JP5218360B2 - Manufacturing method of cosmetic material - Google Patents

Description

Relates to a manufacturing method of the present invention is the decorative material using the sheet with impregnation of paper or the like, the sheet due to the fact that it fluoroscopy underlying colored state by transparency by impregnation, production of decorative material having a three-dimensional sense of depth It is about the method .

  Various decorative materials are used for interior and exterior of buildings, interior and exterior of ships and vehicles, or for attaching surfaces of furniture and home appliances. For example, there is a doubling sheet obtained by heat-sealing a colored sheet of a polyvinyl chloride resin and a transparent sheet with a pattern sandwiched between them. Thermosetting resin decorative board produced by printing on impregnated colored paper, overlaying the resin impregnated on the base material, and heating and pressurizing with a press as having excellent mechanical and chemical durability There is.

  The former doubling sheet is usually manufactured by printing on the colored sheet side, laminating a pattern layer, then overlaying a transparent sheet, heat-sealing them using a heatable embossing roll and embossing them. However, the heat sealing and embossing processes can be performed only at a relatively low speed, and the production efficiency is not good. In addition, in order to prepare a cosmetic material having the same pattern but different overall color tone (referred to as “different color scheme”), it must be printed on a colored sheet of a different hue each time and heat-sealed with a transparent sheet. .

  The latter thermosetting resin decorative plate is excellent in physical and chemical durability, but it takes a long time to heat and press with a press, and the production efficiency is not good, and the obtained product is a hard plate shape. Therefore, application to a curved surface is difficult. In addition, in order to prepare a cosmetic material having a different color scheme, it is necessary to print on colored paper of a different hue each time, impregnate the resin, and heat and press with a press.

  In the present invention, it is an object of the present invention to solve the problem that conventional cosmetic materials are not good in production efficiency and the difficulty of preparing cosmetic materials having different color schemes. Moreover, when trying to solve these problems, it is an object to eliminate the point that it is difficult to apply to a curved surface in a thermosetting resin decorative board or the like.

  In the present invention, by impregnating the resin into a transparent paper that is transparentized by impregnation with the resin, and pasting it on a colored colored substrate, or by pasting using a colored adhesive as an adhesive, the above We were able to solve the problem.

  According to a first aspect of the present invention, after impregnating an ionizing radiation curable resin as a transparent resin composition for impregnation into a transparent paper that is transparentized by impregnation with a resin, A makeup characterized by laminating and irradiating an electron beam from the transparent paper side using an electron beam irradiation device to cure the ionizing radiation curable resin impregnated in the transparent paper and the ionizing radiation curable coloring adhesive The present invention relates to a method for manufacturing a material. A second invention relates to a method for producing a cosmetic material according to the first invention, wherein the impregnating transparent resin composition is made of an ionizing radiation curable resin that loses its adhesiveness when dried at room temperature. . According to a third invention, in the first or second invention, after the pattern layer is formed on the transparent paper, the impregnation transparent resin composition is impregnated in the pattern layer by impregnating the transparent resin composition for impregnation. The method for producing a cosmetic material according to claim 1, wherein a product is impregnated.

  According to the invention of claim 1 or 2, since the ionizing radiation curable resin and the ionizing radiation curable adhesive can be cured at a time by irradiating the electron beam only once, the strength or durability. Can be produced with good productivity. According to the invention of claim 3, in addition to the effect of the invention of claim 1 or 2, it is possible to provide a decorative material having an excellent decoration effect due to the addition of the pattern layer pattern.

It is sectional drawing of the Example which uses a coloring adhesive agent. It is sectional drawing of the Example using a colored layer and an adhesive agent. It is sectional drawing of the Example which has a transparent resin layer on the uppermost surface. It is sectional drawing of another Example which has a transparent resin layer in the uppermost surface.

  1-4 is a figure which shows the cross-section of the decorative material of the Example of this invention.

  In the decorative material in FIG. 1, the uppermost layer is the transparent paper 4, and the pattern layer 3 is laminated on the lower surface of the transparent paper 4. The transparent paper 4 has a property of being transparent by resin impregnation. Here, the transparent paper 4 is subjected to resin impregnation, and the impregnated resin is solidified. The transparent paper 4 processed in this way has the lower surface on the side with the pattern layer 3 pasted on the substrate 1 via the colored adhesive 2C. In addition, as shown in FIG. 1, the unevenness | corrugation 5 may be further formed in the upper surface of the transparent paper 4. As shown in FIG. The same applies to the embodiments described with reference to the following drawings, but the pattern layer 3 may be laminated on the upper surface of the transparent paper 4.

