JP2018164991A - Resin articles and release sheets - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin article having a velvety surface and easily and stably manufactured, and a mold release sheet used for manufacturing the resin article. SOLUTION: A resin article having a velvety surface includes a support layer and a resin layer provided on the support layer, and the resin layer has a plurality of extending in the longitudinal direction in one direction. A concavo-convex structure including a ridge is formed, and in a cross-sectional view along the lateral direction of the ridge, the ridge has a substantially isosceles triangle shape, and the angle of the apex angle of the ridge is 60. ° or less. [Selection diagram] Fig. 1

Description

  The present disclosure relates to a resin article and a release sheet used for manufacturing the resin article.

  Resin leather, also called artificial leather, synthetic leather, etc., is a vehicle such as clothing, bag, shoes, wallet, smartphone cover skin material, interior material, instrument panel material, car seat skin material, steering wheel skin material, etc. Used as articles such as interior materials for automobiles and seats for motorcycles. The resin leather is manufactured by applying a resin composition such as a polyurethane resin or a vinyl chloride resin on a release sheet having peelability on the surface and curing the resin composition, and then peeling the release sheet. The resin leather has a texture, color, and the like similar to natural leather due to the skin layer formed of the resin composition.

  In recent years, resin leathers are required to have various appearances. For example, it is required to have a velvety appearance that has a smooth surface, deep color luster, and glossiness, and various measures for obtaining such an appearance are applied to the surface of the resin leather. . Conventionally, for example, by forming fine irregularities on the surface of a resin layer provided on one surface of a substrate, the regular reflectance of the resin layer with respect to visible light is set within a predetermined range and has a velvety surface Resin leather has been proposed (see Patent Document 1).

  In addition, thermosetting resin decorative boards using thermosetting resins such as melamine resin, diallyl phthalate (DAP) resin, and polyester resin are widely used as decorative boards used on the surface of various articles such as furniture. Yes. These thermosetting resin decorative boards have excellent surface properties such as impact resistance, stain resistance, and pencil hardness, and are widely used for table tops, sinks, desk tops, and the like. Thermosetting resin decorative boards generally have a pattern layer or are coated or impregnated with a thermosetting resin such as melamine resin, diallyl phthalate (DAP) resin, polyester resin, etc. Accordingly, overlay paper and core paper impregnated with a thermosetting resin are stacked and sandwiched between metal plates, and are produced by pressure molding or heat pressure molding. The thermosetting resin decorative board is also required to have various appearances like the resin leather.

Japanese Patent Laid-Open No. 2015-206154

  The resin leather described in Patent Document 1 can have a velvety surface by setting the regular reflectance of the resin layer to visible light within a predetermined range. In order to set the regular reflectance of the resin layer with respect to visible light within a predetermined range, fine irregularities are formed on the surface of the resin layer. Since these fine irregularities are in the form of a pyramid (conical shape, pyramid shape, etc.) whose size and arrangement are random, there is a high possibility that the fine irregularities will be deformed when the release sheet is peeled off, and the regular reflectance within a predetermined range There exists a problem that the difficulty with respect to forming the resin layer which shows this is very high.

  In view of the above-described problems, the present invention provides a resin article having a velvety surface, which can be easily and stably produced, and a release sheet used for producing the resin article. One purpose.

  As one embodiment of the present invention, it is provided with a support layer and a resin layer provided on the support layer, and the resin layer includes irregularities including a plurality of ridges whose longitudinal direction extends in one direction. In the cross-sectional view along the short direction of the ridge portion, the ridge portion has a substantially isosceles triangle shape, and the vertex angle of the ridge portion is 60 ° or less. A resinous article is provided.

  The angle of the vertical angle of the ridge portion can be 30 ° or more and 60 ° or less, and the support layer passes through the apex angle of the ridge portion in a cross-sectional view along the short direction of the ridge portion. When the angle between the perpendicular to the first side constituting the apex angle is the first angle and the angle between the perpendicular and the second side constituting the apex angle is the second angle, the first angle The difference between one angle and the second angle can be 0 ° or more and 30 ° or less.

