JP4765132B2 - Cosmetic material and method for producing cosmetic material - Google Patents

Cosmetic material and method for producing cosmetic material Download PDF

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Publication number
JP4765132B2
JP4765132B2 JP19816899A JP19816899A JP4765132B2 JP 4765132 B2 JP4765132 B2 JP 4765132B2 JP 19816899 A JP19816899 A JP 19816899A JP 19816899 A JP19816899 A JP 19816899A JP 4765132 B2 JP4765132 B2 JP 4765132B2
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Japan
Prior art keywords
paper
layer
thermosetting resin
surface
base material
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JP19816899A
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Japanese (ja)
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JP2001018331A (en
Inventor
正樹 塚田
潔 川井
一郎 川幡
一弘 高橋
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大日本印刷株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a decorative material used for a building interior material such as a wall, a fitting such as a door, and a surface material of furniture such as a bag.
[0002]
[Prior art]
Conventionally, a paper substrate is used as a substrate, and in order to impart scratch resistance and stain resistance, a pattern layer is formed on the surface of the paper substrate by printing or the like, and then a cross-linked product of ionizing radiation curable resin. A cosmetic material formed by forming a surface protective layer made of is known.
[0003]
For example,
1) In Japanese Patent Publication No. 49-31033, a pattern layer is formed on a paper-based substrate, and an unsaturated polyester prepolymer coating is formed on the outermost surface thereof to form a coating film. A cosmetic material is described which is crosslinked and cured with an electron beam or ultraviolet rays to form a surface protective layer.
[0004]
2) In addition, in Japanese Patent No. 2856862, a picture layer is formed on a paper-based substrate, and a (meth) acrylate prepolymer, a (meth) acrylate monomer and a silicone acrylate lubricant are formed on the outermost surface thereof. A cosmetic material is described in which a coating film is formed by coating a paint containing, and the coating film is crosslinked and cured with an electron beam or ultraviolet rays to form a surface protective layer.
[0005]
3) Furthermore, JP-A-8-183147 describes a decorative sheet having abrasion resistance as a surface protective layer.
[0006]
[Problems to be solved by the invention]
However, although these decorative materials have a surface protective layer on the surface, they have insufficient scratch hardness, and there is a problem that dents are likely to occur when pressed from the surface of the decorative material with a pencil or the like.
[0007]
Therefore, the present invention is a cosmetic material in which a paper base material is laminated on a base material in order to solve such problems, and has excellent scratch hardness and is pressed with a pencil or the like from the surface of the cosmetic material. An object is to provide a cosmetic material that is less prone to dents.
[0008]
[Means for Solving the Problems]
  The present invention, first,The paper base layer having a pattern layer on the surface, and a universal hardness value of 150 to 1,000 N / mm on the back side of the paper base layer 2 A thermosetting resin layer comprising a paper-based substrate portion containing the thermosetting resin formed by impregnating the thermosetting resin composition, and a substrate formed on the back side of the thermosetting resin layer A paper base layer containing a thermosetting resin on the back side of the paper base layer, and a paper base portion not containing a thermosetting resin. BecomeProvide cosmetic materials.
[0009]
  The decorative material of the present invention preferably has a surface protective layer on the outermost surface, and the surface protective layer is more preferably made of an ionizing radiation curable resin.
[0010]
  Also according to the invention,A step of impregnating the back surface of the paper-based substrate with the thermosetting resin composition; and the base material on the surface impregnated with the thermosetting resin composition in an uncured state of the thermosetting resin composition.The thermosetting composition is laminated and heat-laminated, and at least a back surface portion in the paper base material contains the thermosetting resin at least on the back surface of the paper base material. Layer andForming, andForming a pattern layer on the surface side of the paper-based substrateManufacturing method of cosmetic materialIs provided.
[0012]
  The first invention isThe paper base layer having a pattern layer on the surface, and a universal hardness value of 150 to 1,000 N / mm on the back side of the paper base layer 2 A thermosetting resin layer comprising a paper-based substrate portion containing the thermosetting resin formed by impregnating the thermosetting resin composition, and a substrate formed on the back side of the thermosetting resin layer A paper base layer containing a thermosetting resin on the back side of the paper base layer, and a paper base portion not containing a thermosetting resin. BecomeThis is a cosmetic material characterized by that.
[0013]
Since the decorative material of the present invention has such a thermosetting resin layer, it has a structure in which dents are unlikely to occur even when pressed from the surface of the decorative material with a pencil or the like.
[0014]
Further, when the decorative material of the present invention has a surface protective layer, preferably a surface protective layer made of an ionizing radiation curable resin, on its outermost surface, it also has excellent scratch resistance.
[0015]
  2nd invention is a manufacturing method of the cosmetics of said 1st invention, Comprising:A step of impregnating the thermosetting resin composition on the back surface of the paper-based substrate; and heating the substrate on the surface impregnated with the thermosetting resin composition in an uncured state of the thermosetting resin composition. Lamination processIt is characterized by having.
[0016]
According to 2nd invention, a base material can be stuck on a paper-type base material, without using an adhesive agent separately. Conventionally, it was common to stick a paper base material and a base material using an adhesive or the like, but according to the present invention, the back surface of the paper base material was impregnated with a thermosetting resin composition. Thereafter, the base material and the back side of the paper base material are superposed and heat laminated (hot press) to form the thermosetting resin layer, and at the same time, the paper base material and the base material can be adhered. .
