JP2019064121A - Size enlargement sheet and manufacturing method of melamine decorative board using the size enlargement sheet - Google Patents

Abstract

To provide a size enlargement sheet for manufacturing a melamine decorative board having an uneven surface low in gloss and excellent in easily cleaning property, fingerprint resistance, and touch feeling, and a method for manufacturing the melamine decorative board using the size enlargement sheet.SOLUTION: There is provided a size enlargement sheet (1) having an uneven surface (10), in which center line average roughness Ra of unevenness constituting the uneven surface (10) is 1.6 μm to 2.7 μm, maximum height Rmax of the unevenness constituting the uneven surface (10) is 11 μm to 16 μm, and average spacing Sm of the unevenness of the uneven surface (10) is 30 μm to 116 μm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a shaped sheet and a method for producing a melamine decorative board using the shaped sheet.

  DESCRIPTION OF RELATED ART Conventionally, the method of manufacturing the melamine decorative board which has an uneven surface is known using the metal plate (embossed board) or shaping sheet which has an uneven surface (for example, patent documents 1-3). In addition, the cured product of the ionizing radiation curable resin has a high crosslink density as compared with a general thermoplastic resin, and the high pressure and high temperature press working performed when producing a melamine decorative board cause degeneration. It is known that the uneven surface of the shaped sheet is preferably formed of a cured product of an ionizing radiation curable resin because it is difficult (for example, Patent Documents 4 and 5).

  In recent years, there has been an increasing demand for melamine decorative boards having a low glossiness of the uneven surface. If the asperities constituting the uneven surface of the melamine decorative board are made finer, the gloss of the uneven surface of the melamine decorative board can be lowered. However, if the irregularities constituting the uneven surface of the melamine decorative board are refined, the easy sweepability and fingerprint resistance of the uneven surface of the melamine decorative board are reduced, and stains and fingerprints attached to the uneven surface of the melamine decorative board are easily made. There is a problem that it can not be removed. Moreover, the problem that the touch feeling of the uneven surface of a melamine decorative board worsens also arises.

JP-A-3-174281 JP-A-8-072214 JP 9-156063 A International Publication No. 2008/111645 Japanese Utility Model Publication No. 61-28628

  Therefore, the present invention provides a shaped sheet for producing a melamine decorative board having a low gloss and having an uneven surface excellent in easy sweepability, fingerprint resistance and touch feeling, and melamine using the shaped sheet. It aims at providing the method of manufacturing a decorative board.

In order to solve the above-mentioned subject, the present invention provides the following inventions.
[1] A shaped sheet having an uneven surface,
The center line average roughness Ra of the unevenness constituting the uneven surface is 1.6 μm or more and 2.7 μm or less,
The maximum height Rmax of the unevenness forming the uneven surface is 11 μm or more and 16 μm or less,
The shaped sheet, wherein the average spacing Sm of irregularities forming the uneven surface is 30 μm or more and 116 μm or less.
[2] The method according to [1], wherein the shaped sheet includes a base sheet and a resin layer provided on the base sheet, and the uneven surface is formed by the surface of the resin layer. Shaped sheet.
[3] The shaped sheet according to [2], wherein the resin layer contains a cured product of an ionizing radiation curable resin.
[4] The shaping according to any one of [1] to [3], wherein the uneven surface has a longitudinal direction and a short direction, and both ends of the uneven surface extending in the longitudinal direction are flat. Sheet.
[5] A method for producing a melamine decorative board having an uneven surface using the shaped sheet according to any one of [1] to [4],
(A) on the uncured melamine resin layer such that the core layer, the uncured melamine resin layer provided on the core layer, and the uneven surface of the shaped sheet are in contact with the uncured melamine resin layer Preparing a laminate comprising the provided shaped sheet;
(B) applying pressure and heat to the laminate to cure the uncured melamine resin layer;
(C) the method including the step of peeling the shaped sheet.

  According to the present invention, a shaped sheet for producing a melamine decorative board having a low gloss, an easy-to-clean surface, an anti-fingerprint property, and an uneven surface excellent in touch feeling, and a melamine using the shaped sheet A method of manufacturing a decorative board is provided.

FIG. 1 is a cross-sectional view schematically showing the configuration of a shaped sheet according to an embodiment of the present invention. FIG. 2 is a partial cross-sectional view schematically showing a configuration of an embodiment of a so-called drum printing system used for manufacturing a formed sheet. FIG. 3A is a view for explaining a method of producing a melamine decorative board using a shaped sheet according to an embodiment of the present invention. FIG. 3B is a view for explaining a method of manufacturing a melamine decorative board using the shaped sheet according to the embodiment of the present invention. FIG. 3C is a figure for demonstrating the method to manufacture a melamine decorative board using the shaping sheet based on one Embodiment of this invention.

  Hereinafter, embodiments of the present invention will be described based on the drawings.

«Composition of shaped sheet»
Hereinafter, based on FIG. 1, the structure of the shaping sheet 1 which concerns on one Embodiment of this invention is demonstrated. FIG. 1 is a cross-sectional view schematically showing the configuration of the shaped sheet 1.

  As shown in FIG. 1, the shaped sheet 1 has an uneven surface 10. The center line average roughness Ra, the maximum height Rmax, and the average interval Sm of the asperities constituting the asperity surface 10 are in the following ranges. As a result, the uneven surface of the melamine decorative board manufactured using the shaping sheet 1 has a low gloss and has excellent easy-to-clean, fingerprint resistance and touch feeling.

  The center line average roughness Ra of the unevenness constituting the uneven surface 10 of the shaped sheet 1 is 1.6 μm or more and 2.7 μm or less, preferably 1.7 μm or more and 2.5 μm or less, and more preferably 1.8 μm or more. It is 3 μm or less. The definition of centerline average roughness Ra follows JIS B0601-1982.

