JP2003237012A - Wipable decorative board and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a decorative board in which a contaminant substance adhered to its surface is easily removed. <P>SOLUTION: A thermosetting resin decorative board (e.g. a melamine resin decorative board) is applied on its surface with a solution containing a polyvinyl alcohol and a water repellent (e.g. a reactive silicone oil, a non-reactive silicone oil), dried, and from which its polyvinyl alcohol film is removed from its surface. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative board, and more particularly to a wiping decorative board from which dirt can be easily removed and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, there is a decorative plate provided on a horizontal surface such as a table, a counter, a kitchen, or a vertical surface such as a wall. For example, a diallyl phthalate resin decorative plate having excellent physical properties such as abrasion resistance and impact resistance. Thermosetting resin decorative boards such as melamine resin decorative boards are widely used.

[0003]

[Problems to be Solved by the Invention] However, JIS
A stain resistance test was conducted based on the “Testing method for thermosetting resin decorative board” of K6902. As a result, even if there was no abnormality or slight change, coffee, soy sauce, etc. were actually attached. It was not able to be easily removed when it became dirty with time, magic, crayon, etc., and it did not fully meet the demand for quick wiping. In particular, if the decorative surface is embossed, you must force it to rub it with a cloth, etc. Even if the surface is flat, the surface of the metal plate is an ultra-fine surface transferred. Since it was a thing, it was not something that could easily and easily remove dirt.

[0004]

SUMMARY OF THE INVENTION The present invention has been studied in view of such circumstances and is characterized by the following. That is, the present invention, on the surface of the thermosetting resin decorative plate,
A wiping decorative board characterized in that a water repellent is transferred, a wiping decorative board in which the water repellent is a modified silicone oil, a wiping decorative board in which the modified silicone oil is a non-reactive silicone oil, To remove the polyvinyl alcohol film by applying a solution containing polyvinyl alcohol and a water repellent to the surface of the wipeable decorative board or thermosetting resin decorative board in which the non-reactive silicone oil is a polyether-modified silicone oil. A method of manufacturing a wiping decorative board characterized by comprising: 1 to 5% by weight of the water repellent in the solution; a wiping property using a modified silicone oil as the water repellent. Manufacturing method of decorative board, manufacturing method of wiping decorative board using non-reactive silicone oil as the modified silicone oil, polyether modified silicone resin as the non-reactive silicone oil A method of wiping of veneer using a corn oil. Hereinafter, the present invention will be described in detail.

[Detailed Description of the Invention] Polyvinyl alcohol used in the present invention is obtained by polymerizing a fatty acid vinyl ester such as vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate, etc. by a known technique and by using an alkali or Saponification with a saponification catalyst such as an acid, polymerization and hydrolysis of vinyl ether such as t-butyl vinyl ether, benzyl vinyl ether and the like by a known technique, and a monomer having copolymerizability with a fatty acid vinyl ester. It is obtained by saponifying a copolymer of a polymer and a fatty acid vinyl ester.

Examples of the monomer copolymerizable with fatty acid vinyl ester include methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, ( (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid decyl, (meth) acrylic acid alkyl ester such as lauryl (meth) acrylic acid, (meth) acrylic acid 2-hydroxyethyl, (meth) acrylic acid, crotonic acid, Maleic acid, itaconic acid, fumaric acid, citraconic acid, glycidyl (meth) acrylate, ethylenically unsaturated acids such as (meth) acrylic acid amide, ethylene glycol mono (meth) acrylate, ethylene glycol di (meth) acrylate ,
Examples thereof include propylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, and other ethylenically unsaturated acids having a double bond; and vinyl monomers such as acrylonitrile and vinyl chloride. In addition, "(meth) acryl" means "acryl" or "methacryl" here. As the polymerization method, solution polymerization,
Examples include bulk polymerization, pearl polymerization, and emulsion polymerization.

Preferably, a saponified product of a homopolymer of vinyl acetate, a saponified product of a copolymer of vinyl acetate and ethylene, an unsaturated acid or a salt thereof, an alkyl ester and an olefin sulfonic acid or a salt thereof is used.

The saponification degree of polyvinyl alcohol is 85.
It is necessary that the content is at least mol% and the saponification degree is 85
If it is less than mol%, it becomes difficult to form a film. The degree of saponification is particularly preferably 87 mol% or more, and the upper limit of the degree of saponification is not particularly limited as long as it is 100 mol% or less, and particularly preferably 98 mol% or less.