[0017]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the decorative material of the present invention will be described in detail.
The decorative material of the present invention is basically impregnated with a thermosetting resin composition on the back side of the paper base layer 1 and on the back side of the paper base layer 1 as shown in FIG. And the base material layer 3 formed on the back side of the thermosetting resin layer 2. In the present invention, the back surface of the paper-based substrate layer 1 and the back surface of the thermosetting resin layer 2 are the surfaces on the side where the decorative material is installed, that is, the pattern layer 4 and the surface protective layer 5 described later. The surface on the opposite side to the surface on the other side.
[0018]
In the decorative material of the present invention, the paper-based base material layer 1 contains a thermosetting resin in at least a part of the back side thereof. That is, the paper-based substrate layer 1 may be composed of a paper-based substrate portion 1 ″ containing a thermosetting resin on the back side and a paper-based substrate portion 1 ′ not containing a thermosetting resin. The thermosetting resin may be contained in the entire paper substrate 1.
[0019]
As the paper-based substrate 1, for example,
(1) Paper such as thin paper, kraft paper, fine paper, linter paper, baryta paper, sulfate paper, Japanese paper,
(2) Nonwoven fabric made of inorganic fibers such as glass fibers, asbestos, potassium titanate fibers, alumina fibers, silica fibers, carbon fibers, or organic fibers such as polyester resins and vinylon fibers,
(3) The paper of the above (1) can be a mixed paper obtained by mixing inorganic fibers such as glass fibers or organic fibers such as polyester resins and vinylon fibers.
[0020]
In addition, when these paper-type base materials are paper, flame retardants, such as aluminum hydroxide powder, can also be added. The basis weight of the paper base is usually 20 to 120 g / m.2Degree.
[0021]
Further, a laminate of the same or two or more kinds of the above-mentioned paper-based substrates can be used as the paper-based substrate 1.
[0022]
The paper substrate 1 can be colored by itself using a colorant. On the paper substrate 1, for example, as shown in FIG. 1B, a pattern layer is formed on the paper substrate 1. 4 is preferably formed. The pattern layer 1 is formed in order to improve the decorativeness (giving a design effect) of the decorative material.
[0023]
The pattern layer 4 can be provided, for example, by printing a pattern on the paper base 1. The pattern can be formed with ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, gravure offset printing, and ink jet printing. The applied amount of ink (paint) is usually 1 to 10 g / m.2(When dry)
[0024]
Examples of the pattern include a wood grain pattern, a stone pattern, a texture pattern, a tile-like pattern, a brick-like pattern, a leather-drawn pattern, a geometric pattern, a character symbol, or a solid pattern, or a combination of these patterns (for example, a solid pattern / Wood grain pattern).
[0025]
As the ink or paint, a vehicle composed of a binder resin or the like, a colorant such as a pigment or a dye, and a mixture of an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like as necessary are used. be able to.
[0026]
Examples of the binder include cellulose resins such as nitrocellulose, cellulose acetate, and cellulose acetate, urethane resins, acrylic resins, vinyl chloride-vinyl acetate copolymers, polyester resins, and the like, or a mixture of two or more of these. be able to.
[0027]
Examples of the colorant include inorganic pigments such as titanium white, yellow lead, carbon black, nickel titanium yellow, dial, ultramarine blue, organic pigments such as quinacridone, isoindolinone, phthalocyanine, bisazo dye, monoazo dye, and titanium dioxide coating. Bright pigments such as foil powders such as mica and aluminum, or other dyes can be used.
[0028]
In addition, a concavo-convex pattern can be embossed on the surface of the paper-based substrate 1, and further, colored ink can be filled in the embossed recesses by a wiping method.
[0029]
The decorative material of the present invention has a thermosetting resin layer 2 on the back side of the paper-based substrate 1. The thermosetting resin resin layer 2 imparts a predetermined hardness to the decorative material, and plays a role of preventing the decorative material from being dented, for example, when a pencil or the like is pressed from the surface of the decorative material. Further, the thermosetting resin resin layer 2 also serves to adhere the paper base material 1 and the base material 3.
[0030]
The thermosetting resin is preferably a resin having a universal hardness value of about 150 to 1,000. When the universal hardness is less than 150, for example, when a pencil or the like is pressed against the surface of the decorative material, the hardness sufficient to withstand it is not obtained, and the entire decorative material is dented, and the initial effect is obtained. Absent. On the other hand, when it exceeds 1,000, the curing shrinkage of the thermosetting resin is large, and the adhesion strength with the substrate is inferior.
[0031]
In the present invention, as a value of universal hardness, a thermosetting resin composition (thermosetting resin composition liquid) is applied on a glass plate to a thickness of 50 μm using a bar coater. A thermosetting resin layer obtained by thermosetting by heating at 170 ° C. for 3 minutes is obtained from a value measured with a Fischer scope H100V (manufactured by H. Fisher).
[0032]
The actual measurement uses a Vickers pyramid indenter as an indenter, and a load of 20 mN (Newton) every 6 seconds from the surface of the resin layer until the thermosetting resin layer formed on the glass plate undergoes irreversible elastic deformation. The measurement is performed by measuring the load value and the penetration depth of the indenter at that time.
[0033]
Maximum load value (Fmax) And maximum penetration depth (hmax), HU = F (N) /26.43h2 [mm2] (Where F (N) represents the maximum value of load and h (mm) represents the maximum value of penetration depth), and universal hardness (HU) can be calculated.