  The maximum height Rmax of the unevenness constituting the uneven surface 10 of the shaped sheet 1 is 11 μm to 16 μm, preferably 12 μm to 16 μm, and more preferably 14 μm to 16 μm. The definition of maximum height Rmax follows JIS B0601-1982.

  The average interval Sm of the unevenness constituting the uneven surface 10 of the shaped sheet 1 is 30 μm to 116 μm, preferably 60 μm to 110 μm, and more preferably 80 μm to 100 μm. The definition of the average interval Sm conforms to JIS B0601-1994.

The measurement of Ra, Rmax and Sm is carried out using a surface roughness measuring instrument (three-dimensional surface roughness measuring instrument SE-30K manufactured by Kosaka Laboratory) and a surface roughness analyzer (surf coder AY-31 manufactured by Kosaka Laboratory) It measured according to the following conditions.
1) Contact diameter and tip diameter of surface roughness detection unit: R 2 μm
・ Skid: R40 mm × R2 mm
· Material: sapphire · needle pressure: 0.7μN
・ Feeding speed of stylus: 0.5 mm / s
2) Measurement condition · Cut-off value (reference length): 0.08 mm
・ Measurement length (cutoff value x 100): 8 mm
・ Vertical magnification: 1000 times ・ Lateral magnification: 10 times

  The 60 ° glossiness of the uneven surface 10 of the shaped sheet 1 is preferably 20 or less, and more preferably 17 or less. The lower limit value of the 60 ° glossiness is not particularly limited, but is preferably 11, and more preferably 12. The 60 ° glossiness is measured in accordance with JIS Z8741: 1997. Specifically, using GMX-202 manufactured by Murakami Color Research Laboratory as a gloss meter, the 60 ° glossiness of the uneven surface 10 of the shaped sheet 1 is measured under the condition of an incident angle = 60 °.

  The whole uneven | corrugated surface 10 of the shaping sheet 1 may have uneven | corrugated formation, and the one part may have uneven | corrugated shape. As an embodiment in which a part of the concavo-convex surface 10 of the shaped sheet 1 has a concavo-convex shape, for example, the concavo-convex surface 10 has a longitudinal direction and a short direction, and both ends of the concavo-convex surface 10 extending in the longitudinal direction Embodiments are flat. In such an embodiment, the uneven surface 10 is, for example, rectangular in plan view. In the uneven surface of the roll mold used in the drum printing system, when both ends extending in the circumferential direction of the roll mold are flat, both ends of the uneven surface 10 extending in the longitudinal direction (MD direction) A shaped sheet 1 can be manufactured. Accordingly, the fact that both ends of the uneven surface 10 extending in the longitudinal direction (MD direction) are flat may be a feature of a shaped sheet manufactured using a drum printing system. If the both ends of the uneven surface of the roll mold used in the drum printing system and extending in the circumferential direction of the roll mold are flat, peeling of the shaped sheet from the roll mold becomes easy. Flat means that the center line average roughness Ra is 0.5 μm or less, the maximum height Rmax is 1.0 μm or less, and the average interval Sm is 20 μm or less. The definitions of the center line average roughness Ra and the maximum height Rmax are in accordance with JIS B0601-1982, and the definition of the average interval Sm is in accordance with JIS B0601-1994. The measurement of Ra, Rmax and Sm is carried out using a surface roughness measuring instrument (three-dimensional surface roughness measuring instrument SE-30K manufactured by Kosaka Laboratory) and a surface roughness analyzer (surf coder AY-31 manufactured by Kosaka Laboratory) In accordance with the above conditions.

  As shown in FIG. 1, the shaped sheet 1 includes a base sheet 11 and a resin layer 12 provided on the base sheet 11.

<Support layer>
Hereinafter, the base material sheet 11 is demonstrated based on FIG.
As shown in FIG. 1, the base material sheet 11 has 1st main surface T1 and 2nd main surface T2 located in the other side of 1st main surface T1.

  The base sheet 11 is not particularly limited as long as it can support the layer provided thereon. The base sheet 11 preferably has flexibility. When the base sheet 11 has flexibility, the shaped sheet 1 is easily peeled off from the shaped body. The base sheet 11 is, for example, a plastic sheet. As a synthetic resin which constitutes a plastic sheet, for example, polyolefin resin such as polyethylene resin, polypropylene resin, polymethylpentene resin, olefin thermoplastic elastomer; polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride- Vinyl resins such as 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, polyester-based thermoplastic resin Polyester resins such as elastomers; methyl poly (meth) acrylate resins, poly (meth) acrylate ethyl resins, poly (meth) acrylate butyl resins etc. acrylic resins; nylon 6 or Polyamide resins represented by nylon 66 and the like; polystyrene resins; polycarbonate resins; polyarylate resin; cellulose triacetate resins, cellulose resins such as cellophane and polyimide resins. Among these, polyester resins such as polyethylene terephthalate, particularly biaxially stretched polyester resins, are preferable in terms of excellent heat resistance and dimensional stability.

  In order to improve the adhesion with the layer provided on the base sheet 11, an easy adhesion layer may be formed on the surface of the base sheet 11. Examples of easy-adhesion resins contained in the easy-adhesion layer (sometimes referred to as primer layer and anchor layer) include acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, urethane resin, chlorinated polypropylene, chlorine Polyethylene and the like.

  In order to improve the adhesion with the layer provided on the base sheet 11, the surface of the base sheet 11 may be subjected to physical or chemical surface treatment such as an oxidation method or a roughening method. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone and ultraviolet ray treatment, and the like, and examples of the surface roughening method include sand blast method and solvent treatment method.

  The thickness of the base sheet 11 is not particularly limited, but when using a plastic sheet as the base sheet 11, the thickness of the plastic sheet is preferably 12 μm or more and 125 μm or less, more preferably 38 μm or more and 100 μm or less.

