JP2003311910A - Decorative material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative material which has a function capable of wiping off (wiping out) a contaminant of subsistence commodities such as aqueous magic inks, oily magic inks, soy sauce, sauce and coffee with a dry cloth such as a cloth and a tissue paper. <P>SOLUTION: The decorative material is characterized by forming a liquid repellent rigid resin layer on a decorative layer prepared by impregnating it with a melamine resin and curing it, and incorporating a melamine resin and/or a silicone resin in a crosslinked cure product of an ionized radiation-curable resin in the liquid repellent rigid resin layer. <P>COPYRIGHT: (C)2004,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative material,
For more information, see Water-based magic ink, oil-based magic in
Wipeability of contaminants such as ki, soy sauce, sauce and coffee
Related to cosmetic materials that are useful for applications that require
Things. [0002] 2. Description of the Related Art Conventionally, a high-pressure melamine decorative board (JP-B-26)
-4540), low-pressure melamine decorative board (JP-B-37)
-6143), DAP decorative board, polyester makeup
Thermosetting decorative boards such as boards are known. [0003] These thermosetting decorative boards have impact resistance and
Has excellent properties in stainability, pencil hardness, etc.
However, in real life, the floor, walls,
Water-based magic ink, oil-based magic
Of household goods such as ink, soy sauce, sauce and coffee
Dyes can be removed with a dry wipe such as cloth or tissue paper
Such a function is also required. [0004] However, the above thermosetting properties
Decorative veneers range from high hardness to flexible veneers.
There are various types of decorative boards,
Thermosetting decorative boards are also available in water-based magic inks and oil-based magic
Contaminants in daily necessities such as ink, soy sauce, sauces and coffee
If quality is present, wipe with a cloth or tissue paper.
There is a problem that it is difficult to wipe off. An object of the present invention is to provide an aqueous magic ink, an oil,
For everyday use such as sex magic ink, soy sauce, sauce, coffee
To provide cosmetic materials with good wiping properties of contaminants by products
Is Rukoto. [0006] The present invention solves the above problem.
As a result of thorough examination to decide, impregnation with melamine resin
A liquid-repellent hard resin layer on the decorative layer
The liquid-repellent hard resin layer is made of an ionizing radiation-curable resin.
Melamine resin and / or silicone resin in the crosslinked cured product
That the cosmetic material is characterized by containing
And completed the present invention. The present invention relates to a method of impregnating a melamine resin and curing the resin.
A liquid-repellent hard resin layer on the decorative layer
The liquid-repellent hard resin layer is formed of a frame of ionizing radiation-curable resin.
Melamine resin and / or silicone resin in the cured bridge
It relates to a cosmetic material characterized by comprising
You. [0008] BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described.
A description will be given of an embodiment of the present invention. First, a method for producing the above-mentioned decorative material of the present invention
Will be described. First, on the decorative layer, a liquid-repellent hard tree
By applying (applying) grease and irradiating with ionizing radiation
To form a liquid-repellent hard resin layer. Like this
The laminated product was inserted between hot plates of a hot press, and the pressure was 80
120kg / cm^Two, Hot platen temperature 150-200 ° C, 3
Press molding for 0 minutes to 2 hours to produce the cosmetic material of the present invention
Is what you do. The above-mentioned decorative layer has a rice basis weight of 100 g / m 2.
^TwoOf titanium paper with pattern printing, if necessary
Decorative paper impregnated with uncured melamine resin
Become a su. Usually, no melamine resin is present on the decorative paper.
Transparent paper impregnated with a cured product (30-100 g of rice basis weight)
/ M^Two) On the back of the decorative paper
Is a core paper impregnated with uncured phenolic resin
Are laminated. A liquid-repellent hard resin is applied on the decorative layer.
(Coating), gravure coater, roll coater
(Size press, gate roll coater, etc.), bar coater
Coating of air coaters, air knife coaters, blade coaters, etc.
Machine can be used. The coating amount is usually the weight after drying.
0.1-100 g / m^Two, Preferably 0.5 to 60 g
/ M^TwoIt is. Drying is performed by heating with hot air or the like.
This drying temperature varies depending on the type of dryer.
However, the temperature inside the dryer is usually 50 to 200 ° C,
Preferably it is 70-150 degreeC. With these coating machines,
When a liquid hard resin is applied, the film thickness depends on the coating machine.
