JP2009196247A - Incombustible melamine decorative laminated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an incombustible melamine decorative laminated sheet in which a fingerprint or the like is inconspicuous. <P>SOLUTION: A water-repellent and oil-repellent and low-refractive layer is formed on the surface of the incombustible melamine decorative laminated sheet. The water-repellent and oil-repellent and low-refractive layer is formed of an ordinary temperature glass coating agent or a siloxane-graft type polymer prepared by compounding fluoro resin or acryl resin and siloxane. A liquid mixture obtained by ionizing an alcohol-soluble organic silicone compound in a solution composed of water, organic solvent, etc. and adding halogen and boron as a catalyst is used as the ordinary temperature glass coating agent. A composition obtained by compounding fluoro resin or acryl resin and siloxane is used as the siloxane-graft type polymer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a nonflammable melamine decorative board having a water / oil repellency / low refractive index layer on the surface.

  Conventionally, a melamine decorative board is excellent in various physical properties such as surface hardness, heat resistance, and wear resistance, and thus is suitably used for horizontal surfaces such as counters and desks. This melamine decorative board generally has a melamine resin-impregnated patterned paper impregnated and dried with a resin liquid mainly composed of melamine-formaldehyde resin on a decorative board pattern base paper, and kraft paper mainly composed of phenol-formaldehyde resin. It is obtained by laminating a phenol resin-impregnated core paper impregnated and dried with a resin liquid, and heating and pressing with a flat plate press.

In recent years, a non-combustible melamine decorative board in which fire resistance and non-combustibility are imparted to this melamine decorative board is known, and a prepreg containing a phenol resin or a melamine resin as a binder component is used for an inorganic fiber non-woven fabric ( Patent Documents 1 to 7).
JP-A-6-199528 JP 2004-230611 A Japanese Patent Laid-Open No. 10-44323 Japanese Patent Application Laid-Open No. 64-56540 JP 2005-146272 A JP 2003-292870 A JP 2000-119354 A

  The non-combustible melamine decorative board has a defect that oil stains such as fingerprints (sebum film) are easily attached while it is excellent in surface hardness, heat resistance, abrasion resistance and the like due to the characteristics of the melamine resin. In particular, in the case of a decorative board with an embossed finish having an uneven surface, the embossed portion has low gloss due to diffused reflection of light, but the fingerprint adhering portion has a wet color, so that the fingerprint is noticeable by contrast with the surroundings. Furthermore, there is a drawback that the pattern of the printed paper cannot be clearly expressed by reflection of light in the melamine resin layer or white blur.

  The present invention has been made in view of such a problem, and an object of the present invention is to provide a non-combustible melamine decorative board in which fingerprints and the like are not noticeable. The present invention includes a melamine resin layer and a core layer. And a low refractive index layer formed in an upper layer than the melamine resin layer, and the gist of the nonflammable decorative melamine decorative board.

Since the low refractive index layer that is a component of the present invention has a lower refractive index than the melamine resin layer,
The refractive index difference between the fingerprint and the low refractive index layer is smaller than the refractive index difference between the fingerprint and the melamine resin layer. Therefore, the fingerprint attached to the nonflammable melamine decorative board of the present invention is less conspicuous than the fingerprint attached directly on the melamine resin layer.

  Further, the low refractive index layer preferably has a low reflectance. In this case, since the low refractive index layer has low reflectance and low refractive index, the reflection of light on the non-combustible melamine decorative board, white blurring is improved, and the non-combustible melamine decorative board has a pattern of printing paper, The design becomes clear and the design is improved.

  The refractive index of the low refractive index layer is preferably 1.55 or less. Since the refractive index of the fingerprint is about 1.4 to 1.5 and the refractive index of the melamine resin layer is about 1.6 to 1.7, the refractive index of the low refractive index layer should be 1.55 or less. Thus, the refractive index difference between the fingerprint and the low refractive index layer can be made smaller than the refractive index difference between the fingerprint and the melamine resin layer, and the fingerprint attached to the incombustible melamine decorative board can be made inconspicuous.

  The low refractive index layer preferably has water and oil repellency. By having water and oil repellency, adhesion of fingerprints to the non-combustible melamine decorative board is reduced. In particular, in the case of a non-combustible melamine decorative board with an embossed finish, the fingerprint is repelled and adheres in a spherical shape due to the water and oil repellency of the low refractive index layer, so that the light is irregularly reflected even at the fingerprint adhering portion.

  When the low refractive index layer has water / oil repellency, the low refractive index layer preferably has a water contact angle of 90 ° or more and an oleic acid contact angle of 45 ° or more. By this, the effect that the adhesion of the fingerprint to a nonflammable melamine decorative board is reduced is still more remarkable.

  The low refractive index layer in the present invention can contain, as a main component, (a) a room temperature glass coating agent, or (b) a siloxane graft polymer in which a fluororesin or an acrylic resin and siloxane are complexed. The low refractive index layer may consist only of the above (a) or (b), or may contain other additive components.

