rubbers, hydrogenated diene rubbers, and olefin elastomers. Among these, hydrogenated diene rubbers are preferable.
[0018]
The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of a double bond of a diene rubber molecule, and is used as a modifier for a polyolefin resin in the present invention. It has the role of suppressing the crystallization of polyolefin resin and improving flexibility and transparency. In general, when a diene rubber is added to a polyolefin resin, the weather resistance and heat resistance are lower than those of a polyolefin resin without the addition of a diene rubber because of the double bond of the diene rubber. Since the double bond is saturated with hydrogen, the polyolefin resin is good without deterioration of the weather resistance and heat resistance.
[0019]
Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene / butadiene rubber. Styrene-butadiene rubber is particularly preferred for the purposes of the present invention. The addition amount is about 1 to 90 parts by weight with respect to 100 parts by weight of the polyolefin resin.
[0020]
Next, in order to obtain a foam layer, for example, a foaming agent is added to a composition such as a plastisol or an organosol of the above-described polyolefin resin, and mechanically foamed by stirring with a stirrer such as a planetary mixer. Or azo compounds such as azodicarbonamide and azobisisobutyronitrile, sulfonyl hydrazide compounds such as paratoluenesulfonyl hydrazide and oxybisbenzenesulfonyl hydrazide, and nitroso compounds such as N, N'-dinitrosopentamethylenetetramine Thermal decomposition foaming agents such as ammonium carbonate, sodium boron hydride, potassium hydrogen carbonate, sodium hydrogen carbonate, etc., or resin shell made of acrylonitrile, methyl (meth) acrylate, etc., hexane, heptane, butane, air, etc. Micro cap containing thermal expansive gas Le foaming agent alone, or a mixture of two or more added about 1 to 10 parts by weight per 100 parts by weight of the resin, by methods such as foaming by heating decompose the blowing agent.
[0021]
When a foam layer is formed using a pyrolytic foaming agent, a foaming accelerator can be added together with the foaming agent as necessary. As the foaming accelerator, a substance that promotes the thermal decomposition and gas generation reaction of the pyrolytic foaming agent to be used is used. For example, when an azo compound such as azodicarbonamide is used as the foaming agent, dibasic lead sulfate, tribasic lead sulfate, tribasic lead maleate, dibasic lead phthalate, stearin are used as the foaming accelerator. Lead acid, zinc white, urea, oxalic acid, ethanolamine and the like can be used alone or in admixture of two or more. When N, N'-dinitrosopentamethylenetetramine is used as the foaming agent, oxalic acid, salicylic acid, phthalic anhydride, urea, ethylene glycol, boric acid, benzoic acid, etc. are used alone or in combination as foaming accelerators. A mixture of more than one species can be used.
[0022]
The foaming ratio of the above foam layer is preferably in the range of 3 to 10 times. The reason is that if it is less than 3 times, the effect of embossing is reduced and the design is poor. Moreover, it is because it will become more than the breaking elongation of resin foamed when it exceeds 10 times, and a puncture phenomenon is seen.
[0023]
An inorganic filler may be added to the polyolefin-based resin to give an increase effect, or a flame retardant may be added to form a foam layer imparted with flame retardancy.
Examples of the inorganic filler include powders such as calcium carbonate, barium sulfate, clay, and talc, and inorganic hollow bodies such as mica, silica, alumina, diatomaceous earth, silica sand, and shirasu balloon.
[0024]
As the flame retardant, a nitrogen compound such as urea, a substance having crystal water such as magnesium hydroxide, and a flame retardant containing self-extinguishing phosphorus or a halogen element are suitable. In particular, by mixing a large amount of a substance having crystal water such as magnesium hydroxide, flame retardancy is achieved by the heat of vaporization of crystal water during combustion decomposition.
Further, it is preferable that 25 to 100 parts by weight of a mixed flame retardant compound composed of a nitrogen compound and a phosphorus compound is blended in the polyolefin resin. This is because the compatibility with polyolefin is good and the thermal stability is also good.
[0025]
As a decorative treatment, it is possible to print a pattern directly on the surface of the foam layer as shown in FIG. 1, but to make the adhesive force between the ink and the foam layer stronger. If necessary, the surface of the foam layer may be subjected to easy adhesion treatment such as application of an easy adhesion layer, corona discharge treatment, or plasma treatment.
