JP2007138403A - Noncombustible base material and noncombustible decorative plate using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a noncombustible base material and a noncombustible decorative plate using the noncombustible base material having excellent scratch resistance, weatherability and productivity hardly causing cracking and chipping in handling. <P>SOLUTION: The noncombustible base material is characterized in that an expanded graphite sheet is laminated on at least one face of the base material for the decorative plate through a first adhesive layer and that the expanded graphite sheet has a thickness of 0.1-1.0 mm and a density of 0.96-1.60 g/cm<SP>3</SP>. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a non-combustible base material and a non-combustible decorative board using the same, and more particularly to a non-combustible decorative board suitably used for a kitchen hanging door installed on a wall surface of a system kitchen such as a furnace. It is.

  Conventionally, as a non-combustible decorative board, (1) the surface of an inorganic board such as a gypsum board, a calcium silicate board, a cement board, or the like, or a thermosetting resin decorative sheet laminated on the inorganic board Heated and pressure molded products are known.

  In addition, as another non-combustible decorative board, (2) a decorative layer molding layer material is laminated and integrated on a multilayer base material molding material consisting of a sheet base material made of inorganic fibers and aluminum hydroxide and a phenol resin. Is known (see, for example, Patent Document 1).

  The non-combustible decorative board (1) described above is hard and brittle, so that it is easy to crack or chip during handling such as processing or construction, or surface irregularities of the inorganic board appear on the surface. Therefore, there has been a problem that the design property cannot be satisfied.

In addition, the above-mentioned nonflammable decorative board (2) has a problem that it does not become a nonflammable material unless the mixing ratio of aluminum hydroxide to phenolic resin is increased, or the melamine resin used for the decorative layer molding layer material is weather resistant. Since it is inferior, there is a problem of yellowing with time, and there has been a demand for solving the various problems described above.
Japanese Patent Application Laid-Open No. 64-56540

  Therefore, the present invention is to provide a non-combustible base material that is unlikely to be cracked or chipped during handling and is excellent in stain resistance, scratch resistance, and weather resistance, and a non-combustible decorative board using the same.

  In order to achieve the above object, the present inventors have found that the nonflammable substrate of the present invention according to claim 1 is an expanded graphite sheet via a first adhesive layer on at least one surface of the decorative plate substrate. It is characterized by being laminated.

The present invention according to claim 2 is the nonflammable substrate according to claim 1, wherein the expanded graphite sheet has a thickness of 0.1 to 1.0 mm and a density of 0.96 to 1.60 g. / Cm ³ .

  According to a third aspect of the present invention, there is provided a nonflammable decorative board according to the present invention, wherein a decorative layer is laminated on the expanded graphite sheet provided on one surface of the nonflammable substrate according to the first aspect via a second adhesive layer. It is characterized by that.

  According to a fourth aspect of the present invention, in the incombustible decorative board according to the third aspect, the decorative layer includes a surface protective layer on the surface layer.

Further, the present invention according to claim 5 is the non-combustible decorative board according to any one of claims 3 and 4, wherein the organic component weight of the first adhesive layer, the second adhesive layer, and the decorative layer is It is characterized by being 300 g / m ² or less.

  Since the non-combustible substrate of the present invention has a structure in which an expanded graphite sheet is laminated on a decorative board substrate via a first adhesive layer, there is no occurrence of cracking or chipping during handling. There is an excellent effect of having.

Moreover, since the non-combustible decorative board of the present invention has a configuration in which a decorative layer is laminated on the expanded graphite sheet via a second adhesive layer, it can be made excellent in design properties with surface smoothness. . In addition, the surface layer of the decorative layer is provided with a surface protective layer, particularly a surface protective layer made of an ionizing radiation curable resin, so that it has excellent performance in contamination resistance, scratch resistance, and weather resistance. be able to. In addition, the non-combustible decorative board of the present invention has fireproof performance that passes the test as a non-combustible material by setting the organic weight of the first and second adhesive layers and the decorative layer to 300 g / m ² or less. It is suitable for applications subject to interior restrictions. Furthermore, the non-combustible decorative board of the present invention is excellent in productivity and inexpensive because it takes a step of sequentially laminating an expanded graphite sheet and a decorative layer through a first and second adhesive layers on a decorative board base material. Can be manufactured.