The average degree of polymerization of polyvinyl alcohol is not particularly limited, but is preferably 500 to 5,000,
If the average degree of polymerization is less than 500, the strength of the coating film during coating will be small, and if it exceeds 5000, the viscosity will be too high when used as an aqueous solution and coating will be difficult, such being undesirable. The lower limit of the average degree of polymerization is further preferably 800, particularly preferably 1000, and conversely, the upper limit thereof is further preferably 4000, particularly preferably 3000.

Solvents for dissolving or dispersing polyvinyl alcohol include water, solvents such as alcohols such as methanol, ethanol, isopropyl alcohol and normal butanol, aromatic organic solvents such as toluene, xylene and ethylbenzene, methyl acetate, Ethyl acetate,
Butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, methyl acetoacetate, ethyl acetoacetate, esters of methyl benzoate, etc., acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, benzohenone, acetophenone, etc. Ketones, lower paraffins such as hexane, pentane, octane, cyclohexane and decane, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl ether, propylene glycol dimethyl ether and other ethers, N, N- Amides such as dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and acetanilide; Pneumoniae, trimethylamine, triethylamine, n-butylamine, di-n-butyl amine, tri-n-butyl Ani down, aniline, N
Amine such as -methylaniline, N, N-dimethylaniline and pyridine can be used. The addition amount of these solvents is appropriately adjusted in consideration of the coating property and the film thickness of the coating film.

Examples of the water repellent used in the present invention include silicone water repellents and fluorine water repellents. The silicone water repellent includes silicone oil and silicone powder, and the silicone oil includes straight silicone oil and modified silicone oil, which may be used alone or in combination. Straight silicone oils and modified silicone oils are classified according to the type of organic substituent bonded to the silicon atom.

The straight silicone oil refers to dimethyl silicone oil, methylphenyl silicone oil and methylhydrogen silicone oil, and has a methyl group, a hydroxyl group, a phenyl group or a hydro group as a substituent. These include various types having different molecular weights.

Further, the modified silicone oil is classified into a reactive silicone oil and a non-reactive silicone oil, and further classified according to the kind of the functional group to be introduced or the position or number of the functional group to be introduced. For example, reactive silicone oils include amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, methyl-modified silicones such as dimethylpolysiloxane and methylphenylpolysiloxane that are reacted with organic groups. Examples include styryl modification and alcohol modification. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty acid ester modification, alkyl / aralkyl modification, alkyl / polyether modification, and fluoroalkyl modification.

In the present invention, any silicone oil can be used and is not particularly limited, but modified silicone oil is preferable, and non-reactive silicone oil is particularly preferable. Among them, the polyether-modified silicone oil is extremely effective in preventing dirt from adhering and wiping off. The polyether-modified silicone is produced by a method such as addition reaction of a silicone oil having a Si-H group with a polyether having a carbon-carbon double bond at its terminal, and the polyether group is a polyethylene oxide, Examples thereof include polypropylene oxide, ethylene oxide-propylene oxide, copolymers having a bisphenol structure, and the like.

As the silicone powder, a silicone rubber powder which is a fine powder of silicone rubber having a structure in which a linear dimethylpolysiloxane is crosslinked, or a three-dimensional siloxane bond represented by (CH ₃ SiO _3/2 ) n There is a silicone resin powder that is a fine powder of so-called polymethylsilsesquioxane, which has a cross-linked structure in a mesh shape, and a silicone composite powder in which the surface of a spherical silicone rubber powder is coated with silicone resin.
Also, hydrophobic silica powder, which is a synthetic silica fine powder obtained by treating the surface of spherical amorphous silica with silicone, can be used as the silicone powder. In the present invention, any of these may be used as a silicone powder for addition and blending, and these may be used alone or in combination of two or more kinds.

The silicone powder preferably has an average particle diameter of 0.1 to 10 μm in consideration of dispersibility in a polyvinyl alcohol solution and wiping property of the product.
When the average particle size is less than the lower limit, the effect on the wiping property of the product surface tends to be lessened, and when the average particle size exceeds the upper limit, dispersibility in the solution becomes poor and it becomes difficult to obtain uniform wiping property. Become.