<Resin layer>
Hereinafter, the resin layer 12 will be described based on FIG.
As shown in FIG. 1, the resin layer 12 is provided on the entire first main surface T1 of the base sheet 11. The resin layer 12 may be provided on a part of the first main surface T1 of the base sheet 11. When the resin layer 12 is provided on a part of the first main surface T1 of the base sheet 11, the area of the first main surface T1 of the base sheet 11 where the resin layer 12 is provided is one continuous area. It may be a plurality of discrete areas. The resin layer 12 may be composed of one continuous layer or may be composed of a plurality of discontinuous layers.

  As shown in FIG. 1, the surface of the resin layer 12 has a concavo-convex shape, and forms the concavo-convex surface 10 of the shaped sheet 1.

  The resin layer 12 is a layer containing a cured resin, and for example, after a composition for forming a resin layer containing a curable resin is applied to the base sheet 11 to form a coating film of the composition for forming a resin layer, It can form by the method (for example, the drum printing method, the nanoimprint method) etc. which press the type | mold which has a predetermined | prescribed uneven surface on a coating film, and hardens a coating film. Among these, the drum printing method is preferable in terms of easy production.

  The resin layer 12 formed by the above method is a layer formed by curing of the composition for forming a resin layer containing a curable resin, and includes a cured product of the curable resin. The curable resin contained in the composition for resin layer formation is preferably an ionizing radiation curable resin, and the resin layer 12 preferably contains a cured product of the ionizing radiation curable resin. The resin layer 12 formed by the above method usually does not contain fine particles that can contribute to the formation of the uneven surface 10 of the shaped sheet 1.

  The composition for forming a resin layer is, for example, a mixture of a solvent or a dispersion medium and a solid content such as an ionizing radiation curable resin.

  Examples of the solvent or dispersion medium include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, methylcyclohexane and the like; ethyl acetate, butyl acetate, butyl 2-methoxyethyl acetate, acetic acid 2-ethoxy Ester organic solvents such as ethyl; alcohol organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol; ketone organics such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Solvents; Ether-based organic solvents such as diethyl ether, dioxane, tetrahydrofuran, etc .; Salts such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. System organic solvent; inorganic solvents such as water. The solvent or the dispersion medium may be used alone or in combination of two or more.

  The ionizing radiation curable resin composition comprises one or more ionizing radiation curable resins. An ionizing radiation curable resin is a resin that undergoes a cross-linking polymerization reaction upon irradiation with ionizing radiation and changes into a three-dimensional polymer structure. Ionizing radiation means any of electromagnetic waves or charged particle beams having energy quantums capable of polymerizing or crosslinking molecules, and usually ultraviolet (UV) or electron beam (EB) is used, but others, X It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays. Among the ionizing radiation curable resins, electron beam curable resins are preferable in that they can be made solventless and stable curing characteristics can be obtained.

  As the ionizing radiation curable resin, for example, one or more kinds of monomers, oligomers, prepolymers, etc. having a polymerizable unsaturated bond crosslinkable by irradiation of ionizing radiation, a cationically polymerizable functional group and the like in the molecule are used. Can. The ionizing radiation curable resin contained in the ionizing radiation curable resin composition may be one type or two or more types.

  As said monomer used as ionizing radiation curable resin, the (meth) acrylate monomer etc. which have a radically polymerizable unsaturated group in a molecule | numerator are mentioned, for example, Especially, a polyfunctional (meth) acrylate monomer is preferable. In addition, "(meth) acrylate" means an acrylate or a methacrylate.

  The polyfunctional (meth) acrylate monomer may be a (meth) acrylate monomer having two or more (bifunctional or more), preferably three or more (trifunctional or more) polymerizable unsaturated bonds in the molecule, It is not limited. As polyfunctional (meth) acrylate, for example, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) Acrylate, ethylene oxide modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate Ethylene oxide modified trimethylolpropane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth ) Acrylate, tris (acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexahex Examples include (meth) acrylates and the like. A polyfunctional (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type. A monofunctional (meth) acrylate may be used in combination with the multifunctional (meth) acrylate for the purpose of lowering the viscosity, etc.

  Examples of the above-mentioned oligomer used as an ionizing radiation curable resin include (meth) acrylate oligomers having a radically polymerizable unsaturated group in the molecule, and in particular, two polymerizable unsaturated bonds in the molecule. The polyfunctional (meth) acrylate oligomer which has the above (two or more functions) is preferable. As a polyfunctional (meth) acrylate oligomer, for example, polycarbonate (meth) acrylate, acrylic silicone (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate And polybutadiene (meth) acrylate, silicon (meth) acrylate, and oligomers having a cationically polymerizable functional group in the molecule (eg, novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether etc.), etc. . Here, the polycarbonate (meth) acrylate is not particularly limited as long as it has a carbonate bond in the polymer main chain and a (meth) acrylate group at the terminal or side chain, for example, polycarbonate polyol (meth) It can be obtained by esterification with acrylic acid. The polycarbonate (meth) acrylate may be, for example, a urethane (meth) acrylate having a polycarbonate skeleton. The urethane (meth) acrylate having a polycarbonate skeleton is obtained, for example, by reacting a polycarbonate polyol, a polyvalent isocyanate compound, and a hydroxy (meth) acrylate. Acrylic silicone (meth) acrylates can be obtained by radical copolymerization of silicone macromonomers with (meth) acrylate monomers. The urethane (meth) acrylate can be obtained, for example, by esterifying a polyurethane oligomer obtained by the reaction of a polyether polyol or a polyester polyol with a polyisocyanate with (meth) acrylic acid. The epoxy (meth) acrylate can be obtained, for example, by reacting (esterification) of (meth) acrylic acid with the oxirane ring of a relatively low molecular weight bisphenol epoxy resin or novolac epoxy resin. In addition, carboxyl-modified epoxy (meth) acrylates obtained by partially modifying this epoxy (meth) acrylate with dibasic carboxylic acid anhydride can also be used. Polyester (meth) acrylate can be obtained, for example, by esterifying the hydroxyl group of a polyester oligomer having hydroxyl groups at both ends obtained by condensation of polyvalent carboxylic acid and polyvalent alcohol with (meth) acrylic acid, or into polyvalent carboxylic acid It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide with (meth) acrylic acid. Polyether (meth) acrylate can be obtained by esterifying the hydroxyl group of polyether polyol with (meth) acrylic acid. Polybutadiene (meth) acrylate can be obtained by adding (meth) acrylic acid to the side chain of a polybutadiene oligomer. Silicon (meth) acrylate can be obtained by adding (meth) (meth) acrylic acid to the terminal or side chain of silicon having a polysiloxane bond in the main chain. Among these, from the viewpoint of further increasing the hardness of the resin layer 12, a urethane (meth) acrylate oligomer is preferable. One of these oligomers may be used alone, or two or more of these oligomers may be used in combination.