  Hereinafter, the present invention will be described in detail. Examples of the method for producing the incombustible melamine decorative board of the present invention include (1) a water / oil repellency / low refractive index layer forming agent (for example, (a) a room temperature glass coating agent, or (b) a fluororesin or an acrylic resin. A melamine resin-impregnated pattern paper coated with a siloxane-grafted siloxane graft polymer and a curing agent is laminated together with the core material and hot-pressed (for example, heated at a temperature of 110 to 180 ° C.). (2) A melamine resin-impregnated overlay paper coated with a water / oil repellency / low refractive index layer forming agent is laminated on a core material and a melamine resin-impregnated pattern paper and subjected to hot-pressure molding ( For example, a heating temperature of 110 to 180 ° C., a pressing condition of 5 to 10 MPa), (3) a transfer sheet is prepared by applying a water / oil / oil repellency / low refractive index layer forming agent to the substrate, The sheet is placed on the melamine resin-impregnated pattern paper as the uppermost layer, laminated together with the core material, and subjected to hot-pressure molding (for example, heating temperature of 110 to 180 ° C., pressurization condition of 5 to 10 MPa). (4) A transfer sheet is prepared by applying a water / oil / oil repellency / low refractive index layer forming agent to a substrate, and the transfer sheet is placed on a melamine resin-impregnated overlay paper, and a core material and a melamine resin. Examples include a method of laminating impregnated pattern paper and hot pressing (for example, heating temperature of 110 to 180 ° C., pressurization condition of 5 to 10 MPa) and removing the base material after molding.

The melamine resin-impregnated patterned paper has a basis weight of about 80 to 140 g / m ^{2 on} decorative paper for decorative board, and impregnation ratio of 70 to 160% by a calculation method represented by Equation 1 with a resin liquid mainly composed of amino-formaldehyde resin. It is obtained by impregnation with and drying.

Furthermore, for the purpose of improving the abrasion resistance on the surface of the melamine decorative board, a melamine resin impregnated overlay paper impregnated with a resin liquid mainly composed of melamine-formaldehyde resin is laminated on the uppermost layer and subjected to hot press molding. May be. The melamine resin-impregnated overlay paper is obtained by, for example, impregnating an overlay base paper having a basis weight of about 20 to 60 g / m ² with a resin liquid mainly composed of melamine-formaldehyde resin at an impregnation rate of 200 to 400% and drying. be able to.

  The core material of the incombustible melamine decorative board used in the present invention is composed of a prepreg in which an inorganic fiber base material is impregnated with a slurry containing an organic resin component and an inorganic filler.

Examples of the inorganic fiber substrate include nonwoven fabrics and woven fabrics made of inorganic fibers such as glass fiber, rock wool, carbon fiber, and ceramic fiber. The basis weight of the inorganic fiber substrate is in the range of 10 to ²⁰⁰ g / m ² . In particular, it is preferable to use a glass fiber nonwoven fabric excellent in heat resistance and flame resistance and excellent in impregnation of slurry.

  As the organic resin component, physical properties such as incombustibility, strength, and heat resistance are improved by using a phenol-formaldehyde resin and an amino-formaldehyde resin in combination.

  A phenol-formaldehyde resin is obtained by reacting phenols and formaldehydes in an amount of 1 to 3 moles of aldehydes with a basic catalyst or an acidic catalyst with respect to 1 mole of phenolic hydroxyl groups. Examples of the class include phenol, cresol, xylenol, octylphenol, phenylphenol, bisphenol A, bisphenol S, and bisphenol F. Examples of the aldehyde include formaldehyde, paraformaldehyde, glyoxal, and trioxal.

  In addition, those modified with a modifying agent that promotes plasticization such as urea, urea derivatives, paratoluene sulfonamide, tung oil, phosphate esters, glycols, etc. can be applied as necessary. Examples include alkali metals such as magnesium, oxides and hydroxides of alkaline earth metals such as magnesium and calcium, amines such as triethylamine and triethanolamine, ammonia, and acidic catalysts include p-toluenesulfonic acid, hydrochloric acid Etc.

  Amino-formaldehyde resins include initial condensates obtained by reacting amino compounds such as melamine, urea, benzoguanamine, and acetoguanamine with formaldehyde, etherification with lower alcohols such as methyl alcohol and butyl alcohol, and paratoluene. Those modified with a reactive modifier that promotes plasticization such as sulfonamide can be applied, and among them, a melamine-formaldehyde resin excellent in durability is preferable.

  As the inorganic filler contained in the slurry, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, which contain crystal water and decompose at high temperature and release heat, release bound water, are essential components, and the average particle size is 0. When the material in the range of 5 to 200 μm is adopted, the suitability of impregnation into the inorganic fiber substrate is excellent.

  The blending ratio of the phenol-formaldehyde resin and amino-formaldehyde resin as the organic resin component in the slurry is desirably a solid content ratio of 1: 0.1 to 5, and the amino-formaldehyde resin is preferably used with respect to the phenol resin. If the amount is small, the strength and adhesion tend to be inferior, and if the amount is large, the warp becomes large. Moreover, it is desirable that the blending ratio of the organic resin component and the inorganic filler is 5 to 20:95 to 80, and if the inorganic filler increases with respect to the organic resin component, the nonflammability performance is improved, but the adhesion is lowered. In addition, when the inorganic filler is decreased, the incombustibility is lowered although the adhesion is improved.