[0034]
As for the universal hardness test, the provisional standard DIN HU-1 and the VDI / VDE standard 2626 sheet ("Materials Testing Technology", Vol. 43, No. 2, April 1998 issue, and this document) (See references cited in).
[0035]
The thermosetting resin constituting the thermosetting resin layer 2 is generally a mixture of low-molecular monomers and a liquid having an appropriate viscosity as a raw material, and is cured into an insoluble and infusible state by heating. Refers to synthetic resin. In any case, the cured resin has a spatial network structure.
[0036]
Examples of such thermosetting resins include urethane resins, acrylic resins, melamine resins, phenol resins, urea resins, xylene resins, diallyl phthalate resins, guanamine resins, unsaturated polyester resins, epoxy resins, alkyd resins, silicon resins, and the like. Can be mentioned.
[0037]
Examples of the urethane resin include a two-component curable urethane resin and a one-component curable (moisture curable) urethane resin.
[0038]
The two-component curable urethane resin is a urethane resin having a polyol as a main component and an isocyanate as a crosslinking agent (curing agent). The polyol has two or more hydroxyl groups in the molecule, and for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like can be used.
[0039]
Moreover, as an isocyanate, the polyvalent isocyanate which has a 2 or more isocyanate group in a molecule | numerator is used. For example, aliphatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Group (or alicyclic) isocyanate and the like. Further, adducts of the above-mentioned various isocyanates or trimers of tolylene diisocyanate can also be used.
[0040]
The one-component curable urethane resin is a composition containing a prepolymer having an isocyanate group at the molecular end as an essential component. The prepolymer is usually a prepolymer having one or more isocyanate groups at both molecular ends, specifically, a polyisocyanate prepolymer having a polycarbonate skeleton, a polyurethane skeleton, a polybutadiene skeleton, a polyester skeleton, or the like as a main skeleton. It is a polymer. Isocyanate groups generate reactants due to moisture in the air and cause chain extension reaction. As a result, isocyanate groups react to form biuret bonds, branch, and form a spatial network structure by cross-linking reaction. .
[0041]
Acrylic resin is the main component of acrylic acid (including methacrylic acid) and its derivatives, such as acrylic resin obtained by polymerizing acrylamide and acrylonitrile, other acrylic acid esters, ethylene, styrene and other monomers. It is a polymer resin.
[0042]
Examples of the acrylic resin include poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, ( (Meth) acrylic acid esters such as methyl (meth) acrylate- (meth) acrylic acid 2-hydroxyethyl copolymer, ethylene- (meth) methyl acrylate copolymer, styrene-methyl (meth) acrylate copolymer The thing which consists of a homopolymer or a copolymer containing is mentioned. Here, (meth) acrylate is used to mean acrylate and methacrylate.
[0043]
The melamine resin is a resin obtained by subjecting methylolmelamine obtained by reacting melamine and formaldehyde to condensation polymerization. Further, melamine resins such as acrylic melamine resin, urea melamine resin, and phenol melamine resin can also be used.
[0044]
  Phenol resin is a resin obtained by polycondensation of phenols such as phenol, cresol and xylenol with aldehydes such as formaldehyde, acetaldehyde and furfural.AhExamples thereof include novolac-type phenol-formalin polymer, resol-type phenol-formalin polymer, rubber phenol resin, and the like.
[0045]
The urea resin is a resin obtained by reacting urea (urea) and formaldehyde under neutrality or basicity to obtain methylol urea, followed by dehydration, heat dehydration, or condensation polymerization with an acid.
[0046]
The xylene resin is obtained by subjecting o-xylene, m-xylene, p-xylene, or a mixture thereof and formalin to methylol xylene by polycondensation with strong acid, and further, phenol, cresol, organic acid, It is a resin obtained by adding amines or the like and adding a metaxylene sulfonic acid catalyst for condensation polymerization.
[0047]
The diallyl phthalate resin is a resin obtained by adding a peroxide catalyst to diallyl phthalate or isophthalic acid allyl ester for polymerization.
[0048]
Unsaturated polyester resin, after obtaining a polycondensation product of unsaturated dibasic acid and polyhydric alcohol, add a crosslinking agent such as styrene monomer, vinyl acetate, acrylic ester, methacrylic ester, etc. The resin obtained by performing vinyl polymerization.
[0049]
As the unsaturated dibasic acid, for example, maleic anhydride, fumaric acid, itaconic acid, citraconic acid and the like can be used, and as the polyhydric alcohol, ethylene glycol, propylene glycol, diethylene glycol, pentaerythritol and the like can be used.
[0050]
Saturated alkyd resins are polyesters obtained by condensation of saturated organic acids and polyhydric alcohols. Examples of saturated alkyd resins include glyphal resins, glyphal modified resins, isophthalic acid resins, fatty acid polyesters, polyethylene terephthalate, and polycarbonates. In addition, aminoalkyd resins can also be used.
[0051]
The epoxy resin is a resin obtained by reacting an initial condensate having two or more epoxy groups in a molecule with a curing agent such as amines, polyamides, polysulfides, or organic acid anhydrides. Examples of the epoxy resin include bisphenol A condensation polymerization type epoxy resin, novolac type epoxy resin, aliphatic epoxy resin, and the like.