Although different, it is usually 0.1 to 100 μm, preferably
Is 0.5 to 60 μm. The above liquid-repellent hard resin is curable with ionizing radiation.
In resin, melamine resin and water repellent material, if necessary
A solvent (10 to 40% by mass based on the resin) is added,
It is made by mixing and stirring. The ionizing radiation-curable resin is specifically
Has a polymerizable unsaturated bond or epoxy group in the molecule.
Prepolymers, oligomers and / or monomers
Appropriately mixed, curable composition by ionizing radiation
You can. Here, ionizing radiation means electromagnetic waves or charges.
Energy that can polymerize or crosslink molecules of the electron beam
Means quantum energy, usually ultraviolet or electron
Lines are used. Examples of the above prepolymers and oligomers
Is, for example, a condensate of an unsaturated dicarboxylic acid and a polyhydric alcohol.
Unsaturated polyesters, polyester methacrylate,
Polyether methacrylate, polyol methacrylate
Methacrylates such as melamine methacrylate,
Ester acrylate, epoxy acrylate, urethane
Tan acrylate, polyether acrylate, polio
Acryle such as cellulose acrylate and melamine acrylate
And cationic polymerization type epoxy compounds. As the urethane acrylate, for example,
Reacting polyether diol with diisocyanate
Polyether-based urethane (meth) aclay
G. The above polyether-based urethane (meth) a
Examples of diisocyanates used in acrylates include
For example, isophorone diisocyanate, dicyclohexyl
Methane diisocyanate, hexamethylene diisocyanate
Salt, diphenylmethane diisocyanate, tolylenedi
And isocyanate. The above polyether di
As an all, polyoxy with a molecular weight of 500-3000
Cypropylene glycol, polyoxyethylene glycol
And polyoxytetramethylene glycol.
You. Hereinafter, a production example of urethane acrylate is shown.
You. Equipped with dropping funnel, thermometer, reflux condenser and stirring rod
In a glass reaction vessel
1000 parts of melalene glycol and isophorone diisocyanate
And 444 parts of anate and reacted at 120 ° C. for 3 hours.
After cooling, the mixture was cooled to
Add 232 parts by weight of acrylate, and
Reaction until the thio group disappears, and urethane acrylate
was gotten. The monomers used in the ionizing radiation-curable resin
Examples include styrene and α-methylstyrene.
Monomer, methyl acrylate, 2-ethyl acrylate
Lehexyl, methoxyethyl acrylate, butyl acrylate
Toxiethyl, butyl acrylate, methoxy acrylate
Acrylic esters such as butyl and phenyl acrylate
, Methyl methacrylate, ethyl methacrylate, methacrylate
Propyl acrylate, methoxyethyl methacrylate, methacrylate
Ethoxymethyl acrylate, phenyl methacrylate, methac
Methacrylic esters such as lauryl acrylate, acrylic
Acid-2- (N, N-diethylamino) ethyl, memetac
2- (N, N-dimethylamino) ethyl acrylate
2- (N, N-dibenzylamino) methyl acrylate
2- (N, N-diethylamino) propyl acrylate
Substituted amino alcohol esters of unsaturated carboxylic acids,
Unsaturated carboxylic acids such as rilamide and methacrylamide;
Mid, ethylene glycol diacrylate, propylene
Glycol diacrylate, propylene glycol dia
Acrylate, neopentyl glycol diacrylate,
1,6 hexanediol diacrylate, triethylene
Compounds such as glycol diacrylate, dipropylene
Recall diacrylate, ethylene glycol diacrylate
Rate, propylene glycol dimethacrylate, diee
Multifunctional compounds such as Tylene glycol dimethacrylate
Having two or more thiol groups in the product and / or molecule
Polythiol compounds such as trimethylolpropane
Trithioglycolate, trimethylolpropane trichi
Opropylate, pentaerythritol tetrathiogly
Call and the like. Usually, one or more of the above compounds may be used if necessary.
Or a mixture of two or more, but ionizing radiation curable
In order to give the resin normal coatability,
5% by weight or more of the monomer or polythiol,
And / or 95% by weight or less of polythiol.
Good. When selecting the monomer, the flexibility of the cured product
If paintability is required, the
Reduce the amount of nomer, mono- or bifunctional
Use a related monomer to make the structure of relatively low crosslink density.
You. In addition, the cured product must have wear resistance, heat resistance, solvent resistance, etc.