  The slurry solid content (%) in the inorganic fiber substrate is a calculation method represented by Equation 2, and is preferably in the range of 500 to 3000%.

  If the upper limit is exceeded, the solid content will drop off, making it difficult to handle, and if the lower limit is not reached, delamination will easily occur.

  As a room temperature glass coating agent used in the present invention, for example, an alcohol-soluble organosilicon compound is ionized in a solution composed of water or an organic solvent, and halogen and boron are added as a catalyst.

The role of B ³⁺ ions is to prevent a decrease in the amount of SiO ₂ due to the formation and volatilization of SiF ₆ by reacting with F ⁻ ions. B ³⁺ ions react with F ⁻ ions to produce BF ₄ ⁻ complex ions, which are very easily exchanged with Si of Si (OR) n to become SiF ⁻ _{n + 1} complex ions. As a result, a metal oxide glass can be obtained in the normal temperature region. The remaining B ³⁺ ion is converted to B (OCH ₃ ) ₃ due to the presence of methanol (CH ₃ ⁺ ), and the F ⁻ ion vaporizes and disappears as HF through contact reaction with the OH ⁻ group and the like contained in the substrate. Here, R is an alkyl group, M is a metal, and X is a halogen.

B ³⁺ + 4X ⁻ → BX ₄ ⁻
_{M (OR) n + BX 4} - + n / 2H 2 O → MX - n + 1 + nROH + B 3+
MX ⁻ _{n + 1} + nH ₂ O → M (OH) n + (n + 1) X ⁻
M (OH) n → metal oxide glass + H ₂ O
Trialkoxyborane B (OR) ₃ is used as the compound that gives boron ions B ³⁺ . Of these, triethoxyborane B (OEt) ₃ is preferred. The B ³⁺ ion concentration in the reaction solution is preferably in the range of 1.0 to 10.0 mol / liter. As the halogen ion, F ^- and Cl ^- or a mixture thereof is used. The compound to be used may be any compound that generates F ⁻ ions and Cl ⁻ ions in the reaction solution. For example, the F ⁻ ion source includes ammonium hydrogen fluoride NH ₄ F · HF, sodium fluoride NaF, and the like, Cl ^−. The ion source is preferably ammonium chloride NH ₄ Cl or the like.

  As a commercial example of a room temperature glass coating agent, Siragusital A6200, Siragusital B4373 (BN) (all manufactured by Bokuto Kasei Kogyo Co., Ltd.) and the like can be mentioned.

Examples of the siloxane graft type polymer in which a fluororesin or an acrylic resin and siloxane are combined include a composite of a fluororesin or acrylic resin and siloxane. Specifically, (α) 2 to 70% by weight of an organic solvent-soluble fluororesin having a radical polymerizable unsaturated bond moiety via a urethane bond, (β) the following chemical formula 1 (in chemical formula 1, R ¹ is a hydrogen atom Or a hydrocarbon group having 1 to 10 carbon atoms, and R ² , R ³ , R ⁴ , R ⁵ , and R ⁶ may be the same as or different from each other, or a hydrocarbon having 1 to 10 carbon atoms A single-end radical-polymerizable polysiloxane represented by the following formula (wherein n is an integer of 2 or more) and / or the following chemical formula 2 (in the chemical formula 2, R ⁷ is a hydrogen atom or a carbon atom having 1 to 10 carbon atoms: R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , and R ¹² are hydrogen atoms which may be the same or different from each other or a hydrocarbon group having 1 to 10 carbon atoms, and p is 0 to 10 And q is an integer of 2 or more) Radically polymerizable monomer 15 which does not react other than the polymerization reaction with the (α) component under the conditions of 4 to 40% by weight of the one-end radical polymerizable polysiloxane and (γ) radical polymerization reaction It is obtained by copolymerizing ˜94% by weight.

  Further, as other siloxane graft type polymer in which a fluororesin or an acrylic resin and a siloxane are combined, (α) an organic solvent-soluble fluororesin 2 having a radically polymerizable unsaturated bond moiety via a urethane bond 70% by weight, (β) 5 to 55% by weight of one-end radical polymerizable polysiloxane represented by the above chemical formula 1 and / or one-end radical polymerizable polysiloxane represented by the above chemical formula 2, and (γ) having an alkoxysilyl group Monomer having a functional group that does not react other than radical polymerization with 5 to 55% by weight of monomer, (δ) 15 to 50% by weight of monomer having a hydroxyl group, and (ε) component (α) to (δ) There are those obtained by copolymerizing 0 to 73% by weight of the body.

  Moreover, as a siloxane graft type polymer in which a fluororesin or an acrylic resin and siloxane are combined, instead of the component (α), it has a radical polymerizable unsaturated bond portion via a urethane bond, and is organic. Examples thereof include those using a curable group-containing acrylic (co) polymer that is soluble in a solvent.