[0052]
Silicon resin is a polymer having silicon (Si) as the main chain, and has a silane chain (—Si—Si—Si—) in the molecule and a siloxane chain (—Si—O—Si—O—). There are types that have in the molecule. Examples thereof include polydimethylsiloxane and polymonomethylsiloxane.
[0053]
A thermosetting resin composition (thermal) in which a low-molecular monomer, oligomer or prepolymer of such a thermosetting resin is added with a crosslinking agent, a polymerization initiator, a solvent, a viscosity modifier, a modified pigment, etc. as necessary. A curable resin liquid) is used as a raw material.
[0054]
As the crosslinking agent, organic sulfonates, isocyanates, amines, organic peroxides, azobisisobutyronitrile and the like can be used.
[0055]
The thermosetting resin layer 2 is obtained by applying such a thermosetting resin composition to, for example, a bar coat, roll coat, curtain flow coat, wire bar coat, reverse bar coat, gravure coat, gravure reverse coat, air knife coat, kiss coat. It can be formed by impregnating (coating) the back side of the paper-based substrate 1 by various coating methods such as blade coating, smooth coating, and comma coating, followed by heat curing. The amount of impregnation of the thermosetting resin composition into the paper-based substrate is usually 30 to 100 g / m.2Degree.
[0056]
When the thermosetting resin composition is applied to the back side of the paper base 1, a part of the thermosetting resin composition is impregnated into the paper base 1 from the back side of the paper base 1, and a part of the paper base 1 is impregnated. A coating film is formed on the back surface. Then, the base material 3 is superposed on the back surface side of the paper base material 1, and the thermosetting resin composition is cured (thermal lamination), whereby at least the back side portion in the paper base material layer 1 is thermoset. The thermosetting resin layer 2 is formed on the back side of the paper substrate 1 and the paper substrate 1 containing the adhesive resin, and the paper substrate 1 and the substrate 3 can be firmly bonded.
[0057]
When the paper substrate 1 is made of a laminate, for example, as shown in FIG. 1 (c), the back surface of the first paper substrate 1 (the surface opposite to the surface on which the pattern layer 4 is formed). ) Is impregnated with the impregnated paper impregnated with the thermosetting resin composition (second paper base material layer 1 ″ ′), and the base material 3 is placed on the back surface of the second paper base material layer 1 ″ ′. It can also be laminated. In this case, the second paper-based substrate layer 1 ″ ′ also serves as the paper-based substrate portion 1 ″ containing the thermosetting resin and the thermosetting resin layer 2. In this case, the impregnation amount of the thermosetting resin is usually 15 to 35 g / m.2(When dry)
[0058]
It is preferable to further form a surface protective layer 5 on the outermost surface of the paper-based substrate 1, for example, as shown in FIG. The surface protective layer 5 is formed to protect the surface of the decorative material and to impart abrasion resistance, stain resistance, and the like to the decorative material.
[0059]
The surface protective layer 5 is preferably formed by applying a liquid ionizing radiation curable resin composition on the surface and crosslinking (curing) the coating film.
[0060]
The ionizing radiation curable resin is a composition that can be cured by ionizing radiation in which prepolymers (including so-called oligomers) having radically polymerizable unsaturated bonds or cationically polymerizable functional groups in the molecule and / or monomers are appropriately mixed. The product is used as a raw material. Here, ionizing radiation means electromagnetic waves or charged particles having energy capable of polymerizing or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used.
[0061]
Specifically, the prepolymer or monomer is a (meth) acryloyl group or (meth) acryloyloxy group in the molecule (for example, (meth) acryloyl group means an acryloyl group or a methacryloyl group). It is made of a compound having a radically polymerizable unsaturated group such as) and a cationically polymerizable functional group such as an epoxy group. These prepolymers and monomers can be used alone or in combination.
[0062]
Further, as the ionizing radiation curable resin, a polyene / thiol prepolymer based on a combination of polyene and polythiol can also be preferably used.
[0063]
Such prepolymers or monomers include, for example,
(1) As a prepolymer having a radically polymerizable unsaturated group in the molecule, polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, silicone ( And (meth) acrylate. These molecular weights are usually about 250 to 100,000.
[0064]
(2) Monomers having a radically polymerizable unsaturated group in the molecule include, as monofunctional monomers, methyl (meth) acrylate, ethyl (methacrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, etc. Can be mentioned.
[0065]
Examples of the polyfunctional monomer include diethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, trimethyl propane tri (meth) acrylate), dipentaerythritol (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. be able to. Here, (meth) acrylate is used to mean acrylate or methacrylate.
[0066]
(3) Examples of prepolymers having a cationically polymerizable functional group in the molecule include epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type prepolymers such as fatty acid vinyl ethers and aromatic vinyl ethers. Can be mentioned.
[0067]
Furthermore, examples of the polythiol include trimethylpropane trithioglycolate and pentaerythritol tetrathioglycolate, and examples of the polyene include those obtained by adding alcohols at both ends of a polyurethane by diol and diisocyanate.
[0068]
In the case of a resin system having a cationic polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metallocene compound, a benzoin sulfonic acid ester, etc., alone or as a mixture, as a photopolymerization initiator Can be used. The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin.
[0069]
Furthermore, in order to give abrasion resistance to the surface protective layer 5, hard inorganic particles can be added as necessary. Examples of such inorganic particles include particles of alumina (such as α-alumina), silica, glass, silicon carbide, diamond, and the like.