  The weight average molecular weight of the ionizing radiation curable resin is preferably 500 or more, more preferably 1000 or more. When the composition for forming a resin layer is applied to the base sheet 11 when the weight average molecular weight of the ionizing radiation curable resin is in the above range, the composition for forming a resin layer is unlikely to penetrate the base sheet 11, It is easy to form the coating film of the composition for resin layer formation.

  The weight average molecular weight of the ionizing radiation curable resin is preferably 80,000 or less, more preferably 50,000 or less. It is easy to adjust the viscosity of the composition for resin layer formation to the viscosity suitable for application | coating that the weight average molecular weight of ionizing radiation curable resin is the said range.

  The "weight average molecular weight" is a value measured by using polystyrene as a standard substance by gel permeation chromatography (GPC).

  The ionizing radiation curable resin is preferably at least one selected from polyfunctional monomers and oligomers having a weight average molecular weight of 500 or more. Examples of such polyfunctional monomers or oligomers include acrylate resins such as dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, urethane acrylate, polyester acrylate, epoxy acrylate and the like.

  The composition for forming a resin layer may optionally contain a component involved in the curing reaction of the ionizing radiation curable resin, for example, a photopolymerization initiator (sensitizer). For example, in the case of curing the ionizing radiation curable resin by irradiation of ultraviolet rays, the composition for forming a resin layer preferably contains a photopolymerization initiator (sensitizer). Since the ionizing radiation curable resin is sufficiently cured by the irradiation of the electron beam, when curing the ionizing radiation curable resin by the irradiation of the electron beam, the composition for forming the resin layer is a photopolymerization initiator (a sensitizer It does not have to include.

  When the ionizing radiation curable resin has a radically polymerizable unsaturated group, examples of the photopolymerization initiator include acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler's benzoyl benzoate, Michler's ketone, diphenyl sulfide, At least one selected from dibenzyl disulfide, diethyl oxalate, triphenyl biimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. When the ionizing radiation curable resin has a cationically polymerizable functional group, examples of the photopolymerization initiator include aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonic acid esters, and freeroxysulfoxonium compounds. At least one such as diallyl iodosyl salt can be used.

  Although the quantity of the photoinitiator contained in the composition for resin layer formation is not specifically limited, It is 0.1 to 10 mass parts normally with respect to 100 mass parts of ionizing radiation curable resin.

  The resin layer 12 may be, if necessary, a solvent-drying resin (a thermoplastic resin or the like, which becomes a film only by drying the solvent added to adjust the solid content at the time of coating). It may contain a resin or the like.

  By adding the solvent-drying resin to the composition for forming a resin layer, it is possible to effectively prevent a coating defect on the application surface of the composition for forming a resin layer when forming the resin layer 12. As the solvent-drying resin, for example, a thermoplastic resin can be used, and as the thermoplastic resin, for example, a styrene resin, (meth) acrylic resin, vinyl acetate resin, vinyl ether resin, halogen-containing resin Alicyclic olefin resin, polycarbonate resin, polyester resin, polyamide resin, cellulose derivative, silicone resin, rubber, elastomer, and the like. As a thermosetting resin, for example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, amino alkyd resin, melamine-urea cocondensation resin, silicon resin, Polysiloxane resin etc. are mentioned.

  The composition for forming a resin layer is for the purpose of increasing the hardness of the resin layer, suppressing curing shrinkage, etc., a dispersant, a surfactant, an antistatic agent, a silane coupling agent, a thickener, a coloring inhibitor, coloring Agents (pigments, dyes), antifoaming agents, leveling agents, flame retardants, UV absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, lubricants and the like.

  The thickness of the resin layer 12 is not particularly limited, but is preferably 10 μm to 500 μm, more preferably 20 μm to 50 μm. In addition, it is preferable that both the minimum thickness and the maximum thickness of the resin layer 12 exist in the said range.

«Production of shaped sheet»
Hereinafter, manufacture of the shaping sheet 1 using a drum printing system is demonstrated.

  The shaping sheet 1 is manufactured, for example, using a so-called drum printing system to which a roll intaglio printing method is applied. The drum printing system (Drum Printing System, hereinafter referred to as DPS) means the fine structure of the ridges on the plate surface, as disclosed in JP-A-5-238196 and JP-B-3083380. It is a rotary-type intaglio printing method that can be faithfully shaped on the surface of the ionizing radiation curable resin layer including the parts.