  Examples of commercially available siloxane graft polymers in which a fluororesin or an acrylic resin and siloxane are combined include ZX-007C, ZX-001, ZX-022, ZX-022H, ZX-028R, and ZX-036 (all Fuji Chemical Industry Co., Ltd.).

  As a curing agent, a curing agent capable of reacting with a hydroxyl group in a siloxane graft type polymer in which a fluororesin or an acrylic resin and a siloxane are combined is appropriately selected. For example, an aniline aldehyde resin, a urea resin, a melamine resin, a polyisocyanate And blocked polyisocyanate. Moreover, when it has a monomer which has an alkoxy silyl group, a silicate type | system | group hardening | curing agent can also be used. The reactive group / OH (equivalent ratio) is preferably 1.0 or more. By being 1.0 or more, curing can be sufficiently performed.

  When applying the water / oil / oil repellency / low refractive index layer forming agent to the surface of melamine resin impregnated pattern paper or melamine resin impregnated overlay paper, known methods such as spray coating, gravure coating, and bar coating A knife coating method, a roll coating method, a blade coating method, a die coating method, a curtain coating method, or the like can be used.

  When the normal temperature glass coating agent is used, the thickness of the coating film of the low refractive index layer after drying is preferably 1 to 10 μm. When a siloxane graft type polymer in which a fluororesin or acrylic resin and siloxane are combined is used, the range is 0.1 to 100 μm, preferably 0.5 to 50 μm. By setting the thickness of the coating film in such a range, the water contact angle of the surface layer of the non-combustible melamine decorative board is 90 ° or more, the oleic acid contact angle is 45 ° or more, and the refractive index is 1.55 or less, which is extremely resistant. It has excellent fingerprint characteristics. If the thickness of the coating film after drying is not more than the above upper limit value, it is difficult to cause an appearance defect due to whitening. Moreover, if the thickness of the coating film after drying is not less than the above lower limit value, unevenness in appearance is unlikely to occur.

  Laminated melamine resin impregnated pattern paper coated with water / oil repellency / low refractive index layer forming agent on core material, or impregnated melamine resin coated with water / oil repellency / low refractive index layer forming agent The overlay paper is laminated on the melamine resin-impregnated pattern paper and the core material, and these are heat-pressed under a molding condition of a heating temperature of 110 to 180 ° C. and a pressing condition of 5 to 10 MPa using a heating and pressing press. A decorative board can be obtained.

  As a base material used when shape | molding the nonflammable decorative melamine board of this invention by a transfer system, a plastic film and metal foil are mentioned, for example. As plastic film, polyester film, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene vinyl alcohol film, Polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyether ketone film, polyether sulfone film, polyetherimide film, polyimide film, fluororesin film, nylon film, acrylic film, and the like can be used.

Examples of the metal foil include gold foil, silver foil, copper foil, zinc foil, indium foil, aluminum foil, tin foil, iron (including stainless steel (SUS) foil) foil, titanium foil, and the like. When applying an oily / low refractive index layer forming agent, known methods such as spray coating, gravure coating, bar coating, knife coating, roll coating, blade coating, die coating, curtain coating, etc. Can be used. The thickness of the coated film after drying is 1 to 10 μm in the case of a room temperature glass coating agent, 0.1 to 100 μm in the case of a siloxane graft type polymer in which a fluororesin or an acrylic resin and siloxane are complexed, preferably 0.00. It applies so that it may become 5-50 micrometers. By making the thickness of the coating film in such a range, the water contact angle of the water / oil repellency / low refractive index layer is 90 ° or more, the oleic acid contact angle is 45 ° or more, and the refractive index is 1.55 or less. It is extremely excellent in fingerprint resistance. If the thickness of the coating after drying is not more than the above upper limit value, it is difficult to cause an appearance defect due to whitening. Moreover, if the thickness of the coating film after drying is not less than the above lower limit value, uneven appearance is unlikely to occur.

  By the above method, a water / oil repellency / low refractive index layer forming agent is applied to the substrate, and the solvent is evaporated by pretreatment drying to obtain a transfer sheet.

  The transfer sheet is placed on a melamine resin-impregnated pattern paper and laminated on the core material, or the transfer sheet is placed on a melamine resin-impregnated overlay paper and laminated on the core material and the melamine resin-impregnated pattern paper, and these are heated. Using a pressure press to obtain a nonflammable melamine decorative board having a water / oil / oil repellent / low refractive index layer formed on the surface thereof by hot pressing under molding conditions of a heating temperature of 110 to 180 ° C. and a pressing condition of 5 to 10 MPa. Can do.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited to the example shown below at all.

1. Preparation of room temperature glass coating agent (A) An alcohol-soluble organosilicon compound (for example, Si (OR) ₄ ) was mixed with an alcohol (for example, isopropanol). Further, boron ions B ³⁺ and halogen ions F ⁻ are added as catalysts, the pH is adjusted to 4.5 to 5.0, and a one-component room temperature glass coating agent (A) (trade name Siragusital A6200 Made by Co., Ltd.).