[0070]
Examples of the shape of the inorganic particles include spheres, polygons, scales, and irregular shapes. The average particle size of the inorganic particles is preferably about 3 to 30 μm. If the average particle size is too small, the effect of improving wear resistance is poor, and if it is too large, the surface smoothness decreases. The addition amount of the inorganic particles is about 5 to 40% by weight with respect to the total amount of the resin.
[0071]
In addition, various additives can be added to the ionizing radiation curable resin as necessary. Examples of these additives include thermoplastic resins such as vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, and cellulose resin, extender pigments composed of fine powders such as calcium carbonate and barium sulfate, and silicone resin. Examples thereof include lubricants such as waxes, dyes, pigments, dispersants, colorants such as reactive silicones, and the like.
[0072]
The ionizing radiation curable resin layer 5 is a resin composition obtained by adding an organic solution or water-based emulsion (water-solubilized) of a mixture obtained by adding the prepolymer or monomer and, if desired, the above-described additives. It can be formed by coating on the substrate 1 (or on the later-described sealer layer 8 or primer layer 6), and curing the coated surface by irradiating with ionizing radiation. The coating amount of the resin composition is 15 to 35 g / m.2(Solid content basis) is preferred.
[0073]
Examples of coating methods include bar coat, roll coat, curtain flow coat, wire bar coat, reverse bar coat, gravure coat, gravure reverse coat, air knife coat, kiss coat, blade coat, smooth coat, comma coat, etc. A coating method is mentioned.
[0074]
In addition, as an ionizing radiation source for curing the ionizing radiation curable resin composition, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide stamp or the like is used as an ultraviolet ray source. Moreover, as a wavelength of ultraviolet rays, a wavelength range of 190 to 380 nm can be used.
[0075]
As the electron beam source, various electron beam accelerators such as a cockcroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The electron beam used is 100 to 1000 keV, preferably 100 to 300 keV. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.
[0076]
In addition, when hardening the said prepolymer or monomer with an ultraviolet-ray or visible light, a photoinitiator is added in the said prepolymer or monomer. As the photopolymerization initiator, in the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ethers can be used alone or in combination.
[0077]
In the case where an electron beam curable resin is used, for example, as shown in FIG. 2 (e), after the pattern layer 4 is formed on the paper substrate 1 by printing, an anchor layer (primer as described later) is used. (6), and (2) a pattern layer 7 is printed thereon with an ink imparted with liquid repellency, and (3) an electron beam curable resin composition is applied ( At this time, the electron beam curable resin on the pattern layer 7 imparted with liquid repellency is repelled.), (4) By irradiating an electron beam from above, the electron beam curable resin is cured. The surface protective layer 5 can also be formed. In this case, the upper portion of the pattern layer 7 becomes a concave portion, and an uneven pattern that synchronizes with the pattern layer 7 is formed (this method is referred to as “repel-tuned printing method” in this application. For example, Japanese Patent Laid-Open No. 7-117182). No., JP-A-8-174770, etc.).
[0078]
The pattern layer 7 is, for example, an amino alkyd resin as a resin binder, and a resin composition to which an additive such as a pigment or silicone is added. The coating amount is 0.5 to 5 g / m.2Can be applied and formed to the extent.
[0079]
Furthermore, in the decorative material of the present invention, in the decorative material of the present invention, if necessary, for example, as shown in FIG. 3 (f), a sealer layer is provided between the paper base material layer 1 and the picture layer 4. (Also referred to as a colored solid layer) 8 is preferably formed.
[0080]
When the surface protective layer 5 is formed on the outermost surface of the decorative material, the sealer layer 8 is absorbed into the paper base 1 by the applied resin composition that becomes an uncured or liquid surface protective layer. , Prevents the surface protective layer 5 from decreasing in thickness, resulting in insufficient surface protective effect, and uneven formation of the paper base material to become uneven gloss of the resin coating (which becomes the surface protective layer) Therefore, it is formed for the purpose of enhancing the adhesion between the ink of the picture layer 4 and the surface protective layer 5 and improving the scratch resistance.
[0081]
As a material constituting the sealer layer 8, one or more of urethane resin, acrylic resin, polyvinyl butyral, epoxy resin, alkyd resin, nitrocellulose and the like can be used.
[0082]
As these urethane resin, acrylic resin, epoxy resin, and alkyd resin, any of those listed as preferable as resins constituting the thermosetting resin layer can be used.
[0083]
In these resins, pigments such as titanium oxide, iron oxide, and carbon may be added. The coating amount of the sealer layer 8 is 1 to 10 g / m.2The degree (when dried) is preferred.
[0084]
Further, in the decorative material of the present invention, for example, as shown in FIG. 3 (g), the pattern layer 4 or the sealer layer 8 (when the pattern layer 4 is partially formed, it is also formed on the paper base material layer 1). It is also preferable to further form a primer layer (also referred to as an anchor layer) 6 between the surface protective layer 5 and the surface protective layer 5. The primer layer 6 relieves the shear stress generated at the interface between the surface protective layer 5 and the picture layer 4 at the time of curing shrinkage when forming the surface protective layer 5, and the surface protective layer 5 and the picture layer by chemical adhesion. It plays the role which improves the adhesiveness between 4. Therefore, when the primer layer 6 is formed, the scratch resistance of the decorative material is further improved, and the pattern layer 4 can be prevented from being distorted.