The above-described present invention will be described in detail below with reference to the drawings.
FIG. 1 is a view schematically showing a basic layer structure of a non-combustible decorative board according to the present invention. The non-combustible decorative board 1 has a first adhesive layer 21 on one side of a base 20 for decorative board. A decorative layer provided with a surface protective layer 40 made of an ionizing radiation curable resin on the surface layer of the non-combustible base material 2 in which the expanded graphite sheet 22 is laminated via the second adhesive layer 3 on the expanded graphite sheet 22 4 is laminated.

  Examples of the decorative board base 20 include well-known wood bases and resin-molded boards. Examples of the wood bases include plywood, particle board, medium density fiber board (MDF), and high density. Fiber boards (HDF), etc., and resin-molded boards such as paper, non-woven fabric, or fiber sheets such as glass fibers, diallyl phthalate resin, benzoguanamine resin, phenol resin, melamine resin, unsaturated polyester resin, epoxy resin , And the like formed by impregnating a resin such as urethane resin, and the thickness is suitably about 2.5 to 30 mm.

The expanded graphite sheet 22 is a cotton obtained by oxidizing a graphite having a developed crystal structure such as natural graphite or cash graphite with an oxidizing agent such as sulfuric acid and / or nitric acid, washing it with water, and then heat-treating it with heat. It is a sheet obtained by pressure-molding (compressing) shaped graphite (expanded graphite), but if necessary, impurities such as sulfur and iron contained in the sheet are removed with halogen gas, etc. A sheet made of expanded graphite may also be used. The expanded graphite sheet 22 has a thickness of 0.1 to 1.0 mm and a density of 0.80 to 1.60 g / cm ³ , preferably 0.2 to 0.8 mm and a density of 0.1. 96-1.3 g / cm ³ . If the thickness is less than 0.1 mm, the handleability is poor, and if it exceeds 1.0 mm, it is desirable to avoid it from the viewpoint of cost effectiveness. On the other hand, if the density is less than 0.80 g / cm ³ , the handling property is poor in terms of brittleness, and if it exceeds 1.60 g / cm ³ , it is desirable to avoid it in terms of cost effectiveness.

Next, the decorative layer 4 will be described. Examples of the decorative layer base material constituting the decorative layer 4 include saturable polyester, low-density polyethylene (linear low-temperature), because of its excellent processability and generation of no harmful gas during combustion. Density polyethylene), medium density polyethylene, high density polyethylene, homopolypropylene, ethylene alpha olefin copolymer, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer Examples thereof include a film-based substrate made of a coalescence, an ethylene-vinyl alcohol copolymer, or a mixture thereof. These are either unstretched or uniaxially or biaxially stretched. The thickness may be about 25 to 250 μm. In addition, if another example of the decorative layer base material is exemplified, a printing paper for building materials (a thin paper for building materials), a pure white paper, or a thin paper obtained by mixing synthetic resin to enhance interlayer strength, titanium oxide, etc. Examples thereof include a paper-based base material such as titanium paper mixed with an opaque pigment, and a basis weight of about 23 to 200 g / m ² is appropriate. These film-based substrates or paper-based substrates may be subjected to appropriate easy-adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment, etc. on necessary surfaces as necessary.

  In addition, the decorative layer 4 is usually made of a gravure printing method, an offset printing method, a pattern such as a wood grain pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric pattern, a character, a symbol, a line drawing, and various abstract patterns. The decorative layer base material is formed using ink by a known printing method such as a silk screen printing method. Inks include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane made of isocyanate and polyol, polyacryl, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and cellulose. 1 type or a mixture of two or more types of resin, polyamide resin, and the like, and pigments, solvents, various auxiliary agents, etc. added thereto can be used as inks. A non-chlorine vehicle in which one or two or more of polyurethane, polyacryl, polyvinyl acetate, cellulose resin, polyamide resin and the like composed of isocyanate and polyol are mixed is suitable, more preferably polyester, isocyanate and polyol. Polyureta It is obtained by mixing polyacrylic, one or two or more kinds of such polyamide-based resin.