Examples of the fluorine-based water repellent used in addition to the silicone-based water repellent include fluorine oil and fluorine howder. Fluorine oil is generally
Represented by a chemical formula in which hydrogen of a hydrocarbon is replaced by fluorine (which may contain a halogen element such as chlorine, oxygen, etc.), is a liquid or grease at room temperature and is a perfluoropolyether or perfluoroalkylpolyether. , Ethylene trifluoride polymer and the like. Particularly, a side chain or straight chain type perfluoroalkyl polyether is preferable.

The fluorine powder is a fluorine resin powder obtained by pulverizing and pulverizing a fluorine resin having a molecular structure in which carbon atoms are surrounded by fluorine atoms. Examples of the fluororesin include polytetrafluoroethylene (PTF)
E), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FE
P), ethylene / tetrafluoroethylene copolymer (E
TFE), polychlorotrifluoroethylene (PCTF
E), ethylene / chlorotrifluoroethylene copolymer (ECTFE), polyvinylidene fluoride (PVDF) and the like.

With respect to the amount of the above-mentioned water repellent, if the amount added is small, it is difficult to obtain the desired wiping performance, and if the amount added is too large, the surface of the finished product is liable to be fogged. Therefore, the addition amount of the water repellent in the solution is preferably in the range of 1 to 5% by weight.

Other components such as a release agent and a surfactant may be added to the solution, and examples of the release agent include hydrocarbon type, fatty acid type, fatty acid amide type, ester type, alcohol type, Metal soaps and the like can be used. Specific examples include hydrocarbon paraffin, liquid paraffin, natural paraffin, microwax, polyethylene wax, etc.
Fatty acid type stearic acid, lauric acid, etc., fatty acid amide type stearic acid amide, palmitic acid amide, methylene bis stearamide, ethylene bis stearoamide, etc., ester type butyl stearate, hydrogenated castor oil, ethylene glycol monostearate. In the alcohol system such as rate, cetyl alcohol, stearyl alcohol, etc.,
Examples of the metal soaps include lead stearate, zinc stearate, calcium stearate and the like.

Further, in order to improve the mixing property of the water repellent, it is effective to add a surface active agent, and as the surface active agent, an anionic surface active agent, a cationic surface active agent, an amphoteric surface active agent or an amphoteric surface active agent is used. Any nonionic surfactant is applicable and is not particularly limited. Examples of the anionic surfactant include alkyl sulfate ester salts, polyoxyethylene alkyl ether sulfate ester salts, alkylbenzene sulfonates, alkyl sulfonates, α-olefin sulfonates, fatty acid salts, α-sulfo fatty acid salts,
Examples thereof include ether carboxylic acid salts and alkyl phosphoric acid ester salts. Examples of the cationic surfactant include alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt and the like. Examples of the amphoteric surfactant include alkyl carboxy betaine and alkyl sulfobetaine. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene phenyl ether, fatty acid alkanolamide, alkyldimethylamine oxide, glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester.

If desired, a plasticizer may be used. For example, ethylene glycol and its oligomers, polyethylene glycol, propylene glycol and their oligomers, glycol derivatives such as polypropylene glycol, glycerin and its oligomers, and polyglycerin. And a glycerin derivative in which ethylene oxide, propylene oxide, etc. are added to glycerin, sorbitol, a sorbitol derivative in which ethylene oxide, propylene oxide, etc. are added to sorbitol, and the like. Among these, polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol and sorbitol, and derivatives thereof are preferably used. These plasticizers may be used alone or in combination of two or more.

The thermosetting resin decorative board to which the polyvinyl alcohol solution is applied is a decorative paper for a decorative board, a core paper for a decorative board, and, if necessary, a surface paper impregnated with a resin solution containing a thermosetting resin. , A resin-impregnated decorative paper, a resin-impregnated core paper, a resin-impregnated surface paper, etc., which are thermocompressively integrated using a flat plate press or a continuous press machine. Examples of the resin include diallyl phthalate resin, unsaturated polyester, amino-formaldehyde resin, and a mixture thereof. It is particularly preferable to use the amino-formaldehyde resin from the viewpoint of surface physical properties such as heat resistance and abrasion resistance.