If required, the goods shall be within the range that does not affect the suitability for coating.
If the amount of
By using a nomer, a structure with a high crosslinking density can be obtained.
it can. In addition, a monofunctional monomer and a trifunctional or higher monomer
To adjust coating suitability and physical properties of the cured product
You can also. The monofunctional acrylate monomer as described above
As 2-hydroxyacrylate, 2-hexyl
Acrylate, phenoxyethyl acrylate, etc.
I can do it. In addition, ethylene bifunctional acrylates
Recall diacrylate, 1,6-hexanediol di
Acrylate, etc., is also a trifunctional or higher acrylate.
The trimethylolpropane triacrylate, pen
Taerythritol tri (tetra) acrylate, dipen
Taerythritol hexaacrylate and the like. Further, the ionizing radiation-curable resin includes a cured product.
Radiation for adjusting physical properties such as flexibility and surface hardness
A non-curable resin can be added. In addition, the ionization
Urethane-based, cellulose-based, poly
Ester, acrylic, butyral, polyvinyl chloride
, Thermoplastic resin such as polyvinyl acetate is used, especially
Cellulose, urethane and butyral are flexible
preferable. Also, the ionizing radiation-curable resin having the above composition
Irradiate ultraviolet or visible light to cure fat
In such cases, acetophenones,
Nzophenones, Michler benzoyl benzoate, α
-Aminoxime ester, tetramethylthiuram monosa
Sulfide, thioxanthones, aromatic diazonium
Salt, aromatic sulfonium salt, metallocene, and photopolymerization
N-butylamine and triethylamine as enhancers (sensitizers)
Min, tri-n-butylphosphine, etc.
Can be used. As the water repellent material, various known substances can be used.
Is used. For example, fluorine resin, silicone resin,
C (wax) or a mixture of these can also be used
You. The amount of water-repellent material added is 1 to 10
Add parts by volume. Examples of the above fluororesin include fluororesin
Polymers of monomers, specifically, Polyvinyl fluoride (PVF) Polyvinylidene fluoride (PVdF) Polychlorinated trifluoroethylene (PCTFE) Polytetrafluoroethylene (PTFE) And two or more containing one or more fluororesin monomers
A copolymer of monomers, specifically, Tetrafluoroethylene / hexafluoropropylene copolymer (FE
P) Ethylene / tetrafluoroethylene copolymer (ETFE) Ethylene chloride / trifluoroethylene copolymer (ECTF
E) Tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride
Den copolymer Tetrafluoroethylene perfluoroalkyl ether
Copolymer (PFA) Fluoroethylene / vinyl ether copolymer (FEVE) Tetrafluoroethylene, hexafluoropropylene,
Perfluoroalkyl vinyl ether copolymer (EP
E) And the like. As the silicone resin, for example,
Rutrichlorosilane, methyltribromosilane, methyl
Trimethoxysilane, methyltriethoxysilane, methyl
Rutriisopropoxysilane, methyltri-t-butoxy
Silane; ethyltrichlorosilane, ethyltribromide
Orchid, ethyltrimethoxysilane, ethyltriethoxy
Silane, ethyltriisopropoxysilane, ethyltri
t-butoxysilane; n-propyltrichlorosilane;
n-propyltribromosilane, n-propyltrimeth
Xysilane, n-propyltriethoxysilane, n-propyl
Propyl triisopropoxysilane, n-propyl tri-t
-Butoxysilane; n-hexyltrichlorosilane, n
-Hexyltribromosilane, n-hexyltrimethoxy
Sisilane, n-hexyltriethoxysilane, n-hex
Siltriisopropoxysilane, n-hexyltri-t-
Butoxysilane; n-decyltrichlorosilane, n-de
Siltribromosilane, n-decyltrimethoxysila
N-decyltriethoxysilane, n-decyltriy
Sopropoxysilane, n-decyltri-t-butoxysila
N-octadecyltrichlorosilane, n-octade
Siltribromosilane, n-octadecyltrimethoxy
Silane, n-octadecyltriethoxysilane, n-o
Kutadecyl triisopropoxysilane, n-octadecyl
Rutri-t-butoxysilane; phenyltrichlorosila
, Phenyltribromosilane, phenyltrimethoxy
Silane, phenyltriethoxysilane, phenyltrii
Sopropoxysilane, phenyltri-t-butoxysila
