JP3908308B2 - Manufacturing method of cosmetic material - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention can be used as a surface decorative material used for building interiors, surface decorations for fittings, vehicle interiors, and the like.
[0002]
[Prior art]
A conventional method for producing a cosmetic material used for such applications is described in JP-A-57-193325. That is, a foamable electron beam curable pattern made of a foamable electron beam curable composition mainly composed of a foaming agent and an electron beam curable compound is formed on the base material, and then foamed by irradiation with an electron beam. A method for producing a decorative material, characterized in that a foaming and curing of a curable electron beam curable pattern is described in claim (1).
[0003]
Furthermore, a foamable electron beam curable pattern made of a foamable electron beam curable composition comprising a foaming agent and an electron beam curable compound as a main component is formed on the base material, and is further superimposed on the entire surface to be transparent over the entire surface. A method for producing a cosmetic material, characterized in that a resin layer is provided and then an electron beam is irradiated to foam and harden the foamable electron beam curable pattern is described in claim (2).
[0004]
Further, in Example 1, “On a vinyl chloride film, an arabesque pattern was printed using ink, and the outline of the arabesque pattern was printed with a foamable electron beam curable resin, and then irradiated with an electron beam. The foamed pattern layer was cured, and foaming was simultaneously performed with the reaction heat at that time to obtain a cosmetic material. Is described.
[0005]
[Problems to be solved by the invention]
Such a conventional decorative material lacks the adhesion between the arabesque pattern printing ink and the ink printed with the arabesque pattern outline foamable electron beam curable resin.
That is, if the adhesive layer between the layer printed with the foaming electron beam curable resin and the pattern layer (pattern ink) is insufficient, or the substrate is a paper-like substrate, the foaming electron beam curing property The layer printed with the resin soaks into the base material, and the volume and unevenness are reduced.
In addition, since the transparent resin layer is formed on the layer printed with the foaming electron beam curable resin, even if the substrate is not paper, the volume feeling and the uneven feeling are reduced.
There was a problem.
[0006]
[Means for Solving the Problems]
The present inventor provided a transparent resin layer between the thick print layer made of ionizing radiation curable resin and the printed layer (pattern layer, pattern ink) in order to improve the adhesion. The transparent resin layer also serves to protect the surface of the printing layer (pattern layer, pattern ink).
Furthermore, when the base material is a permeable base material such as paper, the thick print layer made of ionizing radiation curable resin soaks into the base material and the unevenness is reduced. Was established.
Further, in order to give a sense of volume, a special capsule foaming agent or the like is put into an ionizing radiation curable resin, and after heat foaming at low temperature, it is cured by irradiation.
The resin is an ionizing radiation curable resin, improving hardness, contamination and productivity.
[0007]
And, in order to solve the above-mentioned problems, in the present invention, “there is a printing layer on at least one side of the substrate, and further a transparent resin layer on the entire surface, and on top of that, the ionization is synchronized with the printing layer. A method of manufacturing a decorative material provided with a thick print layer mainly composed of a radiation curable resin , wherein the thick print layer is irradiated with ionizing radiation after drying and foaming with ink containing a capsule foaming agent. And forming a cured film, a method for producing a cosmetic material. ”Was developed.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a cross-sectional view showing an example of a decorative material according to a reference example . FIG. 2 is a cross-sectional view showing another example of the decorative material according to the present invention.
[0009]
Examples of the substrate 5 in the present invention include a paper substrate, a plastic substrate, a nonwoven fabric, a metal substrate, and a wood substrate.
Thin paper, inter-paper reinforced paper, impregnated paper, titanium paper, coated paper, corrugated paper, linter paper, kraft paper, fine paper, etc. are used as the paper base material, from the viewpoint of resin permeability and ionizing radiation curability Preferably have a basis weight of 20 to 300 g / m ² .
As the plastic substrate, various plastic sheets and films such as polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile butadiene styrene, and polyvinyl chloride can be used. The plastic substrate is preferably colored.
As a metal base material, what made the undercoat of a coloring agent on a steel plate, aluminum, stainless steel etc. can be commercialized as a base material.
Examples of the wood-based substrate include plywood, particle board, medium density fiber board, and the like.
[0010]
The print layer (design layer) may be either a print pattern layer or a solid print layer. The printing layer is mainly formed from a resin and a pigment.