  FIG. 2 is a partial cross-sectional view schematically showing a configuration of an embodiment of a drum printing system used for manufacturing a formed sheet. As shown in FIG. 2, the drum printing system 2 according to the present embodiment includes a roll mold 21 having an uneven surface 210 on its surface, guide rolls 22 a and 22 b for guiding the traveling of the base sheet 11, and a roll mold. 21 for forming a resin layer containing an ionizing radiation curable resin toward the nip roll 23a disposed on the upstream side of the roll 21, the nip roll 23b disposed on the downstream side of the roll mold 21, and the uneven surface 210 of the roll mold 21 The supply unit 24 for supplying the composition L, and the irradiation unit 25 for irradiating the ionizing radiation R toward the uneven surface 210 of the roll mold 21 are provided. In FIG. 2, the uneven shape of the uneven surface 210 of the roll mold 21 and the uneven shape formed on the surface of the resin layer 12 by the uneven surface 210 of the roll mold 21 are omitted. Moreover, in FIG. 2, the arrow regarding a sheet | seat shows the advancing direction (MD direction), and the arrow regarding a roll shows the rotation direction.

  The center line average roughness Ra of the asperities constituting the asperity surface 210 of the roll mold 21 is usually 1.6 to 4.0 μm, preferably 1.7 to 4.0 μm, and more preferably 1.8 to 3 μm. .0 μm or less. The definition of centerline average roughness Ra follows JIS B0601-1982.

  The maximum height Rmax of the asperities constituting the asperity surface 210 of the roll mold 21 is usually 11 μm to 16 μm, preferably 12 μm to 16 μm, and more preferably 14 m to 16 μm. The definition of maximum height Rmax follows JIS B0601-1982.

  The average interval Sm of the unevenness forming the unevenness surface 210 of the roll mold 21 is usually 30 μm to 116 μm, preferably 60 μm to 110 μm, and more preferably 80 μm to 100 μm. The definition of the average interval Sm conforms to JIS B0601-1994.

  The measurement of Ra, Rmax and Sm is carried out using a surface roughness measuring instrument (three-dimensional surface roughness measuring instrument SE-30K manufactured by Kosaka Laboratory) and a surface roughness analyzer (surf coder AY-31 manufactured by Kosaka Laboratory) In accordance with the above conditions.

  The method of manufacturing the shaped sheet 1 by the drum printing system 2 includes the following steps (1) to (4).

  The step (1) is a step of supplying the resin layer-forming composition L containing an ionizing radiation curable resin from the supply unit 24 to the uneven surface 210 of the rotating roll mold 21.

  In the step (2), the base sheet 11 traveling in synchronization with the rotational direction of the roll mold 21 is pressed against the uneven surface 210 of the roll mold 21 by the upstream nip roll 23 a, In this step, the resin layer-forming composition L supplied to the uneven surface 210 of the mold 21 is brought into contact with the uneven surface 210. In the step (2), the mold side surface of the coating film of the composition L for forming a resin layer is shaped in a concavo-convex shape along the concavo-convex surface 210 of the roll mold 21.

  Before the step (2), when the composition L for forming a resin layer contains a solvent or a dispersion medium, the composition L for forming a resin layer supplied to the uneven surface 210 of the roll mold 21 is dried (not shown) May be dried.

  In the step (3), the ionizing radiation R is irradiated from the irradiation unit 25 to the second main surface T2 of the base sheet 11 up to the nip roll 23b downstream, and the base sheet 11 and the roll mold 21 And curing the ionizing radiation curable resin in the composition L for forming a resin layer interposed therebetween.

  When ultraviolet light is used as the ionizing radiation R for curing the ionizing radiation curable resin, for example, ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc lamp, black light fluorescent lamp, metal halide lamp And other light sources can be used. The wavelength of the ultraviolet light is usually 190 nm or more and 380 nm or less. In the case of using an electron beam as the ionizing radiation R for curing the ionizing radiation curable resin, for example, a Cockcroft-wald type, a bande graft type, a resonant transformer type, an insulating core transformer type, a straight line as an electron beam source Type, dynamitron type, high frequency type electron beam accelerators can be used. The energy of the electron beam is generally 100 keV to 1000 keV, preferably 100 keV to 300 keV. The irradiation dose of the electron beam is usually 2 Mrad or more and 15 Mrad or less.

  In the step (3), the cured product of the ionizing radiation curable resin adheres to the base sheet 11, and the shaped sheet 1 including the base sheet 11 and the resin layer 12 provided on the base sheet is formed. Ru. The surface of the resin layer 12 has a concavo-convex shape imparted by the concavo-convex surface 210 of the roll mold 21 and forms the concavo-convex surface 10 of the shaped sheet 1.

  The step (4) is a step of peeling the shaped sheet 1 from the uneven surface 210 of the roll mold 21 by the downstream nip roll 23b. The shaped sheet 1 peeled off from the roll mold 21 may be taken up by a discharge roll (not shown).

«Use of shaped sheet»
The shaping sheet 1 is used to manufacture a melamine decorative board having an uneven surface. Hereinafter, based on FIG. 3A-FIG. 3C, one Embodiment of the method of manufacturing the melamine decorative board which has an uneven surface using the shaping sheet | seat 1 is described. FIGS. 3A to 3C are diagrams for explaining a method of manufacturing the melamine decorative board 4 using the shaped sheet 1.

  The method for producing a melamine decorative board according to the present embodiment includes (a) preparing the laminate 3, (b) pressurizing and heating the laminate 3, and (c) peeling the shaped sheet 1 Including the steps.

  As shown to FIG. 3A, the laminated body 3 prepared by process (a) is provided on the core layer 31, the unhardened melamine resin layer 32 provided on the core layer 31, and the unhardened melamine resin layer 32. And the shaped sheet 1. The shaping sheet 1 is provided on the uncured melamine resin layer 32 such that the uneven surface 10 of the shaping sheet 1 is in contact with the uncured melamine resin layer 32. As a result, the surface on the shaping sheet side of the uncured melamine resin layer 32 is shaped in a concavo-convex shape along the concavo-convex surface 10 of the shaping sheet 1.