Dimethoxydiethoxysilane; dimethyldichlorosi
Orchid, dimethyldibromosilane, dimethyldimethoxy
Orchid, dimethyldiethoxysilane; diphenyldichloro
Silane, diphenyldibromosilane, diphenyldimethoate
Xysilane, diphenyldiethoxysilane;
Tildichlorosilane, phenylmethyldibromosilane,
Phenylmethyldimethoxysilane, phenylmethyldie
Toxysilane; trichlorohydrosilane, tribromhi
Drosilane, trimethoxyhydrosilane, triethoxy
Hydrosilane, triisopropoxyhydrosilane, tri
t-butoxyhydrosilane; vinyltrichlorosilane,
Vinyltribromosilane, vinyltrimethoxysilane,
Vinyl triethoxysilane, vinyl triisopropoxy
Silane, vinyltri-t-butoxysilane; γ-glycid
Xypropylmethyldimethoxysilane, γ-glycidol
Cypropylmethyldiethoxysilane, γ-glycidoxy
Propyltrimethoxysilane, γ-glycidoxypropyl
Rutriethoxysilane, γ-glycidoxypropyl tri
Isopropoxysilane, γ-glycidoxypropyl tri
t-butoxysilane; γ-methacryloxypropyl
Tyldimethoxysilane, γ-methacryloxypropyl
Methyldiethoxysilane, γ-methacryloxypropyl
Rutrimethoxysilane, γ-methacryloxypropyl
Triethoxysilane, γ-methacryloxypropyl
Lysopropoxysilane, γ-methacryloxypropyl
Rutri-t-butoxysilane; γ-aminopropylmethyl
Dimethoxysilane, γ-aminopropylmethyldiethoxy
Sisilane, γ-aminopropyltrimethoxysilane, γ
-Aminopropyltriethoxysilane, γ-aminopro
Piltriisopropoxysilane, γ-aminopropyl
Tert-butoxysilane; γ-mercaptopropylmethyl
Dimethoxysilane, γ-mercaptopropylmethyldie
Toxic silane, γ-mercaptopropyl trimethoxy
Orchid, γ-mercaptopropyltriethoxysilane, γ
-Mercaptopropyltriisopropoxysilane, γ-
Mercaptopropyltri-t-butoxysilane; β-
(3,4-epoxycyclohexyl) ethyltrimethoxy
Sisilane, β- (3,4-epoxycyclohexyl)
Tiltriethoxysilane; and their partial hydrolysis
And mixtures thereof. [0027] As the above solvent, paints, inks and the like are used.
Commonly used ones can be used.
Aromatic hydrocarbons such as acetone and xylene, acetone, methyl ether
Tyl ketone, methyl isobutyl ketone, cyclohexano
Ketones, ethyl acetate, isopropyl acetate, acetic acid
Acetates such as butyl and amyl acetate, methyl alcohol
Coal, ethyl alcohol, n-propyl alcohol,
i-propyl alcohol, n-butyl alcohol, i-
Butyl alcohol, 2-ethylbutanol, 2-ethyl
Alcohols such as hexanole, dioxane, tetra
Ethers such as hydrofuran and diisopropyl ether
, Water and mixtures of two or more of these. A preferred embodiment of the method for producing a cosmetic material of the present invention
As an embodiment, first, the uncured melamine resin is impregnated.
Melamine resin on the surface of overlay paper
10 to 50 parts by mass of a silicone resin and / or
1 to 5 parts by mass of fluorine resin and urethane acrylate prepoly
Polymer, polyester acrylate and / or epoxy resin
Electron beam curing type with 50 to 85 parts by mass of acrylate
5-30 g / m of paint ^Two(After drying) applied, accelerating voltage 17
Irradiate 3 Mrad with an electron beam of 5 ev, and the electron beam curing type
Do not crosslink and cure the paint to form a liquid-repellent hard resin layer.
Prepare an overlay to Next, phenol resin
100 g of rice basis weight on a core paper impregnated with a cured product
/ M^TwoImpregnated with uncured melamine resin on titanium paper
The decorative paper consisting of
Place the side of the overlay where the liquid-repellent hard resin layer is not formed
These laminates are inserted between the hot plates of a hot press
Force 100kg / cm^Two, Hot platen temperature 170 ° C, 1 hour
We perform less molding and produce cosmetics. Evaluate wiping properties
As a magic contamination test, oil-based black magic
Apply to the surface of the cosmetic material on which the liquid-repellent hard resin layer is formed, and dry after 1 minute
Test whether it can be wiped off with a damp cloth
You. [0029] The present invention will be further described with reference to examples.