[0085]
The primer layer 6 is preferably made of one or a mixture of two or more of urethane resin, acrylic resin, polyvinyl butyral, and the like. As the urethane resin and the acrylic resin, those similar to those listed as preferable in the thermosetting resin layer 2 and the sealer layer 8 can be used.
[0086]
The primer layer 6 is formed by applying a resin composition in which one or a mixture of these resins is an organic solution or an aqueous emulsion (water-solubilized) by a gravure coating, a roll coating method, etc. It can be formed by drying. Moreover, the primer layer 6 can also be formed by the whole surface solid printing by gravure printing etc. The coating amount is usually 0.1 to 10 g / m.2(Solid content basis) is preferred.
[0087]
The decorative material of the present invention can be produced by laminating the base material 3 on the paper base material 1 having the back surface coated with the thermosetting resin composition. As a method for laminating the base material 3, after the thermosetting resin composition is impregnated (coated) on the back surface of the paper base material 1, the base material 1 is cured before the thermosetting resin composition is cured. It is preferable to heat press (heat laminate) the coated surface. As conditions for hot pressing, heating is performed at 120 to 200 ° C. for several tens of seconds to 1 hour, and 5 kg / cm.2~ 100Kg / cm2It can carry out on the pressurization conditions of a grade.
[0088]
As described above, when the thermosetting resin composition is applied on the back surface of the paper substrate 1, a part of the thermosetting resin composition is impregnated inside the paper substrate substrate 1, and a part of the material is paper quality. It remains on the substrate to form a coating film. Then, before the coating film is cured, the base material 1 is overlapped and heated and pressurized, whereby the thermosetting resin composition is cured and a three-dimensional space network structure (thermosetting resin). Can be formed. Thus, a strong bond between the paper substrate 1 and the substrate 3 can be formed by the thermosetting resin. The state can be obtained.
[0089]
Such a thermosetting resin layer 2 imparts a hardness sufficient to withstand the cosmetic material even when some local pressure is applied from the surface of the decorative material, and the paper base material 1 and the base material 3 are provided. Combines the role of bonding.
[0090]
According to the method of laminating the base material on the back surface of the paper-based base material 1 by this heat laminating method, no additional adhesive is required and the step of applying the adhesive can be omitted. It is preferable from the viewpoint of manufacturing the material.
[0091]
In addition, after impregnating (coating) the thermosetting resin composition on a paper base material, the thermosetting resin layer is once formed by heating, and then the base material is made of a paper base material using an adhesive or the like. Of course, it is possible to attach it to the back side.
[0092]
In this case, examples of the adhesive that can be used include those made of vinyl acetate resin, polyamide resin, one-pack or two-pack curable urethane resin, epoxy resin, polyester resin, and the like.
[0093]
The base material 3 is not particularly limited in material, shape and the like as long as it can be attached to the paper base material 1. Examples of the shape of the substrate include a flat plate shape, a curved plate shape, and a polygonal column shape.
[0094]
Examples of the base material include timber veneer, wood plywood, particle board, medium density fiber board (MDF) and other wood fiber boards made of various tree species such as cedar, firewood, firewood, firewood, lawan, teak, and melapie. Wood board, iron, iron alloy, copper, copper alloy, aluminum and other metals, acrylic, polycarbonate, ethylene-vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS resin, phenol resin, polyvinyl chloride, Cellulose resins, rubber and other resins, ceramics such as various glasses and ceramics, cements such as ALC (foamed lightweight concrete), non-cement ceramic materials such as calcium silicate and gypsum, fine paper, Japanese paper, paper for wallpaper, etc. , Carbon, asbestos, potassium titanate, glass, non-woven fabric or woven fabric made of fibers such as synthetic resinMoreover, the base material may consist of these laminated bodies, and may be colored with the coloring agent.
[0095]
The decorative material of the present invention configured as described above is used for interior materials of buildings such as walls and ceilings, surface materials of fittings such as doors, door frames and window frames, surfaces of artificial members such as curbs and baseboards. It can be used as a surface material for furniture such as wood, baskets and cabinets.
[0096]
【Example】
Next, the decorative material of the present invention will be described in more detail by way of examples. The following is an example of the decorative material of the present invention, and the decorative material of the present invention is a paper-based substrate, base material, thermosetting resin, surface protection without departing from the gist of the present invention. It is possible to appropriately change the design of the type of resin or the like constituting the layer, the formation method of each layer, the layer configuration, and the like.
[0097]
In addition, the value of universal hardness of each thermosetting resin used in the following Examples and Comparative Examples is that each thermosetting resin composition (uncured) is made to a thickness of 50 μm using a bar coater. A thermosetting resin layer obtained by coating on a glass plate and heat-curing by heating at 170 ° C. for 3 minutes is measured with a Fischer scope H100V (manufactured by H. Fisher). Is used.
[0098]
That is, using a Vickers pyramid indenter as an indenter, a load of 20 mN (Newton) is continuously applied from the surface of the resin layer every 6 seconds until the thermosetting resin layer formed on the glass plate undergoes irreversible elastic deformation. Measure the load value at that time and the penetration depth of the indenter, and obtain the maximum load value (Fmax) And maximum penetration depth (hmax), HU = F (N) /26.43h2 [mm2] (Where F (N) represents the maximum value of the load and h (mm) represents the maximum value of the penetration depth).