First, as the resin for forming the printing layer, ionizing radiation curable resin, chlorinated polyethylene such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane, acrylic, vinyl acetate, vinyl chloride / vinyl acetate copolymer, Cellulose resin is used, and one or a mixture of two or more are used. To this, a material added with known pigments as listed below is used.
[0011]
Here, as the acrylic, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate propyl, poly (meth) acrylate butyl, methyl (meth) acrylate / (meth) acryl Such as butyl acrylate copolymer, (meth) ethyl acrylate / (meth) butyl acrylate copolymer, ethylene / (meth) methyl acrylate copolymer, styrene / (meth) methyl acrylate copolymer, etc. ) Acrylic resin composed of a homopolymer or a copolymer containing an acrylate ester (here, (meth) acryl means acryl or methacryl, and the same shall apply hereinafter).
[0012]
Polyurethane is a resin having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent).
[0013]
As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.
[0014]
As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, aromatic isocyanates such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate are used.
[0015]
Pigments used in the printing layer include titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone, Hansa Yellow A, quinacridone, and permanent red. Pearl luster made of 4R, organic pigments (including dyes) such as phthalocyanine blue, Induslenbury RS, aniline black, metal pigments such as aluminum and brass, titanium dioxide-coated mica, and foil powder such as basic lead carbonate ( Pearl) pigments and the like.
These are added and dispersed as powder or scaly foil pieces.
[0016]
As pattern printing of the printing layer, a pattern is formed with ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, or the like.
Examples of the pattern include a wood grain pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, or a solid surface. The pattern is provided on the front surface, back surface, both front and back surfaces, or between layers of the sheet.
[0017]
As the ionizing radiation curable resin, a composition in which a polymerizable unsaturated bond or a prepolymer having an epoxy group, an oligomer, and / or a monomer is appropriately mixed in the molecule is used.
Examples of the prepolymer and oligomer include unsaturated polyesters such as unsaturated dicarboxylic acid and polyhydric alcohol condensates, polyester methacrylates, polyether methacrylates, polyol methacrylates, methacrylates such as melamine methacrylates, polyester acrylates and epoxy acrylates. Acrylates such as urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate.
[0018]
Examples of the monomer include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, acrylic acid Acrylic esters such as methoxybutyl and phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate and the like, acrylic Acid-2- (N, N-diethylamino) ethyl, methacrylate-2- (N, N-dimethylamino) ethyl, acrylic acid-2- (N, N-dibenzylamino) ethyl, methacrylic acid (N, N -Dimethylamino) methyl, acrylic acid-2 Substituted amino alcohol esters of unsaturated acids such as (N, N-didiethylamino) propyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1 , 6-hexanediol diacrylate, compounds such as diethylene glycol diacrylate, triethylene glycol diacrylate, polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol acrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or Polythiol compounds having two or more thiol groups in the molecule, such as trimethylolpropane trithioglycolate, trimethylo And propane trithiopropylate, pentaerythritol tetrathioglycol and the like.
[0019]
The above compounds are used alone or in combination of two or more as required. In order to impart ordinary coating suitability to the resin composition, 5% by weight or more of the prepolymer or oligomer, the monomer and It is preferable that the polythiol is 95% by weight or less.
[0020]
When selecting the monomer, if the flexibility of the cured product is required, the amount of the monomer is reduced within the range that does not hinder the suitability of coating, or a monofunctional or bifunctional acrylate monomer is used. A structure with a relatively low crosslink density. In addition, when the heat resistance, hardness, solvent resistance, etc. of the cured product are required, the amount of the monomer is increased within a range that does not hinder coating suitability, or an acrylate monomer having three or more functions is added. It is preferable to use a high crosslink density structure. It is also possible to adjust the coating suitability and the physical properties of the cured product by mixing a monofunctional monomer and a trifunctional or higher monomer.
[0021]
Examples of the monofunctional acrylate monomers as described above include 2-hydroxy acrylate, 2-hexyl acrylate, phenoxyethyl acrylate, and the like. Examples of bifunctional acrylate monomers include ethylene glycol diacrylate and 1,6-hexanediol diacrylate. Examples of trifunctional or higher acrylate monomers include trimethylolpropane triacrylate, pentaerythritol hexaacrylate, and dipenta Examples include erythritol hexaacrylate.