2. Manufacture of melamine resin-impregnated pattern paper (B) A resin liquid mainly composed of melamine-formaldehyde resin is impregnated into a black base paper for decorative board with a basis weight of 100 g / m ² and dried to obtain a melamine resin-impregnated pattern paper (B ) The impregnation rate of the resin was 100% by the calculation method represented by the above formula 1.

3. Manufacture of prepreg (C) Slurry in which 50 g / m ² of glass fiber nonwoven fabric is blended with 4.5 parts of phenol-formaldehyde resin, 3.5 parts of amino-formaldehyde resin and 92 parts of aluminum hydroxide having an average particle diameter of 12 μm. Was impregnated so that the slurry solid content in the formula 2 was 1200%, to obtain a prepreg (C).

4). Production of room temperature glass coating melamine resin impregnated pattern paper (D) The room temperature glass coating agent (A) was applied to the surface of melamine resin impregnated pattern paper (B) by a bar coating method so that the dry film thickness was 1 μm. Pretreatment drying was performed to obtain a room temperature glass coated melamine resin impregnated pattern paper (D). A room temperature glass coating agent (A) layer (hereinafter referred to as a room temperature glass coating layer (E)) is formed on the surface of the room temperature glass coated melamine resin-impregnated patterned paper (D).
5. Manufacture of non-combustible melamine decorative board In order from the bottom, 1 sheet of room temperature glass coated melamine resin impregnated pattern paper (D), 5 sheets of prepreg (C) and 1 sheet of room temperature glass coated melamine resin impregnated pattern paper (D) are laminated. Then, the non-combustible melamine decorative board of Example 1 was obtained by hot pressing under conditions of 140 ° C. and 10 MPa for 80 minutes.

  In Example 1, a non-combustible material having a water / oil / oil repellency / low refractive index layer formed on the surface of Example 2 was carried out in the same manner except that the dry film thickness of the room temperature glass coating layer (E) was 5 μm. A decorative melamine decorative board was obtained.

  In Example 1, the non-combustible material was formed in the same manner as in Example 3 except that the dry film thickness of the room temperature glass coating layer (E) was 10 μm, and the surface of the water-oil / oil-repellent / low-refractive index layer of Example 3 was formed. A decorative melamine decorative board was obtained.

A room temperature glass coating agent (A) was applied to the surface of an OPP (stretched polypropylene) film having a thickness of 30 μm so as to have a dry film thickness of 1 μm by a bar coating method to prepare a transfer sheet. A room temperature glass coating layer (E) is formed on the surface of the transfer sheet.
Subsequently, the transfer sheet, the melamine resin-impregnated pattern paper (B), the prepreg (C), the melamine resin-impregnated pattern paper (B), and the transfer sheet were laminated in this order and subjected to hot-pressure molding in the same manner as in Example 1. Finally, the transfer sheet was removed to obtain a nonflammable melamine decorative board having a water / oil / oil repellency / low refractive index layer formed on the surface of Example 4.

  In Example 4, the same procedure was performed except that the dry film thickness of the room temperature glass coating layer (E) was changed to 5 μm, and the nonflammable layer of Example 5 in which the water / oil repellency / low refractive index layer was formed on the surface. A decorative melamine decorative board was obtained.

  In Example 4, a non-combustible melamine makeup having a water / oil repellent / low refractive index layer formed on the surface of Example 6 was carried out in the same manner except that the dry film thickness of the room temperature glass coating layer was 10 μm. I got a plate.

In place of the room temperature glass coating agent (A), the following room temperature glass coating agent (B) was used in the same manner to form a water / oil repellency / low refractive index layer on the surface of Example 7. Incombustible melamine decorative board was obtained.
Room temperature glass coating agent (B)
Two-component coating agent (trade name: Siragusital B4373 (BN), Bokuto Kasei Kogyo Co., Ltd.) containing alcohol-soluble organosilicon compound (for example, Si (OR) ₄ ) as the main agent and boron ion B ³⁺ and halogen ion X- as catalysts Company-made). The main agent and the catalyst are mixed at a ratio of main agent: catalyst = 10: 1 and diluted to an arbitrary concentration with a diluting solvent.

  In Example 7, the non-flammable surface was formed in the same manner as in Example 8 except that the dry film thickness of the room temperature glass coating layer (E) was 10 μm, and the surface was provided with a water / oil repellent / low refractive index layer. A decorative melamine decorative board was obtained.

1. Preparation of Siloxane Graft Polymer Coating Solution (A) ZX-022H (hydroxyl value 120, acid value 0, solvent type; xylene / butyl acetate / isopropanol, Fuji) Kasei Kogyo Co., Ltd.) was used. Moreover, the polyisocyanate type hardening | curing agent (A brand name, Coronate HX, Nippon Polyurethane Industry Co., Ltd. product) was used as a hardening | curing agent. Mix siloxane graft type polymer and curing agent so that NCO / OH = 1.2, and add 0.1 wt% of dibutyltin dilaurate as a catalyst based on the solid content of the main agent, and dilute arbitrarily with isopropanol Thus, a siloxane graft type polymer coating solution (A) was obtained.