The core layer 31 is, for example, a phenol resin impregnated paper or a laminate thereof. As a phenol resin impregnated paper, a kraft paper having a basis weight of about 150 to 300 g / m ² , a resin containing a phenol resin as a main component, and an impregnation rate of about 30 to 80% calculated by a formula described later It is obtained by impregnating and drying.

  The core layer 31 may be a glass cloth or a glass non-woven fabric, or a prepreg having a glass cloth or a glass non-woven fabric as a base. The prepreg is obtained, for example, by impregnating a resin composition containing a thermoplastic resin, a thermosetting resin or the like with a glass cloth or a glass non-woven fabric.

  The uncured melamine resin layer 32 is obtained by impregnating an uncured material of a melamine resin on a base paper for decorative board. The uncured material of the melamine resin is obtained by reacting melamine and formaldehyde under neutral or alkaline conditions, and the reaction product of melamine and formaldehyde is methylolmelamines (monomethylolmelamine, dimethylolmelamine, Containing hexamethylolmelamine). Melamine resins are also referred to as melamine-formaldehyde resins.

The uncured melamine resin layer 32 is, for example, melamine resin impregnated paper or a laminate thereof. The melamine resin-impregnated paper is, for example, a base paper for decorative board having a basis weight of about 70 to 140 g / m ² , an uncured material of melamine resin, typically a resin having methylolmelamine as a main component, It is obtained by impregnating so that the impregnation rate to be achieved may be about 70 to 160% and drying.

The uncured melamine resin layer 32 may be a laminate including melamine resin impregnated overlay paper or melamine resin impregnated overlay paper. The melamine resin-impregnated overlay paper is, for example, an overlay base paper having a basis weight of about 23 to 60 g / m ² and a resin mainly composed of non-acidified melamine resin, typically methylolmelamine, calculated by the formula described later. To obtain an impregnation rate of about 200 to 400% and drying. The melamine resin-impregnated overlay paper can be used, for example, as the uncured melamine resin layer 32 after being laminated on a decorative board.

  The uncured melamine resin layer 32 may be a laminate including both melamine resin impregnated paper and melamine resin impregnated overlay paper.

The impregnation rate in the phenol resin-impregnated paper and the melamine resin-impregnated paper is determined based on the following equation.
Impregnation rate (%) = [(mass of impregnated paper after impregnation) − (mass of base paper before impregnation)] / (mass of base paper before impregnation × 100)

  The pressurization and heating of the laminate 3 in the step (b) are performed, for example, in a state in which the laminate 3 is sandwiched between two mirror-finished metal plates P1 and P2 as shown in FIG. 3B. By pressing and heating the laminate 3, the uncured material of the melamine resin contained in the uncured melamine resin layer 32 is cured. The pressure and heating of the laminate 3 cure the uncured melamine resin layer 32 in a state in which the surface is shaped in the concavo-convex shape along the concavo-convex surface 10 of the shaping sheet 1, and cure the cured melamine resin. A cured resin layer is formed. The cured resin layer becomes the surface layer 42 after peeling of the shaping sheet 1. The core layer 31 is formed from the core layer 31 by pressing and heating the laminate 3. When a phenol resin-impregnated paper or a laminate thereof is used as the core layer 31, the phenol resin contained in the core layer 31 is also cured at this stage.

  In the step (c), by peeling the shaped sheet 1 from the remaining part of the laminate 3, as shown in FIG. 3C, the melamine decorative board 4 having the uneven surface 40 is manufactured. The melamine decorative board 4 comprises a core layer 41 and a surface layer 42 containing a cured product of a melamine resin. The surface of the surface layer 42 has a concavo-convex shape imparted by the shaped sheet 1 and forms the concavo-convex surface 40 of the melamine decorative board 4. The precursor layer of the core layer 41 is the core layer 31 of the laminate 3, and the core layer 41 is generated from the core layer 31 by pressing and heating the laminate 3 in the step (b). The precursor layer of the surface layer 42 is the uncured melamine resin layer 32 of the laminate 3 and is made of a cured product of the uncured melamine resin layer 32 by the laminate 3 being pressurized and heated in step (b). A surface layer 42 is produced.

  The center line average roughness Ra, the maximum height Rmax and the average interval Sm of the asperities constituting the asperity surface 40 of the melamine decorative board 4 are preferably in the following ranges. As a result, the uneven surface 40 of the melamine decorative board 4 has low gloss, and also has excellent easy-to-clean, fingerprint resistance and touch feeling.

  The center line average roughness Ra of the asperities constituting the asperity surface 40 of the melamine decorative board 4 is preferably 1.4 μm or more and 2.3 μm or less. The definition of centerline average roughness Ra follows JIS B0601-1982.

  The maximum height Rmax of the unevenness constituting the uneven surface 40 of the melamine decorative board 4 is preferably 10 μm to 16 μm, and more preferably 11 μm to 14 μm. The definition of maximum height Rmax follows JIS B0601-1982.

  The average interval Sm of the unevenness forming the uneven surface 40 of the melamine decorative board 4 is preferably 30 μm or more and 100 μm or less, more preferably 50 μm or more and 100 μm or less. The definition of the average interval Sm conforms to JIS B0601-1994.

  The measurement of Ra, Rmax and Sm is carried out using a surface roughness measuring instrument (three-dimensional surface roughness measuring instrument SE-30K manufactured by Kosaka Laboratory) and a surface roughness analyzer (surf coder AY-31 manufactured by Kosaka Laboratory) In accordance with the above conditions.

  The melamine decorative board 4 exhibits, for example, a dark color. Whether or not the melamine decorative board 4 exhibits a dark color can be determined by visually recognizing the melamine decorative board 4 from the uneven surface 40 side of the melamine decorative board 4. "Dark color" means that the color tone is a low lightness chromatic or achromatic color. For example, achromatic colors such as black and dark gray, and chromatic colors such as amber, brownish brown, yellowish brown, deep green, deep purple, and resin color correspond to dark. The dark color is preferably black.