[0026]
Here, acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, and chlorinated polyethylene are used as the easy adhesion layer (also referred to as primer layer or anchor layer). Chlorinated polypropylene is preferred.
[0027]
Acrylics include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) propyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate and butyl (meth) acrylate. (Meth) acrylic acid such as polymer, (meth) ethyl acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, styrene / methyl (meth) acrylate copolymer It is the acrylic resin which consists of a single or copolymer containing ester. However, (meth) acryl here means acryl or methacryl, and so on.
[0028]
Polyurethane is a composition having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent).
[0029]
As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.
[0030]
As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate. Group) isocyanates are used.
[0031]
As a method for applying the decoration treatment to the wallpaper 4 of the present invention, there is a method of adding a pigment to the foam layer 2 to give transparent coloring or opaque coloring.
[0032]
Examples of pigments to be added include titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, and phthalocyanine. Pearl, pearlescent pigments made of organic pigments (including dyes) such as blue, Induslenbury RS, and aniline black, metal pigments such as aluminum and brass, titanium dioxide-coated mica, and basic lead carbonate Depending on the application, either a transparent colored pigment or an opaque colored pigment is selected. These are added and dispersed as powder or scaly foil pieces.
[0033]
Moreover, as another method of performing the decoration process on the wallpaper 4 of the present invention, for example, a method of providing a decoration layer (pattern 1 and wood grain pattern 11) on the foam layer as shown in FIGS. The decorative layer can be formed by printing or laminating metal thin films. As a printing method, the pattern 1 is formed with ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like.
[0034]
As the pattern 1 (pattern), there are a wood grain pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, a solid pattern, and the like. The pattern is provided on the front surface, back surface, both front and back surfaces, or layers of the foam layer.
[0035]
Ink for decorative layer (including wiping ink 12 in FIG. 2) or paint, binder (vehicle), chlorinated polyolefin such as chlorinated polyethylene, chlorinated polypropylene, polyester, polyurethane, acrylic, vinyl acetate, vinyl chloride -A vinyl acetate copolymer, a cellulose resin, etc. are used, and it uses 1 type or in mixture of 2 or more types. To this is used a known pigment added as listed above. The protective layer 10 of FIG. 2 is the same component as the ink of the decorative layer not containing a pigment.
[0036]
As shown in FIG. 1, when printing directly on the foam layer, acrylic, chlorinated polyolefin, polyurethane, etc. are preferable as the binder from the viewpoint of adhesiveness. Even if other binders are used, sufficient adhesion is provided.
[0037]
In the case where the decoration layer is formed of a metal thin film, a method of laminating the metal thin film entirely or partially in a pattern can be mentioned. The metal thin film is formed by a method such as vacuum deposition or sputtering using a metal such as aluminum, chromium, gold, silver, or copper. Or a combination of these may be used.
The metal thin film may be provided on the entire surface or partially in a pattern.
[0038]
Next, the decorative layer may be a gloss adjusting layer. The gloss adjusting layer gives a preferable gloss to the surface of the foam layer, and can be formed by applying a paint using an appropriate vehicle. The vehicle is the same as that of the ink used for the decorative layer.
As the paint for forming the gloss adjusting layer, a gloss (gloss) type paint which does not contain any matting agent is sometimes used, although an appropriate amount of matting agent is usually dispersed to give a desired matting degree. Matting agents that can be used include inorganic hollow bodies such as mica, silica, alumina, calcium carbonate, diatomaceous earth, silica sand, and shirasu balloon.
[0039]
In the wallpaper 4 of the present invention, in order to give better weather resistance (light resistance), an ultraviolet absorber and / or a light stabilizer may be added to the foam layer or the protective layer as necessary. The addition amount is usually about 0.5 to 10% by weight for both the ultraviolet absorber and the light stabilizer, but it is generally preferable to use the ultraviolet absorber and the light stabilizer in combination.
[0040]
As the ultraviolet absorber, organic substances such as benzotriazole, benzophenone, and salicylic acid ester, or inorganic substances such as fine particle zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used. As the light stabilizer, a radical scavenger such as a hindered amine radical scavenger such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate or a piperidine radical scavenger can be used.
[0041]
As the adherend for attaching the wallpaper 4, for example, plaster boards, pearlite boards, flat plates such as creases and doors, plate materials such as curved plates, and articles of various shapes such as three-dimensional articles (molded articles) are targeted. .