2. Manufacture of melamine resin-impregnated pattern paper (B) A resin liquid mainly composed of melamine-formaldehyde resin is impregnated into a black base paper for decorative board with a basis weight of 100 g / m ² and dried to obtain a melamine resin-impregnated pattern paper (B ) The impregnation rate of the resin was 100% by the calculation method represented by the above formula 1.

3. Manufacture of prepreg (C) Slurry in which 50 g / m ² of glass fiber nonwoven fabric is blended with 4.5 parts of phenol-formaldehyde resin, 3.5 parts of amino-formaldehyde resin and 92 parts of aluminum hydroxide having an average particle diameter of 12 μm. Was impregnated so that the slurry solid content in the formula 2 was 1200%, to obtain a prepreg (C).

4). Manufacture of siloxane graft type polymer coating melamine resin impregnated pattern paper (D) The surface of melamine resin impregnated pattern paper (B) is coated with a siloxane graft type polymer coating solution (by a bar coating method) so that the dry film thickness becomes 0.5 μm. A) was applied and pretreated and dried to obtain a siloxane-grafted polymer-coated melamine resin-impregnated patterned paper (D). Siloxane Graft Polymer Coating A siloxane graft polymer layer (hereinafter referred to as siloxane graft polymer coating layer (E)) is formed on the surface of the melamine resin-impregnated patterned paper (D).

5. Manufacture of incombustible melamine decorative board In order from the bottom, 1 sheet of siloxane graft type polymer coated melamine resin impregnated pattern paper (D), 5 sheets of prepreg (C), siloxane graft type polymer coated melamine resin impregnated pattern paper (D) One sheet was laminated and hot-press molded under conditions of 140 ° C. and 10 MPa for 80 minutes to obtain a nonflammable decorative melamine decorative board of Example 9.

  In Example 9, except that the dry film thickness of the siloxane graft type polymer coating layer (E) was set to 10 μm, the same procedure as in Example 10 was performed to form a water / oil repellent / low refractive index layer on the surface. Incombustible melamine decorative board was obtained.

  In Example 9, except that the dry film thickness of the siloxane graft type polymer coating layer (E) was changed to 50 μm, the same procedure as in Example 11 was performed to form a water / oil repellent / low refractive index layer on the surface. Incombustible melamine decorative board was obtained.

  In Example 10, ZX-007-C (hydroxyl value 58, acid value 5, solvent type; xylene / butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) was used as a siloxane graft polymer in which a fluororesin and siloxane were combined. The same procedure as in Example 12 was carried out except that a nonflammable decorative melamine decorative board having a water / oil / oil repellency / low refractive index layer formed on the surface was obtained.

  In Example 10, ZX-001 (hydroxyl value 94, acid value 0, solvent type; xylene / isobutanol, manufactured by Fuji Kasei Kogyo Co., Ltd.) is used as a siloxane graft polymer in which a fluororesin and siloxane are combined. Except that, a nonflammable decorative melamine decorative board having a water / oil / oil repellency / low refractive index layer formed on the surface was obtained.

  In Example 10, ZX-028-R (hydroxyl value 100, acid value 5, solvent type; butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) is used as a siloxane graft polymer in which an acrylic resin and siloxane are combined. Except that, a nonflammable decorative melamine decorative board having a water / oil repellent / low refractive index layer formed on the surface was obtained.

  In Example 10, ZX-022 (hydroxyl value 120, acid value 5, solvent type; xylene / butyl acetate, manufactured by Fuji Kasei Kogyo Co., Ltd.) was used as a siloxane graft polymer in which a fluororesin and siloxane were combined. Except that, a nonflammable decorative melamine decorative board having a water / oil / oil repellency / low refractive index layer formed on the surface was obtained.

  In Example 10, except that ZX-036 (hydroxyl value 119, solvent type butyl acetate / 2-propanol, manufactured by Fuji Kasei Kogyo Co., Ltd.) was used as a siloxane graft type polymer in which an acrylic resin and siloxane were combined. In the same manner, an incombustible melamine decorative board having a water / oil / oil repellency / low refractive index layer formed on the surface of Example 16 was obtained.

  In Example 10, a blocked polyisocyanate curing agent (trade name Coronate 2507, manufactured by Nippon Polyurethane Industry Co., Ltd.) was used as the curing agent, and the dry film thickness of the siloxane graft type polymer coating layer (E) was 10 μm. In the same manner, an incombustible melamine decorative board having a water / oil / oil repellency / low refractive index layer formed on the surface of Example 17 was obtained.

  In Example 10, the same procedure was carried out except that a blocked polyisocyanate-based curing agent (trade name Sumidur BL3173, manufactured by Sumika Bayer Urethane Co., Ltd.) was used as the curing agent. A nonflammable decorative melamine decorative board having a water / oil repellency / low refractive index layer was obtained.

  In Example 10, the same procedure was followed except that a blocked polyisocyanate-based curing agent (trade name Death Module BL4265SN, manufactured by Sumika Bayer Urethane Co., Ltd.) was used as the curing agent. A nonflammable decorative melamine decorative board having a water / oil repellency / low refractive index layer was obtained.