As the amino-formaldehyde resin, an amino compound such as melamine, urea, benzoguanamine and acetoguanamine is reacted with formaldehyde to form an initial condensate, as well as etherification with lower alcohol such as methyl alcohol and ethyl alcohol. Those modified with a reactive modifier that promotes plasticization such as paratoluene sulfonamide can be applied.

The decorative paper has a basis weight of 20 to 200 g / m.
^{In 2} , the various kinds of patterns that are colored or printed are used, and the surface paper has a basis weight of 16 to 40 g / m ² ,
A material that becomes transparent after thermocompression molding is used.

Examples of the core paper include kraft paper, non-woven fabric, cloth, etc., which are used for decorative boards, phenol resin,
A resin liquid containing a thermosetting resin such as an unsaturated polyester resin or an amino-formaldehyde resin is impregnated and dried, and a phenol resin having excellent strength and heat resistance is particularly preferable. Phenolic resins can be obtained by reacting phenols and aldehydes with 1 mol of phenolic hydroxyl groups at a ratio of 1 to 1.3 mol of aldehydes under a basic catalyst.

Phenols include phenol, cresol, xylenol, octylphenol, phenylphenol, bisphenol A, bisphenol S, bisphenol F and the like, and aldehydes include formaldehyde, paraformaldehyde, glyoxal, trioxal and the like. If necessary, parasulfonamide, tung oil, DOP, TC
Those modified with a modifier that promotes plasticization such as P (tricresyl phosphate) can also be applied. As the basic catalyst, oxidation of alkali metals such as sodium and potassium and alkaline earth metals such as magnesium and calcium can be applied. And hydroxides, and amines such as triethylamine and triethanolamine.

The method of applying the above composition to the thermosetting resin decorative board is not particularly limited, and examples thereof include gravure coating method, gravure reverse coating, reverse roll coating,
Known methods such as roll coating, comma coating, bar coating, spray coating, air knife coating, and curtain coating can be applied, and these may be appropriately combined. The coating amount is preferably 40g / m ² ~70g / m ² in wet state, low peel strength is less than 40 g / m ^2, The film when dry - swelling occurs cosmetic plates, 70 g
If it is more than / m ² , the drying property is poor, and the formation of a polyvinyl alcohol film tends to be supported, which is not preferable.

The present invention will be described in detail below with reference to examples.

Example 1 Blending of composition (I) Amino-modified silicone 3 parts by weight (Shin-Etsu Chemical Co., Ltd.) Polyvinyl alcohol (Denki Kagaku Co., Ltd.) (Polymerization degree 3000 Saponification degree 98) Mol%) 23 parts by weight To 74 parts by weight of water, a surfactant (Chukyo Yushi Co., Ltd.) was added,
The mixture was stirred at 0 ° C. for 3 hours to obtain a polyvinyl alcohol solution (I) having a viscosity of 800 cps. Then, using a curtain flow coater, the polyvinyl alcohol solution (I) is applied to the surface of the 1.2 mm-thick melamine resin decorative board so that the application amount is 60 g / m ^{2 in a} wet state, and the coating is dried.
The polyvinyl alcohol film was removed to obtain the wiping decorative board of Example 1.

Example 2 A wiping decorative board of Example 2 was obtained in the same manner as in Example 1 except that epoxy-modified silicone was used instead of amino-modified silicone.

Example 3 Example 3 was repeated except that polyether modified silicone was used instead of amino modified silicone.
The wiping decorative board of Example 3 was obtained.

Comparative Example 1 A decorative board of Comparative Example 1 was obtained in the same manner as in Example 3, except that the blending amount of the polyether-modified silicone was changed to 0.5 part by weight.

Comparative Example 2 A decorative board of Comparative Example 2 was obtained in the same manner as in Example 3, except that the amount of the polyether-modified silicone was 6 parts by weight.

Comparative Example 3 A decorative board of Comparative Example 3 was obtained in the same manner as in Example 3 except that the polyether modified silicone was not used and the blending amount of polyvinyl alcohol was 26 parts by weight.

The evaluation results are shown in Table 1.