[0022]
Moreover, in order to adjust the physical properties such as flexibility and surface hardness of the cured product, the following ionizing radiation non-curable resin is used in an amount of 1 to 70 with respect to at least one of the prepolymer, oligomer and monomer. The mixture can be used by weight%, preferably 5 to 50% by weight.
As the ionizing radiation non-curable resin, a thermoplastic resin such as urethane, fiber, polyester, acrylic, butyral, polyvinyl chloride, and polyvinyl acetate can be used. Of these, urethane, butyral are preferred.
[0023]
In order to apply the above ionizing radiation curable resin composition, various known methods, for example, gravure printing, roll coating, curtain flow coating, wire bar coating, reverse coating, gravure coating, gravure reverse coating, air knife coating, A method such as kiss coating, blade coating, smooth coating, comma coating, etc. is used, and the coating thickness is about 0.1 to 100 μm when dried.
[0024]
Next, the transparent resin of the transparent resin layer includes phenol, urea, diallyl phthalate, melamine, guanamine, unsaturated polyester, polyurethane, epoxy, aminoalkyd, melamine-urea cocondensation, silicon, polysiloxane, and the above ionization. A radiation curable resin is used. Further, fine particles such as silica, alumina and kaolin, beads such as urethane beads and acrylic beads may be added for gloss adjustment.
[0025]
The vehicle of the build-up ink for the thick print layer is preferably the ionizing radiation curable resin. This ionizing radiation curable resin includes foaming agents, pigments (same as the pigments in the above printing layer), dyes, fillers, flame retardants, ultraviolet absorbers, thermoplastic resins, thermoplastic elastomer resins, toluene as necessary. Add a solvent such as xylene or isopropyl alcohol.
[0026]
Irradiate with ionizing radiation after drying or dry foaming. The irradiation method is preferably an electron beam from the viewpoint of productivity. The irradiation method is preferably an electron beam from the viewpoint of productivity. The irradiation condition is 100 to 300 Kv, 1 to 10 Mrad, preferably 3 to 5 Mrad.
[0027]
The ink in which the foaming agent is added to the curable resin is heated to foam the foaming agent. Examples of the blowing agent include azodicarbonamide, azobisisobutyronitrile, NN′-dinitrosopentamethylenetetramine, oxybisbenzenesulfonylhydrazide, sodium hydrogen carbonate, potassium hydrogen carbonate, and the like, or chlorinated. A capsule foaming agent (microcapsule type) in which a thermally expandable gas such as hexane or isobutane is enclosed in a resin spherical shell made of vinylidene, acrylonitrile or a copolymer thereof is used. The amount added is usually 1 to 20 parts by weight per 100 parts by weight of the resin.
The foaming temperature is selected to foam within the range of 100 to 180 ° C.
In addition, foaming agents described in JP-A-57-193325, page 2, right column can also be used.
[0028]
In order to improve the ink breakage and transferability, powders such as silica, calcium carbonate, barium sulfate, clay, talc and the like are used as a filler for imparting thixotropic properties. Add an appropriate amount if necessary.
As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used, and these are added when it is necessary to impart flame retardancy.
The addition amount is about 1 to 25 parts by weight with respect to 100 parts by weight of the resin.
[0029]
In order to improve the stain resistance of the thick print layer, silicon oil, reactive silicon, silicon acrylate and fluorine resin may be added.
[0030]
[Ultraviolet absorber / light stabilizer]
In order to give better weather resistance (light resistance) to the resin, an ultraviolet absorber and / or a light stabilizer can be added, and the addition amount is usually 0.5 to 5 for both the ultraviolet absorber and the light stabilizer. Although it is about 10% by weight, it is generally preferable to use a UV absorber and a light stabilizer in combination.
[0031]
As the ultraviolet absorber, organic substances such as benzotriazole, benzophenone, and salicylic acid ester, or inorganic substances such as fine particle zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used. As the light stabilizer, a radical scavenger such as a hindered amine radical scavenger such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate or a piperidine radical scavenger can be used.
[0032]
The method for forming the thick print layer is the same as the method for forming the print layer, but it is preferable to perform gravure printing or silk screen printing. In the case of gravure printing, the viscosity is 500 to 4000 cps, and in the case of silk screen printing, the viscosity is 2000 to 10,000 cps.
[0033]
In the case of performing thick build printing (ie, build up printing) by gravure printing, the gravure plate performs direct etching. A plate with a depth of 50-200 μm is desirable.