  In Example 10, a silicate-based curing agent (trade name: methyl silicate 51, manufactured by Colcoat Co., Ltd.) was used as a curing agent, and 20 parts of this was mixed with 100 parts of the main agent. Further, 7 parts of aluminum ethyl acetoacetate diisopropylate (trade name: ALCH, manufactured by Kawaken Fine Chemical Co., Ltd.) was used as a catalyst, and 20 parts of acetylacetone was added as a reaction terminator. In other respects, the nonflammable decorative melamine decorative board having the water / oil / oil repellency / low refractive index layer formed on the surface was obtained in the same manner as in Example 10.

In the same manner as in Example 9, a siloxane graft polymer coating solution (A), a melamine resin-impregnated pattern paper (B), and a prepreg (C) were produced.

A siloxane graft polymer coating solution (A) was applied to the surface of an OPP (stretched polypropylene) film having a thickness of 30 μm so as to have a dry film thickness of 0.5 μm by a bar coating method to prepare a transfer sheet. A siloxane graft polymer coating layer (E) is formed on the surface of the transfer sheet.
Subsequently, the transfer sheet, the melamine resin-impregnated pattern paper (B), the prepreg (C), the melamine resin-impregnated pattern paper (B), and the transfer sheet were laminated in this order, and hot-press molded in the same manner as in Example 9. Finally, the transfer sheet was removed to obtain a nonflammable decorative melamine decorative board having a water / oil repellent / low refractive index layer formed on the surface of Example 21.

  Except that the dry film thickness of the siloxane graft type polymer coating layer (E) in Example 21 was set to 10 μm, a water / oil / oil repellency / low refractive index layer was formed on the surface of Example 22 in the same manner. An incombustible melamine decorative board was obtained.

  The same procedure as in Example 21 was performed except that the dry film thickness of the siloxane graft polymer coating layer (E) was 50 μm, and the water / oil / oil repellency / low refractive index layer was formed on the surface of Example 23. Incombustible melamine decorative board was obtained.

  The same procedure as in Example 1 was repeated except that 10.0 parts of phenol-formaldehyde resin and 9.0 parts of amino-formaldehyde resin were used, and the surface of Example 24 was provided with a water / oil repellency / low refractive index layer. An incombustible melamine decorative board was obtained.

  The same procedure as in Example 1 was carried out except that 2.5 parts of phenol-formaldehyde resin and 2.5 parts of amino-formaldehyde resin were used, and the surface of Example 25 was provided with a water / oil repellency / low refractive index layer. An incombustible melamine decorative board was obtained.

Experimental example 1
In Example 1, except that the dry film thickness of the room temperature glass coating layer (E) was changed to 0.5 μm, the same procedure was performed to form a water / oil repellent / low refractive index layer on the surface of Experimental Example 1. Incombustible melamine decorative board was obtained.

Experimental example 2
In Example 1, the non-flammable surface was formed in the same manner as in Example 2, except that the dry film thickness of the room temperature glass coating layer (E) was 15 μm, and the surface of the surface was formed with a water / oil repellent / low refractive index layer. A decorative melamine decorative board was obtained.

Experimental example 3
In Example 9, except that the dry film thickness of the siloxane graft type polymer coating layer (E) was changed to 0.05 μm, the water repellent / oil repellent / low refractive index layer on the surface of Experimental Example 3 was formed. A formed incombustible melamine decorative board was obtained.

Experimental Example 4
In Example 9, except that the dry film thickness of the siloxane graft type polymer coating layer (E) was 150 μm, the same procedure was carried out to form a water / oil repellent / low refractive index layer on the surface of Experimental Example 4. Incombustible melamine decorative board was obtained.

Experimental Example 5
In Example 1, it implemented similarly except having changed amino-formaldehyde resin into 0.3 part.

Experimental Example 6
In Example 1, it carried out similarly except having made amino-formaldehyde resin into 21 parts.

Experimental Example 7
In Example 1, it implemented similarly except having made phenol-formaldehyde resin 13.5 parts and amino-formaldehyde resin 10.5 parts.

Experimental Example 8
Example 1 was carried out in the same manner except that 2.5 parts of phenol-formaldehyde resin and 2 parts of amino-formaldehyde resin were used.
Comparative Example 1
In order from the bottom, 1 sheet of melamine resin-impregnated pattern paper (B), 5 sheets of prepreg (C), and 1 sheet of melamine resin-impregnated pattern paper (C) are laminated and heated at a temperature of 140 ° C., a pressure of 10 MPa, and a time of 80 minutes. The decorative board of Comparative Example 1 was obtained by pressure molding.

Next, the nonflammable melamine decorative boards produced in Examples 1 to 25, Experimental Examples 1 to 8 and Comparative Example 1 were evaluated.
(Evaluation methods)
Evaluation of fingerprint resistance
1) Evaluation with actual fingerprints The fingerprints are actually attached to the surface of the substrate and checked visually.
○: The fingerprint is inconspicuous.
Δ: The fingerprint is slightly conspicuous.
X: The fingerprint is conspicuous.
2) From the viewpoint of quantification and reproducibility of evaluation with artificial fingerprint liquid, fingerprint resistance was evaluated using artificial fingerprint liquid. The evaluation method is shown below.