  Next, the surface protective layer 40 formed on the surface layer of the decorative layer 4 will be described. The surface protective layer 40 is provided for imparting surface physical properties such as scratch resistance, stain resistance, abrasion resistance, and water resistance required for the nonflammable decorative board 1. The resin to be formed is suitably formed using a curable resin such as a thermosetting resin or an ionizing radiation curable resin, but more preferably has a hard surface hardness and is an oxidized vegetable or animal oil. It is an ionizing radiation curable resin because it can be easily wiped off even if it adheres and is excellent in productivity.

  The ionizing radiation curable resin is a resin that undergoes a cross-linking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. Ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, such as visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-ray, electron beam, ion beam, etc. is there. Usually, ultraviolet rays or electron beams are used. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength range of 190 to 380 nm can be used. As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The electron beam used is 100 to 1000 keV, preferably 100 to 300 keV. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

  An ionizing radiation curable resin is a monomer or prepolymer having in its molecule a radically polymerizable unsaturated group such as (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as epoxy group. Or a polymer (hereinafter collectively referred to as a compound). These monomers, prepolymers, and polymers are used alone or in combination. In this specification, (meth) acrylate is used in the meaning of acrylate or methacrylate.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, silicone (meth) acrylate, polyvinyl Examples include pyrrolidone and the like. This prepolymer usually has a molecular weight of about 10,000 or less. When the molecular weight exceeds 10,000, the cured resin layer has insufficient surface properties such as scratch resistance, abrasion resistance, chemical resistance, and heat resistance. The acrylate and methacrylate can be used in common, but the acrylate is more advantageous for the purpose of curing efficiently at a high speed and in a short time because the acrylate is faster in terms of the crosslinking curing rate with ionizing radiation.

  Examples of the prepolymer having a cationically polymerizable functional group include epoxy resins such as bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, urethane vinyl ethers, and ester vinyl ethers. And prepolymers such as vinyl ether resins, cyclic ether compounds, and spiro compounds.

  Examples of monomers having a radically polymerizable unsaturated group include (meth) acrylate compound monofunctional monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl ( (Meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N , N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, ethyl carbitol ( Me ) Acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2 -(Meth) acryloyloxypropyl hydrogen terephthalate and the like.

  In addition, as a polyfunctional monomer having a radical polymerizable unsaturated group, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tripropylene Glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, tris (meth) acryloyloxyethyl A phosphate etc. are mentioned. As the monomer having a cationic polymerizable functional group, a prepolymer monomer having the cationic polymerizable functional group can be used.

The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam. However, when cured by irradiation with ultraviolet rays, a photopolymerization initiator is added as a sensitizer. In the case of a resin system having a radically polymerizable unsaturated group, photopolymerization initiators are acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide, diethyl Oxite, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used alone or in combination. In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, a freeloxysulfoxonium diallyl iodosyl salt, or the like is used alone or as a mixture. be able to. In addition, generally the addition amount of these photoinitiators is about 0.1-10 weight part with respect to 100 weight part of ionizing radiation curable resins. Moreover, as a method of forming the surface protective layer 40 with this ionizing radiation curable resin, for example, by adjusting the viscosity to allow application of this ionizing radiation curable resin, a known coating method such as a gravure coating method or a roll coating method is used. It can form by apply | coating. As a coating amount, about 3-15 g / m < ² > is suitable as solid content.