[0034]
Further, the decorative material of the present invention can be laminated on another adherend (backing material).
In the lamination, the adherend and the decorative paper are laminated with an appropriate adhesive.
[0035]
If the adherend is the final product and there is a case where a decorative material is laminated for the surface makeup, if necessary, the back surface of the decorative material is coated to reinforce the mechanical strength of the cosmetic material or to provide concealment. In some cases, a kimono is laminated.
[0036]
As the adherend, plate materials of various materials, plate materials such as curved plates, three-dimensional shaped articles [molded products], articles of various shapes such as sheets (or films) are targeted. As materials used for both board materials, three-dimensional shaped articles, and sheets (films), wood boards such as wood single boards, wood plywood, particle boards, medium density fiber boards (MDF), and wood boards such as wood fiber boards Metals such as iron and aluminum, acrylic, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS, phenol resin, polyvinyl chloride, cellulose resin, rubber and other resins, exclusively plate materials As materials used as three-dimensional articles, ceramics such as glass and ceramics, cements such as ALC (foamed lightweight concrete), non-cement ceramic materials such as calcium oxalate and gypsum, exclusively as sheets (or films) The materials used are fine paper, Japanese paper, carbon, Cotton, there potassium titanate, glass, consisting of fibers such as synthetic resin nonwoven fabric or woven fabric or the like.
[0037]
As a method for laminating these various adherends, for example, (1) a method of laminating by pressing with a pressure roller on a plate-like substrate with an adhesive layer in between, (2) Japanese Patent Publication No. 50-19132 As described in Japanese Patent Publication No. 43-27488, a decorative paper is inserted between both male and female molds for injection molding, both molds are closed, and molten resin is injected and filled from a male mold gate. Thereafter, cooling is performed, and a decorative paper is adhered and laminated on the surface of the resin molded product at the same time as molding, so-called injection molding simultaneous laminating method, described in (3) JP-B 56-45768, JP-B 60-58014, etc. The decorative paper is placed on the surface of the molded article so as to face or be placed with an adhesive layer interposed therebetween, and the decorative paper is laminated on the surface of the molded article by a pressure difference due to vacuum suction from the molded article side. Vacuum press lamination method, (4) Japanese Patent Publication No. 61-5895, As described in Japanese Patent Publication No. 3-2666, a plurality of rollers with different directions are supplied while supplying decorative paper via an adhesive layer in the longitudinal direction of a columnar substrate such as a cylinder or a polygonal column. Thus, decorative paper is sequentially pressure-bonded and laminated on a plurality of side surfaces constituting the columnar body, so-called wrapping method, (5) Japanese Utility Model Publication No. 15-31122, JP-A-48-47972 First, the decorative paper is laminated on the plate-like base material via the adhesive layer, and then the decorative paper and the plate-like base material are disposed on the surface of the plate-like base material opposite to the decorative paper. A so-called V-cut that cuts a V-shaped or U-shaped groove that reaches the interface, and then applies an adhesive into the groove and then folds the groove to form a box or columnar body. Or there is a U-cut processing method.
[0038]
In particular, as a method of bonding the decorative material of the present invention to the three-dimensional object, (a) lapping method, (b) V-cut method, (c) injection molding simultaneous laminating method, (d) vacuum A molding simultaneous lamination method or the like is preferable.
[0039]
The decorative material of the present invention is laminated on various adherends, subjected to a predetermined molding process, etc., and used for various applications. For example, interior decorations for buildings such as walls, ceilings, floors, surface decorations for furniture such as window frames, doors, handrails, surface decorations for furniture or cabinets for light electrical / OA equipment, vehicle interiors for cars, trains, aircraft interiors, windows Glass makeup.
[0040]
【Example】
Examples of the present invention will be described in detail below.
[0041]
On one side of the paper between the reinforced paper of Reference Example basis weight 30 g / m ^2, in gravure plate of 150-line and acrylic nitrocellulose-based inks, grain pattern printing of one color solid printing, and three colors (yellow, brown, black) Did. Next, a transparent resin having the following composition [A] was coated on the printed surface by a gravure printing method with a diagonal plate having a plate depth of 60 μm to form a transparent resin layer.