A 20% triolein solution is prepared using methoxypropanol as a diluent, and 4 parts of Kanto Loam is added to obtain an artificial fingerprint solution. The artificial fingerprint liquid is uniformly applied on the acrylic plate with a bar coater and dried at 100 ° C. for 3 minutes. A silicon stopper (diameter 50 mm) is placed on an acrylic plate, a load is applied at 300 g / cm ^{2 for} 10 seconds, and the artificial fingerprint liquid is transferred to the silicon stopper. Thereafter, a silicon stopper is placed on the test specimen, and a load is applied at 300 g / cm ^{2 for} 10 seconds to transfer the artificial fingerprint liquid to the test specimen. The surface color difference before and after the artificial fingerprint liquid transfer is measured, and the fingerprint resistance is evaluated by the ΔE value (small ΔE value = excellent fingerprint resistance).
Using a CA-X contact angle meter manufactured by Kyowa Interface Chemical Co., Ltd. as a contact angle device, about 5 μl of deionized water and oleic acid were placed on the substrate surface, and the contact angle at this time was measured. The contact angle was obtained by measuring five points by changing the mounting position, calculating the average value of the five points, and rounding off.
Evaluation of sharpness The sharpness of the printed pattern on the decorative board is visually confirmed by oblique light.
○: The printed pattern can be clearly confirmed.
Δ: Slight reflection and white blurring.
Measurement of refractive index The refractive index was measured with a multiwavelength Abbe refractometer DR-M2 (Atago Co., Ltd.). Measurement wavelength: 589 nm.
Measurement of abrasion resistance Measured based on JIS K 6902; 1998 (Testing method for thermosetting resin high-pressure decorative board).
Evaluation of nonflammability Exothermic test of 20-minute test using a corn calorimeter based on ISO5660. In the evaluation method, the total heat generation amount is 8 MJ / m ² or less, the maximum heat generation rate continues for 10 seconds or more and does not exceed 200 kW / m ² , and there are cracks, cracks, etc. penetrating to the back surface in the test specimen after the test. The case where there was not was set as ○. Those that did not satisfy even one of these three conditions were marked with x.
Heat-resistant adhesion: A hot body maintained at 200 ° C. was brought into contact with the surface of the decorative plate for 10 minutes.
Strength: A 500 g iron ball was dropped from 20 cm above the sample.

(Evaluation results)
Tables 1 and 2 show the evaluation results of the decorative surface.

Table 3 shows the evaluation results of nonflammability, heat-resistant adhesion, and strength.

  In Tables 1 and 2, “Coating method (1)” means a method of applying to the surface of impregnated paper in the production of a decorative board, and “Coating method (2)” means a method of using a transfer sheet. Means.

  As shown in Table 1 and Table 2, the melamine decorative boards of Examples 1 to 25 have less fingerprints, a large contact angle of water and oleic acid (having water and oil repellency), and excellent sharpness. Low refractive index and high wear resistance. Moreover, the external appearance of the melamine decorative board of Examples 1-25 was favorable, and whitening and curvature did not generate | occur | produce.

  On the other hand, in the decorative melamine board of Comparative Example 1, fingerprints were conspicuous, the contact angles of water and oleic acid were small, the sharpness was inferior, and the refractive index was large.

  Moreover, in the melamine decorative board of Experimental Example 1, the application | coating nonuniformity appeared in the external appearance and the external appearance was not favorable.

  In addition, the melamine decorative board of Experimental Example 2 had good fingerprint resistance and sharpness, but whitening was partially observed and the appearance was not good.

  Moreover, in the melamine decorative board of Experimental Example 3, application unevenness appeared in the appearance, and the appearance was not good.

Moreover, in the melamine decorative board of Experimental Example 4, the impregnated paper warped and the result was slightly inferior compared with Examples 1 to 25 in terms of handling.

Claims (6)

A non-combustible decorative board comprising a melamine resin layer and a core layer, comprising: a refractive index lower than that of the melamine resin layer, and a low refractive index layer formed above the melamine resin layer. Incombustible melamine decorative board. The incombustible melamine decorative board according to claim 1, wherein the low refractive index layer has a refractive index of 1.55 or less. The incombustible melamine decorative board according to claim 1 or 2, wherein the low refractive index layer has water and oil repellency. The nonflammable melamine decorative board according to claim 3, wherein the low refractive index layer has a water contact angle of 90 ° or more and an oleic acid contact angle of 45 ° or more. The low refractive index layer is
(A) Room temperature glass coating agent, or
The nonflammable melamine decorative board according to any one of claims 1 to 4, comprising (b) a siloxane graft type polymer in which a fluororesin or an acrylic resin and siloxane are combined as a main component. The core layer is made of a prepreg impregnated with a slurry containing, as an essential component, a phenol-formaldehyde resin, an amino-formaldehyde resin, and a metal hydroxide as an organic resin component on an inorganic fiber base material. The incombustible melamine decorative board according to any one of 1 to 5.