In addition, the decorative layer 4 can be provided with a primer layer for ink or a primer layer for the surface protective layer 40 on a necessary surface as necessary, thereby improving the adhesive strength between the layers. These primer layers may be formed by a known coating method such as a gravure printing method or a roll coating method using a two-component curable polyurethane adhesive composed of a polyol component and an isocyanate component. Examples of the polyol component include polyester polyol, polyester polyurethane polyol, polyether polyol, polyether polyurethane polyol, and the like, and examples of the isocyanate component include diisocyanates such as TDI, MDI, HDI, PIDI, and XDI, and starting materials thereof. The modified body which can be mentioned can be mentioned. The coating amount after drying of the primer layer is 0.1 to 5.0 g / m ^2, preferably from 0.5 to 1.0 g / m ^2.

  Next, the first adhesive layer 21 and the second adhesive layer 3 will be described. As the first adhesive layer 21 and the second adhesive layer 3, the decorative board substrate 20 and the expanded graphite sheet 22, and the expanded graphite sheet 22 and the decorative layer 4 are firmly bonded. The adhesive is not particularly limited as long as it is an adhesive that can be used, and a well-known or commercially available adhesive can be used, and is formed of a two-component curable polyurethane adhesive composed of a polyol component and an isocyanate component described in the previous stage. In consideration of the coating amount, workability, and working environment, a moisture curable hot melt adhesive is preferable.

  The moisture-curing hot melt adhesive 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 ends, and is in the state of a thermoplastic resin that is solid at room temperature. Isocyanate groups react with each other by moisture in the air to cause chain extension reaction, resulting in a reaction product having a urea bond in the molecular chain, and the isocyanate group at the end of the molecule reacts with this urea bond, causing a burette bond. Branches 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. Adhesive properties can be adjusted by appropriately employing one or more skeleton structures. In addition, when there is a urethane bond in the molecular chain, the terminal isocyanate group reacts with this urethane bond to produce an allophanate bond, and this allophanate bond also causes a crosslinking reaction.

  Specific examples of the polyisocyanate prepolymer include a urethane prepolymer having a polyurethane skeleton having an isocyanate group at a molecular terminal obtained by reacting an excess isocyanate with a polyol and having a urethane bond in the molecular chain. Further, as disclosed in JP-A No. 64-14287, a polyester skeleton and a polybutadiene skeleton obtained by adding a polyester polyol and a polyol having a polybutadiene skeleton to polyisocyanate in an arbitrary order and performing an addition reaction A crystalline urethane prepolymer having a structure in which is bonded by a urethane bond and having an isocyanate group at the molecular end, or a polycarbonate-based polyol and a polyisocyanate as disclosed in JP-A-2-305882 A polycarbonate urethane prepolymer having two or more isocyanate groups in the molecule obtained by reacting the polyester, and a polyester urethane having two or more isocyanate groups in the molecule obtained by reacting the polyester polyol and polyisocyanate. Emissions prepolymers, and the like.

In addition to the above-mentioned various polyisocyanate prepolymers, the moisture-curable hot-melt adhesive may include a thermoplastic resin and a tackifier as necessary in order to adjust the various physical properties. Various sub-materials such as plasticizers and fillers can also be added. Examples of these secondary materials include ethylene-vinyl acetate copolymer, low molecular weight polyethylene, modified polyolefin, atactic polypropylene, linear polyester, ethylene-ethyl acrylate (EAA), ethylene-methacrylate (EMA), 2-hydroxy. Thermoplastic resins such as ethyl methacrylate (HEMA), terpene-phenol resins, tackifiers such as rosin ester of abietic acid, fillers (external pigments) composed of fine powders such as calcium carbonate, barium sulfate, silica, and alumina, coloring pigments , Curing catalyst, moisture remover, storage stabilizer, anti-aging agent and the like. The coating amount of the first adhesive layer 21 and the second adhesive layer 3 is generally 20 to 60 g / m ² as a solid content.

  Next, the present invention will be described in more detail with reference to the following examples.