[0042]
Composition [A]
(1) Acrylic polyol ... 80 parts by weight (2) XDI (xylene diisocyanate) ... 20 parts by weight (3) Silica ... 2 parts by weight
Next, an ink made of an ionizing radiation curable resin having the following composition [B] was raised and printed on the surface of the transparent resin layer with a direct gravure plate having a plate depth of 100 μm to form a thick print layer.
[0044]
Composition [B]
(1) Urethane oligomer ... 40 parts by weight (2) HEA (2-hydroxyethyl acrylate) ... 20 parts by weight (3) 1,6-hexanediol diacrylate ... 20 parts by weight (4) oxidation Titanium: 20 parts by weight (5) 2 parts by weight of a benzotriazole ultraviolet absorber
Next, the cosmetic material of the reference example was obtained by performing irradiation of 3 Mrad of an electron beam accelerated to 175 KV only once from the application surface of the ionizing radiation curable resin in a nitrogen atmosphere having an oxygen concentration of 300 ppm or less. Obtained. Further, this decorative material was hot pressed at 160 ° C. with a urea adhesive on a medium density fiber board having a thickness of 20 mm to obtain a decorative board.
[0046]
Example 1
One-color solid printing and three-color (yellow, brown, black) wood grain pattern printing with 100-line gravure printing of acrylic / nitrified cotton-based ink on one side of a paper-reinforced paper with a basis weight of 45 g / m ² . Next, a transparent resin having the following composition [A] was coated on the printed surface by a gravure printing method with a diagonal plate having a plate depth of 60 μm to form a transparent resin layer.
[0047]
Composition [A]
(1) Acrylic polyol ... 80 parts by weight (2) XDI (xylene diisocyanate) ... 20 parts by weight (3) Silica ... 2 parts by weight
Next, on the surface of the transparent resin layer, an ink made of an ionizing radiation curable resin having the following composition [B] is raised and printed with a direct gravure plate having a plate depth of 100 μm to form a thick print layer, In the drying zone, the capsule foaming agent was foamed to triple the thickness.
[0049]
Composition [B]
(1) Urethane oligomer: 40 parts by weight (2) HEA (2-hydroxyethyl acrylate): 20 parts by weight (3) 1,6-hexanediol diacrylate: 15 parts by weight (4) Oxidation Titanium: 20 parts by weight (5) Benzotriazole-based UV absorber: 2 parts by weight (6) Capsule foaming agent (shell is made of vinylidene chloride and expansion agent is isobutane): 5 parts by weight [0050]
Next, the cosmetic material of the present invention can be obtained by irradiating 3 Mrad of an electron beam accelerated to 175 KV only once in a nitrogen atmosphere having an oxygen concentration of 300 ppm or less from the application surface of the ionizing radiation curable resin. Obtained.
Further, this decorative material was hot pressed at 160 ° C. with a urea adhesive on a medium density fiber board having a thickness of 20 mm to obtain a decorative board.
[0051]
【The invention's effect】
The decorative material of the present invention has the following effects.
(1) The transparent resin layer improves the adhesion between the thick print layer made of ionizing radiation curable resin and the print layer (pattern layer, pattern ink).
(2) The surface of the printed layer (pattern layer, pattern ink) is protected by the transparent resin layer.
(3) Due to the transparent resin layer, even when the base material is a paper-permeable base material, the thick print layer made of ionizing radiation curable resin soaks into the base material, reducing the feeling of unevenness. There is no end to it.
(4) A volume feeling can be obtained by putting a special capsule foaming agent or the like into ionizing radiation curable resin, and curing by irradiation after low temperature heating and foaming.
(5) The resin is an ionizing radiation curable resin, which improves hardness, contamination and productivity.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing an example of a decorative material according to a reference example .
FIG. 2 is a cross-sectional view showing another example of a decorative material according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Raising ink 2 Transparent resin layer 3 Pattern ink 4 Solid printing 5 Base material 6 Cosmetic material 7 Print layer 10 Raising ink 11 before foaming 11 Cosmetic material 20 Raising ink 21 after foaming Cosmetic material

Claims (1)

A decorative material having a printing layer on at least one surface of a substrate, a transparent resin layer on the entire surface, and a thick printing layer mainly composed of an ionizing radiation curable resin, which is in synchronization with the printing layer. A method for producing a cosmetic material , characterized in that the embossed printing layer is formed as a film obtained by drying and foaming an ink containing a capsule foaming agent and then irradiating with ionizing radiation. Way .

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