[0099]
Example 1
On the back side (surface opposite to the pattern layer) of urethane-coated paper in which a pattern layer is formed on 50 g of base paper by the repelling synchronized printing method and a surface protective layer is further formed by a two-component curable urethane resin. After impregnating 60 g of a melamine acrylic resin (uncured) having a value of 200, a particle board substrate (thickness 30 mm) was laminated on the impregnated surface, and hot pressing (30 kg / cm2The cosmetic material of Example 1 was obtained by applying a pressure of 150 ° C. for 60 seconds.
[0100]
Example 2
The back side of the EB coated paper in which a pattern layer is formed on a 60 g base paper by a repelling synchronized printing method and a surface protective layer made of an electron beam curable resin is further formed thereon (the surface on which the surface protective layer is formed) The opposite surface) was impregnated with 80 g of a melamine resin (uncured) having a universal hardness value of 400, and then a particle board base material (thickness 30 mm) was bonded to the impregnated surface, followed by hot pressing ( 30 kg / cm2The decorative material of Example 2 was obtained by heating at 150 ° C. for 60 seconds.
[0101]
Example 3
On the back side of the urethane-coated paper (surface opposite to the pattern layer) on which the pattern layer is formed on 30g of base paper by the repelling synchronous printing method and the surface protective layer is further formed by two-component curable urethane resin. An impregnated paper (100 g) impregnated with 60 g of a melamine resin (uncured) having a value of 500 is laminated, and a particle board substrate (thickness 30 mm) is laminated on the impregnated paper, followed by hot pressing (30 kg / cm2The decorative material of Example 3 was obtained by heating at 150 ° C. for 60 seconds.
[0102]
Example 4
  First, a pattern layer is formed on a 60 g base paper by a repelling synchronized printing method, and further, an electron beam hardener having the following composition A is used.Chemical treeThe fat composition is 25 g / m on the pattern layer using a roll coater.2 The surface protective layer was formed by irradiating the coated surface with an electron beam at 175 keV and 5 Mrad using an electron beam irradiation apparatus to cure the coating film. Next, after impregnating 50 g of a melamine resin (uncured) having a universal hardness value of 600 on the back surface of the obtained abrasion-resistant EB-coated paper, an MDF base material (thickness 30 mm) was used. Lamination, heat press (30kg / cm2The cosmetic material of Example 4 was obtained by heating at 150 ° C. for 60 seconds.
[0103]
[0104]
Example 5
Universal hardness value on the back side (surface opposite to the pattern layer) of urethane-coated paper in which a pattern layer is formed on 30g of base paper by gravure printing and a surface protective layer is formed by two-component curable urethane resin Was impregnated with 80 g of phenolic resin (uncured) having a thickness of 300, and then an MDF substrate (thickness 30 mm) was laminated on the impregnated surface, followed by hot pressing (30 kg / cm2The cosmetic material of Example 5 was obtained by heating at 150 ° C. for 60 seconds.
[0105]
Comparative example1
On the back side of the urethane-coated paper (surface opposite to the pattern layer) on which a pattern layer is formed on 50g of base paper by the repelling synchronized printing method and a surface protective layer is formed with a two-component curable urethane resin. After impregnating 60 g of a mixed resin (uncured) of an acrylic resin and a melamine resin having a value of 80, a particle board substrate (thickness 30 mm) was bonded to the impregnated surface, and hot pressing (30 kg / cm2The cosmetic material of Comparative Example 1 was obtained.
[0106]
Comparative Example 2
The back side of the EB coated paper in which a pattern layer is formed on a 60 g base paper by a repelling synchronized printing method and a surface protective layer made of an electron beam curable resin is further formed thereon (the surface on which the surface protective layer is formed) After impregnating 80 g of acrylic melamine resin (uncured) with a universal hardness value of 120 on the opposite surface), a particle board substrate (thickness 30 mm) is pasted on the impregnated surface, and hot press (30kg / cm2The decorative material of Comparative Example 2 was obtained.
[0107]
Comparative Example 3
On the back side of the urethane-coated paper (surface opposite to the pattern layer) on which the pattern layer is formed on 30g of base paper by the repelling synchronous printing method and the surface protective layer is further formed by two-component curable urethane resin. An impregnated paper (100 g) impregnated with 60 g of a mixed resin (uncured) of an acrylic resin and a melamine resin having a value of 100 is laminated, and a particle board substrate (thickness 30 mm) is laminated on the impregnated paper, Hot press (30kg / cm2The decorative material of Example 3 was obtained by heating at 150 ° C. for 60 seconds.
[0108]
Comparative Example 4
A pattern layer is formed on 60 g of base paper by a repelling synchronized printing method, and further, an electron beam curable resin composition having the same composition as that of the composition [A] used in Example 4 is used thereon. Similarly, 50 g of an acrylic melamine resin (uncured) having a universal hardness value of 120 was impregnated on the back surface of the abrasion-resistant 1B coated paper on which the surface protective layer was formed, and then the MDF substrate ( Laminate 30mm thick) and heat press (30kg / cm2The cosmetic material of Example 4 was obtained by heating at 150 ° C. for 60 seconds.
[0109]
Comparative Example 5
A pattern layer is formed on 60 g of base paper by a repelling synchronized printing method, and further, an electron beam curable resin composition having the same composition as that of the composition [A] used in Example 4 is used thereon. Similarly, after impregnating 50 g of a melamine-based resin (uncured) having a universal hardness value of 600 on the back surface of the abrasion-resistant EB-coated paper on which the surface protective layer is formed, at 180 ° C. for 10 minutes. The melamine resin was cured by drying to form a thermosetting resin layer. Then, an MDF base material (thickness 30 mm) was laminated on the thermosetting resin layer, and hot pressing (30 kg / cm2However, the MDF substrate was not adhered to the abrasion-resistant EB coated paper.