  When the surface layer 42 exhibits a dark color, the melamine decorative board 4 can exhibit a dark color. When the uncured melamine resin layer 32 contains a dark color pigment, the surface layer 42 can exhibit a dark color. Dark color pigments are contained, for example, in decorative base paper used as pattern paper. The dark pigment can be suitably selected from known dark pigments. Dark pigments may be used alone or in combination of two or more. As a black pigment, an organic black pigment, an inorganic black pigment, etc. are mentioned, for example. Examples of organic black pigments include azomethine azo black pigments, perylene black pigments, azo black pigments, aniline black, acetylene black, carbon black, lamp black, benzimidazolone pigment brown 25 (brown) and phthalocyanine blue (blue). And mixed pigments thereof and the like. As an inorganic black pigment, complex oxide, iron black, titanium black etc. are mentioned, for example. The complex oxide is an oxide containing at least two metal elements. The composite oxide is preferably a composite oxide containing at least a manganese element, that is, an oxide containing a manganese element and at least one metal element other than the manganese element. The metal element other than the manganese element contained in the composite oxide is not particularly limited, and can be appropriately selected. The metal elements other than the manganese element contained in the complex oxide may be used alone or in combination of two or more. As metal elements other than the manganese element contained in the complex oxide, for example, group 2 elements such as calcium element and barium element; yttrium element, lanthanum element, praseodymium element; group 3 element such as neodymium element, titanium element, Group 4 elements such as zirconium elements; Group 13 elements such as boron elements, aluminum elements, gallium elements, and indium elements; metal elements such as Group 15 elements such as antimony elements and bismuth elements. Among these, Group 2 elements, Group 4 elements and Group 15 elements are preferable, a calcium element, a titanium element and a bismuth element are more preferable, and a calcium element and a titanium element are more preferable. Particularly preferable specific examples of the composite oxide include composite oxides containing a manganese element, a calcium element and a titanium element.

  When the melamine decorative board 4 exhibits a dark color, the 60 ° glossiness of the uneven surface 40 of the melamine decorative board 4 is preferably 5 or less, more preferably 3 or less. The lower limit of the 60 ° gloss is not particularly limited, but is preferably 0.1, and more preferably 1.

  The 60 ° glossiness of the uneven surface 40 of the melamine decorative board 4 is measured in accordance with JIS Z8741: 1997. Specifically, using GMX-202 manufactured by Murakami Color Research Laboratory as a gloss meter, the 60 ° glossiness of the uneven surface 40 of the melamine decorative board 4 is measured under the condition of incident angle = 60 °.

  Hereinafter, the present invention will be described based on examples.

[Examples 1 to 6 and Comparative Examples 1 to 3]
(1) Production of Shaped Sheet An uneven shape is formed on the surface of a metal roll matrix formed by forming a copper plating layer on the surface of a hollow cylindrical iron core by etching, and a roll mold having an uneven surface is prepared. did. The characteristics of the uneven surface of the roll die used in Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1.

  A shaped sheet was manufactured by a drum printing system using a roll mold having an uneven surface. Specifically, a shaped sheet was manufactured by the following procedure using DPS shown in FIG.

A composition for forming a resin layer comprising 50 parts of a mixed resin of 50 parts of polyethylene glycol diacrylate (PEG), a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (PETA), and 5 parts of a photoinitiator is roll gold While being supplied to the uneven surface of the mold, a 125 μm-thick biaxially stretched polyethylene terephthalate (PET) substrate (A4100 manufactured by Toyobo Co., Ltd.) was superposed on the composition for forming a resin layer and pressure-bonded. Next, using a Fusion D-bulb (600 W / inch), the resin is irradiated with ultraviolet light under conditions of 180 mJ / cm ² to cure the resin layer-forming composition, and the cured product of the ionizing radiation curable resin is It adhered to the material sheet. Thus, it is a shaped sheet comprising a base material sheet and a resin layer provided on the base material sheet, wherein the surface of the resin layer has an uneven shape imparted by the uneven surface of the roll mold, A shaped sheet was formed to form the irregular surface of the shaped sheet. Then, the shaped sheet was peeled from the roll mold. The characteristics of the uneven surface of the shaped sheets manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1. The thickness of the resin layer was 30 μm.

(2) Production of a melamine decorative board using a shaped sheet 100 parts by mass of a water-soluble methylolmelamine (Nika Resin S-260 manufactured by Nippon Carbide Co., Ltd.) is diluted with 60 parts by mass of water to form a melamine-formaldehyde aqueous solution (uncured melamine resin after preparing the uncured melamine resin liquid composition) containing the goods, dried impregnated such that the basis weight of 80 g / m wet pickup 80 g / m 2 relative to the ^second veneer sheet ^(dry) And melamine resin impregnated paper were produced. Under the present circumstances, when using a titanium paper as a base paper for decorative boards and manufacturing a white decorative board, when manufacturing a black decorative board as KJ special paper company KW-801P as a titanium base paper, a titanium base paper is manufactured. As PM, PM-802PK manufactured by KJ Specialty Paper Co., Ltd. was used.

Two sheets of phenol resin impregnated core paper (Ota core made by Ota Sangyo Co., Ltd.) having a basis weight of 245 g / m ² prepared by impregnating a resin composition containing a phenol resin with kraft paper are laminated, and phenol resin impregnated core paper Forming a laminated sheet on which the melamine resin-impregnated paper is laminated, and further forming the molded sheet on the melamine resin-impregnated paper so that the uneven surface of the resin layer (the shaping surface of the shaped sheet) contacts the melamine resin-impregnated paper Stacked.

The laminate thus formed was sandwiched by a press plate consisting of two mirror-finished sheet metal plates P1 and P2 and press-worked for 30 minutes under conditions of a temperature of 135 ° C. and a press pressure of 9.8 N / m ² . After pressing, the shaped sheet was peeled off to obtain a melamine decorative board having an uneven surface. The characteristics of the melamine decorative board manufactured in Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1.