The decorative material in FIG. 2 is the same as that in FIG. 1 in that the pattern layer 3 is laminated on the transparent paper 4 and is impregnated with the resin, but the base material 1 is placed on the lower surface via the colored adhesive 2C. Instead of pasting on top, the colored layer C and the adhesive 2 are pasted on the base material 1 in this order. That is, the adhesive function of the colored adhesive 2C is divided into the adhesive 2 and the colored function is divided into the colored layer C. In addition, as shown in FIG. 2, the unevenness | corrugation 5 may be further formed in the upper surface of the transparent paper 4. As shown in FIG.

  The decorative material in FIGS. 3 and 4 is obtained by forming a transparent resin layer 6 on the top surface of the decorative material in FIG. 1 for the purpose of surface protection or the like. Among these, as shown in FIG. 3, the unevenness | corrugation 5 may be formed in the transparent paper 4, and the transparent resin layer 6 with a flat upper surface may be laminated | stacked, and as shown in FIG. Concavities and convexities 5 and 5 ′ may be formed on both upper surfaces of the resin layer. Further, although not shown, the transparent paper 4 and the upper surface of the transparent resin layer 6 are not formed with irregularities and may be flat, or the transparent paper 4 has no irregularities. Irregularities may be formed on the upper surface of the transparent resin layer 6.

The transparent paper 4 refers to paper that is generally white and not transparent in the state of the paper alone, but becomes transparent by resin impregnation. Specifically, it is mainly composed of pulp and contains substantially no filler other than pulp, which becomes opaque by resin impregnation. The basis weight (mass per unit area) of the transparent paper 4 is preferably 50 to 300 g / m ² , more preferably 50 to 300 g / m ² . The transparent paper 4 is impregnated with an impregnating resin composition, and is dried and solidified as necessary.

  As the resin component in the impregnating resin composition, diallyl phthalate resin, melamine resin, phenol resin, epoxy resin, benzoguanamine resin, alkyd resin, or acrylate ester can be used. These resins are mixed with a solvent or a diluent and an additive to be added as necessary, dissolved or dispersed to form a resin composition for impregnation, and impregnated on the transparent paper 4 described above.

  In addition to the above-mentioned examples, the impregnation composition includes rubber, natural rubber, recycled rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, stereo. Those containing rubber (synthetic natural rubber), ethylene propylene rubber, block copolymer rubber (SBS, SIS, SEBS, etc.) can also be used.

  The impregnation is performed by dip coating performed by immersing the transparent paper 4 in a container in which the resin composition for impregnation is stored, or coating performed from the front side and / or the back side. In general, an excessive amount of the impregnating resin composition is applied and infiltrated into the inside, and the excess impregnating resin composition is scraped off with a doctor or a smoothing bar or the like and transferred to the drying step. The amount of impregnation is preferably 100 to 300% when the basis weight (mass per unit area) of the transparent paper 4 is 100.

  Drying is performed by air-drying or hot-air drying with wind at a predetermined temperature, or irradiation with near infrared rays or far infrared rays. Alternatively, depending on the resin composition for impregnation, the resin composition for impregnation may be configured by solidifying by means such as irradiation with ultraviolet rays or electron beams, or by using a resin that is easy to touch and dry. These drying means may be used in combination. For example, irradiation with ultraviolet rays or electron beams is performed after air drying or hot air drying.

  When a high durability characteristic is required for the decorative material, an ionizing radiation curable resin composition may be used as the resin composition for impregnation. As the ionizing radiation curable resin composition, a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in the molecule are appropriately mixed. The ionizing radiation refers to an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually an ultraviolet ray or an electron beam is used.

  Examples of prepolymers and oligomers in the ionizing radiation curable resin composition include unsaturated polyesters such as unsaturated dicarboxylic acid and polyhydric alcohol condensates, polyester methacrylate, polyether methacrylate, polyol methacrylate, melamine methacrylate, etc. Examples include methacrylates, polyester acrylates, epoxy acrylates, urethane acrylates, polyether acrylates, polyol acrylates, acrylates such as melamine acrylate, and cationic polymerization type epoxy compounds.