[0110]
Pencil hardness test and scratch hardness test
The following scratch hardness test and pencil hardness test were performed using the decorative materials obtained in the above Examples and Comparative Examples (excluding Comparative Example 5).
[0111]
(1) Scratch hardness test
A scratch hardness test according to the JAS special plywood scratch hardness A test was performed. That is, after scratching the cosmetic material surface with a diamond needle while applying a load of 200 g, the depth of the scratch on the cosmetic material surface was determined using a two-dimensional surface roughness meter (manufactured by Kosaka Laboratory Ltd.). It was measured.
[0112]
(2) Pencil hardness test
A pencil dent test according to JISK5400 was performed. That is, while applying a load of 600 g, a pencil core having a hardness of 9H was placed on the surface of the decorative material, and the dent ratio was measured.
The test results are summarized in Table 1 below.
[0113]
[Table 1]
[0114]
From Table 1, it can be seen that the decorative materials of Examples 1 to 5 have superior scratch hardness and pencil dent hardness compared to the decorative materials of Comparative Examples 1 to 4.
[0115]
【The invention's effect】
As described above, according to the first invention, there is provided a cosmetic material that has a thermosetting resin layer having a predetermined hardness and is less likely to be depressed even when pressed with a pencil or the like from the surface of the cosmetic material. Is done.
[0116]
Further, when the decorative material of the present invention has a surface protective layer, preferably a surface protective layer made of an ionizing radiation curable resin, on its outermost surface, it also has excellent scratch resistance.
[0117]
According to 2nd invention, a base material can be stuck on a paper-type base material, without using an adhesive agent separately. Conventionally, it was common to stick a paper base material and a base material using an adhesive or the like, but according to the present invention, a coating film of a thermosetting resin composition ( After forming the uncured), the base material and the back side of the paper base material are overlapped and hot pressed (heat laminate) to form the thermosetting resin layer, and at the same time, the paper base material and the base material are pasted. Can be dressed.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a decorative material of the present invention.
FIG. 2 is a cross-sectional view of the decorative material of the present invention.
FIG. 3 is a cross-sectional view of the decorative material of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Paper quality base material layer, 1 '... Paper quality base material part which does not contain thermosetting resin, 1 "... Paper quality base material part containing thermosetting resin, 1"' ... 2nd paper quality base material layer DESCRIPTION OF SYMBOLS 2 ... Thermosetting resin layer, 3 ... Base material layer, 4 ... Pattern layer, 5 ... Surface protective layer, 6 ... Primer layer (anchor layer), 7 ... Pattern layer, 8 ... Sealer layer (entire solid layer)

Claims (4)

  1. A paper-based substrate layer having a pattern layer on the surface;
    A paper base material portion containing the thermosetting resin formed by impregnating the back surface side of the paper base material layer with a thermosetting resin composition having a universal hardness value of 150 to 1,000 N / mm 2 A thermosetting resin layer comprising:
    A base material layer formed on the back side of the thermosetting resin layer,
    The paper-based substrate layer is a paper-based substrate portion containing a thermosetting resin on the back side of the paper-based substrate layer;
    A decorative material comprising a paper-based substrate portion that does not contain a thermosetting resin.
  2. Having a surface protective layer on the outermost surface,
    The cosmetic material according to claim 1.
  3. The surface protective layer is made of an ionizing radiation curable resin.
    The cosmetic material according to claim 2.
  4. Impregnating the thermosetting resin composition on the back surface of the paper substrate; and
    In the uncured state of the thermosetting resin composition, a base material is superposed on the surface impregnated with the thermosetting resin composition, and the thermosetting composition is thermally laminated, and the paper base material A step of forming a paper base material portion containing the thermosetting resin in at least the back surface portion therein, and a thermosetting resin layer on the back surface of the paper quality base material ;
    Forming a pattern layer on the surface side of the paper substrate;
    The manufacturing method of the cosmetics which has this .
JP19816899A 1999-07-12 1999-07-12 Cosmetic material and method for producing cosmetic material Expired - Fee Related JP4765132B2 (en)

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Application Number Priority Date Filing Date Title
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Publication number Priority date Publication date Assignee Title
JP4620200B2 (en) * 1999-11-10 2011-01-26 大日本印刷株式会社 Cosmetic sheet and cosmetic material
WO2003101734A1 (en) * 2002-05-30 2003-12-11 Dai Nippon Printing Co., Ltd. Decorative material and decorative sheet
US8313824B2 (en) 2003-12-18 2012-11-20 Dai Nippon Printing Co., Ltd. Decorative multilayer material impregnated with resin
JP4522805B2 (en) * 2004-09-22 2010-08-11 大日本印刷株式会社 Manufacturing method of decorative board
EP1920914B1 (en) 2005-08-12 2016-01-20 Dai Nippon Printing Co., Ltd. Decorative plate and method for manufacture thereof
JP5765093B2 (en) * 2010-06-30 2015-08-19 大日本印刷株式会社 Decorative plate manufacturing method
KR101207513B1 (en) * 2010-12-29 2012-12-03 주식회사 한샘 Manufacturing method of wood panel improved scratch-resistance

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