(3) Evaluation method The evaluation method of the characteristic of a shaping sheet and a melamine decorative board is as follows.

[Surface roughness]
The centerline average roughness Ra (JIS B 0601-1982) of the concavities and convexities constituting the concavo-convex surface, and the concavo-convexity constituting the concavo-convex surface regarding the shaped sheet and the melamine decorative board (melamine decorative board manufactured using black titanium paper) The maximum height Rmax (JIS B0601-1982) and the average interval Sm (JIS B0601-1994) of the concavities and convexities constituting the concavo-convex surface were measured using a surface roughness tester (three-dimensional surface roughness tester SE- made by Kosaka Laboratory). It measured according to the following conditions using 30 K) and surface roughness analyzer (Kosaka Labs make surf coder AY-31).
1) Contact diameter and tip diameter of surface roughness detection unit: R 2 μm
・ Skid: R40 mm × R2 mm
· Material: sapphire · needle pressure: 0.7μN
・ Feeding speed of stylus: 0.5 mm / s
2) Measurement condition · Cut-off value (reference length): 0.08 mm
・ Measurement length (cutoff value x 100): 8 mm
・ Vertical magnification: 1000 times ・ Lateral magnification: 10 times

[60 ° glossiness]
With respect to the shaped sheet and the melamine decorative board (a melamine decorative board manufactured using a melamine decorative board manufactured using black titanium paper), the 60 ° glossiness of the uneven surface is measured according to JIS Z8741: 1997 did. Specifically, using a GMX-202 manufactured by Murakami Color Research Laboratory as a gloss meter, the 60 ° glossiness of the uneven surface was measured under the condition of an incident angle of 60 °.

[Easy sweepability]
With regard to a melamine decorative board (melamine decorative board manufactured using white titanium paper), after writing characters on the uneven surface using an aqueous sign pen (manufactured by Pentel Co., Ltd.), it is wiped off with a dry cloth to easily wipe the uneven surface Sex was evaluated according to the following criteria.
A: The letters written with a stylus were wiped off, and no ink contamination occurred.
B: The character written with a stylus can not be wiped off, and ink contamination has occurred.

[Fingerprint resistance]
With respect to a melamine decorative board (melamine decorative board manufactured using black titanium paper), an artificial fingerprint liquid (according to JIS-K2246. 500 mL of purified water, 500 mL of methanol, containing 7 g of sodium chloride, 1 g of urea and 4 g of lactic acid) After applying to a surface, it was naturally dried, and the uneven surface after drying was visually observed, and the fingerprint resistance of the uneven surface was evaluated based on the following criteria.
A :: Almost no difference in the surface condition is observed between the area where the artificial fingerprint liquid was applied and the area where the artificial fingerprint liquid was not applied.
B: The area where the artificial fingerprint liquid was applied became whiter than the area where the artificial fingerprint liquid was not applied, and the surface condition was between the area where the artificial fingerprint liquid was applied and the area where the artificial fingerprint liquid was not applied. Differences are observed.

[Feeling to touch]
With respect to the melamine decorative board (melamine decorative board manufactured using black titanium paper), the uneven surface was touched by hand, and the touch feeling of the uneven surface was evaluated according to the following criteria.
A: There is no rough feeling.
B: There is a rough feeling.

Comparative Example 4
A melamine decorative board was manufactured using a shaped sheet in the same manner as described above except that a chemically etched film (Totoro matte film manufactured by Toyo Cross Co., Ltd.) was used as the shaped sheet. The properties of the shaped sheet and the properties of the melamine decorative board are shown in Table 1.

  As shown in Table 1, the irregularities constituting the concavo-convex surface of the shaped sheet are 1.6 μm or more and 2.7 μm or less, the maximum height Rmax is 11 μm or more and 16 μm or less, and the average spacing Sm is 30 μm or more and 116 μm The gloss is low (when the melamine decorative board has a black color, the 60 ° glossiness of the uneven surface of the melamine decorative board is 3 or less), and the unevenness is excellent in easy sweepability, fingerprint resistance and touch feeling. It is possible to produce a melamine decorative board having a surface.

DESCRIPTION OF SYMBOLS 1 ... shape formation sheet 10 ... uneven surface 11 ... base material sheet 12 ... resin layer 2 ... drum printing system 3 ... laminated body 31 ... core layer 32 ... not Cured melamine resin layer 4 ... melamine decorative board 41 ... core layer 42 ... surface layer

Claims (5)

A shaped sheet having an uneven surface,
The center line average roughness Ra of the unevenness constituting the uneven surface is 1.6 μm or more and 2.7 μm or less,
The maximum height Rmax of the unevenness forming the uneven surface is 11 μm or more and 16 μm or less,
The shaped sheet, wherein the average spacing Sm of irregularities forming the uneven surface is 30 μm or more and 116 μm or less.   The shaping according to claim 1, wherein the shaping sheet comprises a base sheet and a resin layer provided on the base sheet, and the uneven surface is formed by the surface of the resin layer. Sheet.   The shaped sheet according to claim 2, wherein the resin layer contains a cured product of an ionizing radiation curable resin.   The shaped sheet according to any one of claims 1 to 3, wherein the uneven surface has a longitudinal direction and a short direction, and both ends of the uneven surface extending in the longitudinal direction are flat. It is a method of manufacturing the melamine decorative board which has an uneven surface using the shaping sheet as described in any one of Claims 1-4,
(A) on the uncured melamine resin layer such that the core layer, the uncured melamine resin layer provided on the core layer, and the uneven surface of the shaped sheet are in contact with the uncured melamine resin layer Preparing a laminate comprising the provided shaped sheet;
(B) applying pressure and heat to the laminate to cure the uncured melamine resin layer;
(C) the method including the step of peeling the shaped sheet.

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