[Table 1]

Test method and evaluation method Wipeability: 2 coils of an oil-based pen (size about 2 cm *
Draw 3 cm) and wipe off with Kimwipe 5 seconds later, once when there is no color residue. Repeatedly measure the number of passes. ⊚ passed 2 times or more, ◯ passed once, △ There is no stain soaking, but it is difficult to wipe it off, × means stain is soaking in. Stain resistance: According to the JISK6902 stain resistance test. ◎ means no pollution. ◯: Contaminating material was contaminated with 1% iodine alcohol solution and 2% mercury chrome aqueous solution. △
Is contaminated with 1% iodine alcohol solution, 2% mercury chrome aqueous solution, crayons, and shoes. × indicates that the pollutant material in most parts is contaminated. Water repellency: Measured with a contact angle meter (model CA-X) of Kyowa Interface Science Co., Ltd., image processing type 3-point click method. Principle of measurement / A liquid sample is taken out from the tip of a needle and brought into contact with an individual sample to form a droplet, and the coordinates of the left end (L) and right end (R) of the droplet and the vertex (T) are obtained. The droplet diameter (2r) and height (h) are obtained from the three points L, R, and T, and the contact angle θ is calculated from the following equation. Tan θ = h / r → θ = 2 Tan-1 (h / r) ◯ is θ of 71 ° or more, Δ is 60 to 70 °, × is less than 60 Cellotape (registered trademark) resistance; Office cellophane tape including air Make sure not to stick it and rub the back surface strongly. Attach the tape and pull it off at an angle of about 45 degrees within 15 minutes. If peeling is not recognized, it is judged as pass ◯, and if there is no abnormality in appearance, it is judged as pass ×. Heat resistance: According to the heat resistance test specified in JIS K6902. ◎ indicates no abnormality, ◯ indicates slight fading, △ indicates gloss change, color change × indicates swelling, and marked discoloration. Surface haze: Condition of the surface of the decorative plate after peeling off the polyvinyl alcohol foil ○: no cloudiness, △: slight clouding, ×: clouding.

[0037]

EFFECTS OF THE INVENTION Since the decorative surface of the wiping decorative board obtained by the present invention is coated with the water-repellent resin, the amount of contaminants attached is greatly reduced due to the low surface free energy effect. Therefore, water repellency, oil repellency, antifouling property, etc. are improved.

Further, it is difficult for contaminants such as soy sauce, oil, cosmetics, magic, and crayons to adhere, and even if such contaminants adhere, the labor and time required for removing the dirt are not required. It is very convenient from a practical point that contaminants can be easily and easily removed by cleaning by wiping with a dry cloth or washing with water. Therefore, the wiping decorative board of the present invention can be widely used for vertical surfaces such as toilets, kitchens, and furniture.

Further, by adding a substance having water repellency such as silicone to the polyvinyl alcohol solution having viscosity as in the present invention, a coating machine can be used uniformly on the decorative surface of the thermosetting resin decorative plate. Can be applied by
The water-repellent substance can be fixed by drying with hot air. Further, the polyvinyl alcohol film has extremely weak adhesion strength to the decorative surface of the thermosetting resin decorative plate, and can be easily peeled by hand after drying with hot air.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F006 AA33 AA35 AB20 AB39 BA11                       DA04 EA05                 4F100 AH06A AK01A AK52A AL06A                       BA01 CA30A EC04A HB00A                       JB13A JK14 JL06

Claims (9)

[Claims] 1. A wiping decorative board characterized in that a water repellent is transferred onto the surface of a thermosetting resin decorative board. 2. The wiping decorative board according to claim 1, wherein the water repellent is a modified silicone oil. 3. The wiping decorative board according to claim 2, wherein the modified silicone oil is a non-reactive silicone oil. 4. The non-reactive silicone oil is a polyether-modified silicone oil.
The wiped decorative plate described. 5. A method for producing a wiping decorative board, which comprises applying a solution containing polyvinyl alcohol and a water repellent to the surface of the thermosetting resin decorative board and drying the solution to remove the polyvinyl alcohol film. 6. The method for producing a wiping decorative board according to claim 5, wherein the water repellent is contained in the solution in an amount of 1 to 5% by weight. 7. The method for producing a wiping decorative board according to claim 5, wherein a modified silicone oil is used as the water repellent. 8. The method for producing a wiping decorative board according to claim 7, wherein a non-reactive silicone oil is used as the modified silicone oil. 9. The method for producing a wipeable decorative board according to claim 8, wherein a polyether-modified silicone oil is used as the non-reactive silicone oil.