You. Embodiment 1 Overlay paper impregnated with uncured melamine resin
On the surface layer of the melamine resin uncured material 100 parts by mass,
3 parts by weight of silicone resin and urethane acrylate prepoly
10 parts by weight of an electron beam-curable coating material
g / m^Two(After drying) applied, electron beam with accelerating voltage of 175 ev
Is irradiated with 3Mrad, and the electron beam-curable paint is cross-linked and cured.
To form a liquid-repellent hard resin layer
Prepare Then, impregnated with uncured phenolic resin
100 g / m2 of rice basis weight on core paper^TwoTitanium
Decorative paper made by impregnating paper with uncured melamine resin
Layer, on the decorative paper, the overlay prepared in advance.
The surface on which the liquid-repellent hard resin layer is not formed is placed, and
Is inserted between the hot plates of the hot press, and the pressure is 100 kg / c.
m^TwoHot plate temperature 170 ° C, press molding for 1 hour,
Manufacture cosmetics. As a magic contamination test, oily black
Apply magic on the side of the cosmetic material where the liquid-repellent hard resin layer is formed,
After one minute, it could be wiped off with a dry cloth. Embodiment 2 Overlay paper impregnated with uncured melamine resin
On the surface layer of 50 parts by mass of the uncured melamine resin.
3 parts by weight of nitrogen resin and 25 parts by weight of polyester acrylate
And 25 parts by mass of epoxy acrylate.
10 g / m of wire-curable paint^Two(After drying)
Irradiation of 3 Mrad with an electron beam having a pressure of 175 ev
Crosslinks and cures curable paint to form a liquid-repellent hard resin layer
Prepare an overlay to be created. Then phenol
On a core paper impregnated with uncured resin, rice basis weight 1
00g / m^TwoContains uncured melamine resin
Lay the soaked decorative paper, and prepare it in advance on the decorative paper.
The side of the overlay where the liquid-repellent hard resin layer is not formed is
And insert these laminates between the hot plates of a hot press.
And pressure 100kg / cm^Two, Hot platen temperature 170 ° C, 1
Performs time press molding to produce decorative materials. Magic dirty
As a dyeing test, oil-based black magic was applied to the liquid repellent hard
Apply to the resin layer side and wipe off with a dry cloth after 1 minute
I was able to. Comparative Example 1 In Example 1, the silicon resin was added to the electron beam-curable paint.
Except not adding fat, it manufactures like Example 1.
Cosmetic materials. As a magic contamination test, use oil-based black magic.
Hardwood made by cross-linking and curing electron beam-curable paint for cosmetics
Apply to the oil layer side and wipe it off with a dry cloth after 1 minute
I tried but could not wipe it. [0033] The melamine resin of the present invention is impregnated and cured.
A liquid-repellent hard resin layer on the decorative layer
The liquid-repellent hard resin layer is formed of a frame of ionizing radiation-curable resin.
Melamine resin and / or silicone resin in the cured bridge
According to the cosmetic material containing, aqueous magic ink, oil
For everyday use such as sex magic ink, soy sauce, sauce, coffee
Wipe off contaminants on the product with a cloth or tissue paper.
With a function that can be wiped off (wiped off)
A cosmetic material can be provided.

Continuation of front page    F term (reference) 2E110 AA65 AB04 AB05 AB23 BA02                       GB42W                 2E220 AA07 AA15 EA02 FA05 GA22X                       GB32X                 4F100 AB12 AH06B AK01B AK25                       AK33 AK36A AK36B AK79B                       AL05B BA02 DG10 EJ08                       EJ082 EJ17 EJ172 EJ42                       EJ422 EJ53 EJ532 EJ82                       EJ822 GB08 GB81 GB90                       HB00A JB12B JB14B JL06                       JL10A

Claims (1)

Claims: 1. A liquid-repellent hard resin layer is formed on a decorative layer formed by impregnating and curing a melamine resin, and the liquid-repellent hard resin layer is cured by ionizing radiation. A decorative material characterized in that a melamine resin and / or a silicone resin are contained in a crosslinked cured product of a hydrophilic resin.