  Examples of the monomer in the ionizing radiation curable resin composition include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, acrylic acid Acrylic esters such as butyl, methoxybutyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate, etc. Esters, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl acrylate, 2- (N, N-dibenzylamino) methyl acrylate, acrylic acid -2- (N, N-diechi Unsaturated substituted amino alcohol esters such as amino) propyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol di Compounds such as acrylate, triethylene glycol diacrylate, polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or two or more thiol groups in the molecule Polythiol compounds having, for example, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol Examples include tetrathioglycolate.

  Usually, as a monomer in an ionizing radiation curable resin composition, the above compounds are used alone or in combination of two or more as required. In order to give it, it is preferable that the prepolymer or oligomer is 5% by weight or more and the monomer and / or polythiol compound is 95% by weight or less.

  When flexibility is required when an ionizing radiation curable resin composition is applied and cured, it is preferable to reduce the amount of monomer or use an acrylate monomer having 1 or 2 functional groups. When wear resistance, heat resistance, and solvent resistance are required when an ionizing radiation curable resin composition is applied and cured, ionizing radiation such as using an acrylate monomer with three or more functional groups A curable resin composition can be designed.

  Here, 2-hydroxy acrylate, 2-hexyl acrylate, and phenoxyethyl acrylate are exemplified as those having one functional group. Examples of those having 2 functional groups include ethylene glycol diacrylate and 1,6-hexanediol diacrylate. Examples of the functional group having 3 or more include trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

  In order to adjust the physical properties such as flexibility and surface hardness when the ionizing radiation curable resin composition is applied and cured, a resin that is not cured by ionizing radiation irradiation should be added to the ionizing radiation curable resin composition. You can also. Specific examples of the resin include the following. Thermoplastic resins such as polyurethane resin, cellulose resin, polyvinyl butyral resin, polyester resin, acrylic resin, polyvinyl chloride resin, and polyvinyl acetate. Among these, addition of a polyurethane resin, a cellulose resin, a polyvinyl butyral resin, or the like is preferable from the viewpoint of improving flexibility.

  When hardening after application | coating of an ionizing radiation curable resin composition is performed by ultraviolet irradiation, a photoinitiator and a photoinitiator are added. As the photopolymerization initiator, in the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like are used alone or in combination. 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 metatheron compound, a benzoin sulfonic acid ester or the like is used as a photopolymerization initiator alone or as a mixture . The addition amount of a photoinitiator is 0.1-10 weight part with respect to 100 weight part of ionizing radiation-curable resin compositions.

  In the decorative material of the present invention, the pattern layer 3 is laminated on the lower layer of the transparent paper 4 as desired. The pattern layer 3 gives decorativeness to the decorative material, and is formed by printing or the like with an appropriate pattern selected according to the application. Examples of the pattern include a natural wood board, a pattern imitating a stone, a pattern imitating a pattern such as a fabric or ceramics, a picture, a photograph, or an abstract pattern. These patterns are formed on a printing plate and printed by a known printing method. As a printing method, in addition to offset printing, gravure printing, letterpress printing, flexographic printing, silk screen printing, etc., electrophotography, an inkjet method, and the like can also be used.

  In the decorative material of the present invention, the pattern layer 3 needs to have transparency of the lower layer so that the colored layer C can be seen through the colored adhesive 2C or the adhesive 2 in the lower layer of the pattern layer 3. When the pattern layer 3 is formed by silk screen printing, since the ink is often light-shielding, the pattern layer 3 needs to be constituted by a portion where the ink has transferred and a portion where the ink has not transferred. In other printing methods, even if the ink has been transferred, the ink film is thin, so it is light transmissive, and since printing is usually performed using halftone dots, there is a gap between the halftone dots. Since the pattern layer 3 is formed, it can be ensured that the lower layer has transparency.

  The pattern layer 3 may or may not be impregnated with the impregnating resin composition impregnated in the transparent paper 4. This difference depends on the type of ink or on the manufacturing process. When the impregnating resin composition is impregnated after printing on the transparent paper 4, if the ink constituting the pattern layer 3 has the permeability of the impregnating resin composition, the resin composition for impregnation in the pattern layer 3 If the ink does not have the permeability of the impregnating resin composition, the patterning layer 3 is not impregnated with the impregnating resin composition. When a cellulose resin or polyvinyl butyral resin is used as the ink vehicle, the resin composition for impregnation can be penetrated. Further, if the transparent layer 4 is impregnated with the impregnating resin composition, dried and solidified, and then formed by printing the pattern layer 3, the impregnating resin composition is not impregnated in the pattern layer 3.