[Production of makeup layer]
A two-part curable polyurethane adhesive is applied to one side of a 50 μm-thick biaxially stretched polyethylene terephthalate film (hereinafter referred to as PET film) by gravure printing so that it becomes 0.5 g / m ² after drying. After forming a primer layer for ink and forming a pattern layer of wood grain pattern by gravure printing method using acrylic ink on the surface of the primer layer for ink, a two-component curable polyurethane system is formed on the other surface of the PET film. The adhesive is applied by gravure printing so as to be 0.5 g / m ² after drying to form a primer layer for a surface protective layer, and an ionizing radiation curable resin is applied to the surface of the primer layer for the surface protective layer by a roll coating method. And then applied with an electron beam (175 KeV, 5 Mrad) to prepare a decorative sheet as a decorative layer having a surface protective layer of 10 g / m ² .

[Test body 1]
Adhesive [made by Chuo Rika Kogyo Co., Ltd .: Rikabond BA-10L (100 parts by weight) to BA-11B (2.5 parts by weight) on one side of a 2.5 mm thick medium density fiberboard (MDF) )) Was applied using a roll coating method so that it would be about 55 g / m ² after drying, and an expanded graphite sheet (manufactured by Toyo Tanso Co., Ltd .: thickness 0.2 mm, density) Of 1.0 g / cm ³ ] was used as a test substrate.

[Specimen 2]
Add adhesive (BA-11B (2.5 parts by weight) to Rikabond BA-10L (100 parts by weight) manufactured by Chuo Rika Kogyo Co., Ltd.) on the surface of the expanded graphite sheet of the incombustible base material prepared above. The adhesive layer] is applied using a roll coat method so as to be about 55 g / m ² after drying, and the decorative sheet prepared as described above is applied to the coated surface so that the woodgrain pattern layer is located on the adhesive surface. The laminate was used as a test decorative board.

[Specimen 3]
A 2.5 mm thick MDF itself was used as a test substrate.

[Test body 4]
Adhesive [made by Chuo Rika Kogyo Co., Ltd .: Rikabond BA-10L (100 parts by weight) to BA-11B (2.5 parts by weight) on one side of a 2.5 mm thick medium density fiberboard (MDF) ))] Is applied using a roll coating method so that it is about 55 g / m ² after drying, and the decorative sheet prepared above is applied to the coated surface with a woodgrain pattern layer on the adhesive surface. The laminate laminated as described above was used as a test decorative board.

  An exothermic test (based on ISO 5660-1) was performed on the specimens 1, 2, 3, and 4 produced above, and the results are summarized in Table 1.

  As is clear from Table 1, the composite base material and the decorative board of the test bodies 1 and 2 using the expanded graphite sheet are suitable as non-combustible materials.

  Up to now, the non-flammable base material and the non-flammable decorative board provided with the expanded graphite sheet 22 and the decorative layer 4 on one surface of the decorative board base material 20 have been described. Reference numeral 4 may be a double-sided non-combustible base material and a non-combustible decorative board provided on the other surface of the base material 20 for decorative plate. By using a non-combustible decorative board provided with a decorative layer 4 on both sides, it can be used as a partition.

It is a figure showing the basic layer composition of the nonflammable decorative board concerning the present invention diagrammatically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Nonflammable decorative board 2 Nonflammable base material 3 Second adhesive layer 4 Cosmetic layer 20 Base material for decorative board 21 First adhesive layer 22 Expanded graphite sheet 40 Surface protective layer

Claims (5)

An incombustible base material, wherein an expanded graphite sheet is laminated on at least one surface of a base material for a decorative board via a first adhesive layer. The nonflammable substrate according to claim 1, wherein the expanded graphite sheet has a thickness of 0.1 to 1.0 mm and a density of 0.96 to 1.60 g / cm ³ . A nonflammable decorative board, wherein a decorative layer is laminated via a second adhesive layer on the expanded graphite sheet provided on one surface of the nonflammable substrate according to claim 1. The non-combustible decorative board according to claim 3, wherein the decorative layer includes a surface protective layer on a surface layer thereof. The nonflammable decorative board according to any one of claims 3 and 4, wherein the organic component weight of the first adhesive layer, the second adhesive layer, and the decorative layer is 300 g / m ² or less. Incombustible decorative board.

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