[0042]
As a method for laminating these various adherends, for example, (1) a method of laminating an adherend with a pressure roller through an adhesive layer, and (2) wallpaper 4 on the surface of the adherend. A so-called vacuum press laminating method in which the wall paper 4 is laminated on the surface of the molded article by a pressure difference caused by vacuum suction from the adherend (molded article) side. ▼ Wallpaper 4 is supplied to a column such as a cylinder or polygonal column via an adhesive layer, and the wall paper 4 is sequentially pressure-bonded to a plurality of side surfaces constituting a columnar body by a plurality of rollers having different directions. There is a so-called lapping method or the like that is laminated.
[0043]
In particular, as a method of attaching the wallpaper 4 to the uneven three-dimensional object, the lapping method is preferable among the above methods.
[0044]
The wallpaper 4 of the present invention is subjected to predetermined molding processing and the like and used for various purposes. For example, interior decorations for buildings such as walls, ceilings, floors, surface decorations for furniture such as window frames, doors, handrails, surface decorations for furniture or cabinets for light electrical / OA equipment, vehicle interiors for cars, trains, aircraft interiors, windows Uses such as glass makeup are listed.
[0045]
【Example】
Examples of the present invention will be described in detail below.
[0046]
Example 1
Add azodicarbonamide as a foaming agent and dibasic lead sulfate as a foaming accelerator to polypropylene resin (Noblen AH-561, manufactured by Sumitomo Chemical Co., Ltd.), knead, heat to 200-220 ° C and melt Was extruded from a T-die and laminated on a fine paper (fibrous substrate sheet).
Next, the polypropylene resin layer side was irradiated with an electron beam for crosslinking. Then, the surface of the cross-linked polypropylene resin layer is subjected to a gravure printing method using a two-component curable polyester-based ink (FPGR Showa Ink Industries) and then heated at 230 ° C. Then, the polypropylene resin layer was foamed 5 times.
Crosslinking with an electron beam broadens the temperature range of polypropylene foaming viscosity, stabilizes production, and the foam layer on the surface is cross-linked with an electron beam, so it is hard and the surface is not damaged. .
[0047]
Example 2
Add azodicarbonamide as a foaming agent and dibasic lead sulfate as a foaming accelerator to polypropylene resin (Noblen AH-561, manufactured by Sumitomo Chemical Co., Ltd.), knead, heat to 200-220 ° C and melt Was extruded from a T-die and laminated on a fine paper (fibrous substrate sheet).
Next, the polypropylene resin layer side was irradiated with an electron beam for crosslinking. And the surface of this crosslinked polypropylene resin layer was heated at 230 degreeC, and the polypropylene resin layer was made to foam 5 times. The foam layer was then embossed with wood grain conduit by heat embossing. Furthermore, black wiping ink was embedded in the recess of the emboss. Next, a two-component curable polyester ink (FPGR Showa Ink Industries Co., Ltd.) is used on the embossed convex portion of the foam layer, and a teak grain pattern is printed in three colors by a gravure printing method, and then a transparent acrylic type The resin layer was formed by gravure coating.
Cross-linking with an electron beam broadens the temperature range of polypropylene foaming viscosity, stabilizes production, and the foam layer on the surface is cross-linked with an electron beam, so the surface is hard and does not dent. It was.
[0048]
【The invention's effect】
The wallpaper of the present invention
Laminate a polyolefin-based resin composition containing a foaming agent on a fibrous base sheet, and crosslink it by irradiating it with ionizing radiation such as an electron beam in order to widen the temperature range of foamable viscosity. Because the wallpaper was made to be stable, the surface foam sheet was cross-linked with an electron beam, so it was hard and the surface was not damaged or dented. In addition, the resin layer was not rubbed strongly with a wipe, and the resin layer was no longer cohesive.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of wallpaper according to the present invention.
FIG. 2 is a cross-sectional view showing an example of wallpaper according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Pattern 2 Foam layer 3 Fiber base material sheet 4 Wallpaper 10 Protective layer 11 Wood grain pattern 12 Wiping ink 13 Foam layer 14 Fiber base material sheet 15 Wallpaper

Claims (1)

  In a wallpaper in which a cross-linked foam layer of a polyolefin resin subjected to decoration treatment is laminated on a fibrous base sheet, the foam layer is made of a polyolefin resin to which hydrogenated diene rubber is added. A wallpaper characterized by

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