  As the base material 1 occupying the lowermost layer of the decorative material of the present invention, any material can be used as long as it is a material used for a decorative material. Or it classify | categorizes into each group, such as a plastic sheet, metal foil, a metal sheet, or a metal plate, wooden boards, such as wood, and various ceramic materials.

  The materials included in each of the above groups may be used alone, but a laminate of any combination of these materials such as a composite of paper or a composite of paper and a plastic film can also be used. The base material 1 may have a surface that is smoothed or roughened, or may be subjected to a ground treatment in order to improve adhesion.

  Examples of various papers that can be used as the substrate 1 include thin paper, kraft paper, titanium paper, and resin-impregnated paper that has been impregnated with a resin in advance for the purpose of strengthening the paper. In addition to these, a group of original fabrics often used in the building material field, such as linter paper, paperboard, base paper for gypsum board, or a vinyl wallpaper raw fabric provided with a vinyl chloride resin layer on the surface of the paper, can be mentioned. Art paper, coated paper, sulfated paper, glassine paper, parchment paper, paraffin paper, Japanese paper, and the like, which are often used in the printing field, office field, or packaging, can also be used.

  Various types of woven fabrics and nonwoven fabrics having the appearance and properties similar to paper can be used as the substrate 1. The various fibers are glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, or inorganic fibers such as carbon fibers, or synthetic fibers such as polyester fibers or vinylon fibers.

  Examples of the plastic film or plastic sheet include those made of various synthetic resins as exemplified below. Various synthetic resins include polyethylene resin, polypropylene resin, polymethylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer. Resin, ethylene-vinyl alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or Polyamide resin represented by nylon 66, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, or polyimide resin.

  The metal foil, metal sheet, or metal plate is made of a metal as exemplified below. That is, aluminum, iron, stainless steel, or copper. Often used with plating.

  Examples of the various wooden boards include wood boards, plywood, particle boards, or medium density fiber boards called MDF.

  Examples of the ceramic material include ceramic building materials such as gypsum board, calcium silicate board, and wood cement board, ceramics, glass, enamel, and fired tile.

  In addition to these, composites of various materials such as a fiber reinforced plastic plate, a paper honeycomb having both sides coated with iron plates, and a polyethylene resin sandwiched between two aluminum plates can also be used as the substrate 1.

  On the substrate 1 as described above, a transparent resin-impregnated paper impregnated and solidified with a transparent paper 4 is laminated, and the lamination is performed via a colored adhesive 2C. Or the adhesive 2 is colorless and transparent, and the upper surface of the substrate 1 has a colored layer C and is laminated.

  The adhesive 2 includes the material of the base material 1 that is the adhesive surface, or the material of the colored layer C when it has the colored layer C, the impregnated oil resin composition impregnated in the transparent paper 4, the material of the pattern layer 3, etc. Use the one selected in consideration of.

  As the adhesive 2, as a thermoplastic resin adhesive, polyvinyl acetate resin, polyvinyl alcohol, polyvinyl acetal (polyvinyl formal, polyvinyl butyral, etc.), cyanoacrylate, polyvinyl alkyl ether, polyvinyl chloride, polyamide, polymethyl methacrylate, Nitrocellulose, cellulose acetate, thermoplastic epoxy, polystyrene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, etc., or thermosetting resin adhesives include urea resin, melamine resin, phenol resin, resorcinol Resin, furan resin, epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide, polyamideimide, polybenzimidazole, or polybenzothiazole Shall can be used, it can also be used as the rubber mentioned when described with respect to impregnating resin composition.

  As the colored adhesive 2C, an adhesive made of the above-described material may be arbitrarily colored with a colorant made of a dye or a pigment.

  When only the adhesive 2 that is not colored is used, the colored layer C is formed on the upper surface of the substrate 1. The colored layer C is formed as a uniform and uniform layer by using a printing method or a coating method using ink in the same manner as when the pattern layer 3 is formed.

  As the ink vehicle for forming the colored layer C, shellac, rosin, rosin modified maleic acid resin, nitrocellulose, cellulose acetate, cellulose butylacetate, ethyl cellulose, polyamide resin, chlorinated rubber, cyclized rubber, polyamide resin, poly A vinyl chloride resin, a vinyl chloride / vinyl acetate copolymer resin, an ethylene / vinyl acetate copolymer resin, a chlorinated polypropylene, an acrylic resin, a polyurethane resin, or the like can be used.

  A transparent resin layer 6 may be laminated on the upper surface of the transparent resin-impregnated paper in the decorative material of the present invention to improve the surface durability. The transparent resin layer 6 may be configured using a thermoplastic resin, but the use of a thermosetting resin is preferable because it has an effect of improving durability. As an example of the thermosetting resin, a polyurethane resin or an epoxy resin is preferable, and a polyurethane resin is more preferable when flexibility is desired. Furthermore, when it is desired to further improve the durability of the surface, it is preferable to form the surface resin layer 6 using an ionizing radiation curable resin composition, and the ionizing radiation curable resin composition mentioned as the resin composition for impregnation is used. Things can be used.

  The decorative material of the present invention may have irregularities on the surface. Unevenness can be formed by applying an embossing plate or an embossing roll to the surface of the transparent resin-impregnated paper. In the case of having the transparent resin layer 6, the surface of the transparent resin-impregnated paper or the surface of the transparent resin layer 6 may have unevenness or both may have unevenness. It may be. If the surface of the transparent resin layer 6 has irregularities, it is only done by embossing from the transparent resin layer 6 or if the surface of the transparent resin-impregnated paper also has irregularities, Alternatively, the unevenness may be formed sequentially from the lower layer, and when performing in this way, both the uneven shapes can be made different.

  A wiping coating may be performed on one or both of the irregularities on the surface of the transparent resin-impregnated paper and / or the surface of the transparent resin layer 6 to fill the recesses with ink or paint.

  The transparent resin layer 6, the resin composition for impregnation, the adhesive, or the colored adhesive is described in each section, but it is advantageous in terms of the strength and durability of the decorative material that it is composed of a curable resin. It is preferable that at least one or more of these are composed of a curable resin. Moreover, when 1 or 2 or more of the part comprised with curable resin is comprised with ionizing radiation curable resin. Even more preferred.

  The present invention will be described in more detail with reference to the following examples.

After printing a pattern on the back side of a transparent paper having a thickness of 30 μm, the front side is coated with 40 g / m ^{2 of} an electron beam curable resin that loses its adhesiveness when dried at room temperature, and then impregnated. Electron beam curable adhesive containing 30% titanium dioxide on the particle board surface
Applying 15g / m ² (converted when dry), laminating using a roll, and using an electron beam irradiation device from the surface side, irradiating with an electron beam so that the acceleration voltage is 200KV and the irradiation dose is 8Mrad, the cosmetic material is applied. Obtained. The obtained decorative material had a sense of depth, and surface durability was superior to that in Reference Example 1 below .

[Reference Example 1]
After printing a pattern on the back side of a transparent paper with a thickness of 50 μm, a melamine resin was coated from the front side, dried and solidified at 170 ° C. for 1 minute after coating, and a medium density fiber board (MDF) as a substrate Applying 10 g / m ^{2 of} urea adhesive containing 30% titanium dioxide on the surface (converted when dried), drying it once, and then laminating it using a roll whose surface was heated to 150 ° C. A certain cosmetic material was obtained .

[Comparative Examples 1 and 2]
As in Example 1 and Reference Example 1 above, however, a white colored layer is formed with an ink containing titanium dioxide following printing on transparent paper, and as an adhesive when pasted on a substrate. A cosmetic material was obtained using an uncolored one. The pattern of the obtained decorative material was the same as that of the corresponding Example 1 and Reference Example 1 , but the feeling of depth was poorer than that of Example 1 and Reference Example 1 .

DESCRIPTION OF SYMBOLS 1 Base material 2C Colored adhesive 2 Adhesive C Colored layer 3 Pattern layer 4 Transparent paper 5 Concavity and convexity 6 Transparent resin layer

Claims (3)

After impregnating a transparent paper, which is a paper to be clarified by impregnation with resin, with an ionizing radiation curable resin as a transparent resin composition for impregnation, laminating it with a substrate via an ionizing radiation curable colored adhesive, the transparent paper side A method for producing a cosmetic material, comprising: curing an ionizing radiation curable resin impregnated with transparent paper and an ionizing radiation curable coloring adhesive by irradiating an electron beam using an electron beam irradiation device . The method for producing a cosmetic material according to claim 1, wherein the impregnating transparent resin composition comprises an ionizing radiation curable resin that loses its adhesiveness when dried at room temperature . 3. The transparent resin composition for impregnation is impregnated in the pattern layer by impregnating the transparent resin composition for impregnation after forming the pattern layer on the transparent paper. A method for producing the cosmetic material according to claim 1 .

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