  The visible light transmittance of the resin material constituting the resin layer may be 10% or less, and the interval between the apex angles between the adjacent ridges may be 20 μm to 80 μm. In a cross-sectional view along the short direction, the concave stripes positioned between the adjacent convex stripes can have a substantially V shape with rounded corners.

  As one embodiment of the present invention, a release sheet used for producing the resin article described above, comprising a release layer having a first surface and a second surface facing the first surface, On the first surface side of the release layer, a release sheet is provided in which a corresponding concavo-convex structure corresponding to the concavo-convex structure of the resin layer is formed on the first surface side.

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the release sheet | seat used for manufacturing the resin-made article which has a velvety surface and can manufacture easily and stably and the said resin-made article.

FIG. 1 is a cross-sectional view showing a schematic configuration of a resin leather which is an aspect of a resin article according to an embodiment of the present invention. FIG. 2 is a partially enlarged cross-sectional view showing a schematic configuration of a resin skin layer of the resin leather in one embodiment of the present invention. FIG. 3 is a perspective view showing a schematic configuration of the resin leather in one embodiment of the present invention. FIG. 4 is a cross-sectional view showing a schematic configuration of a release sheet in one embodiment of the present invention. FIGS. 5A to 5D are process flow diagrams illustrating the method for producing resin leather in one embodiment of the present invention in cross-sectional views. FIG. 6 is a schematic view showing an example of a method for producing a release sheet in one embodiment of the present invention. FIG. 7 is a cross-sectional view showing a schematic configuration of a thermosetting resin decorative board which is an aspect of a resin article according to an embodiment of the present invention. 8 (A) to 8 (B) are process flow diagrams showing the method for manufacturing a thermosetting resin decorative board in one embodiment of the present invention in cross-sectional views.

  Embodiments of the present invention will be described with reference to the drawings. In the drawings attached to this specification, in order to facilitate understanding, the shape, scale, vertical / horizontal dimensional ratio, etc. of each part may be changed from the actual one or may be exaggerated.

  In this specification and the like, terms such as “film”, “sheet”, and “plate” are not distinguished from each other on the basis of the difference in names. For example, the “plate” is a concept including members that can be generally called “sheet” and “film”.

[Resin leather]
FIG. 1 is a cross-sectional view illustrating a schematic configuration of a resin leather which is an aspect of a resin article according to the present embodiment, and FIG. 2 is a partially enlarged view illustrating a schematic configuration of a resin skin layer of the resin leather according to the present embodiment. FIG. 3 is a cross-sectional view, and FIG. 3 is a perspective view showing a schematic configuration of the resin leather in the present embodiment.

  As shown in FIGS. 1 to 3, the resin leather 1 in this embodiment includes a support layer 2 and a resin skin layer 3 laminated on the support layer 2. On the surface of the resin skin layer 3, a concavo-convex structure 4 including a plurality of ridges 41 and ridges 42 is formed.

  Examples of the support layer 2 include natural fibers such as cotton, hemp, and wool; regenerated or semi-synthetic fibers such as rayon and acetate; and woven fibers made of synthetic fibers such as polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, and polyolefin. Cloth, non-woven fabric, net cloth, paper, resin films such as polyester and polyolefin, metal plates, glass plates, etc., which are generally used for resin leather (synthetic leather, artificial leather), depending on the type and use of resin leather It can be appropriately selected. The thickness of the support layer 2 is not particularly limited as long as it can support the resin skin layer 3.

  The resin skin layer 3 is composed of a resin material and a resin composition containing an additive as required. Examples of the resin material include resin materials generally used for the production of resin leather (synthetic leather, artificial leather), such as polyurethane resin, nylon resin, and polyvinyl chloride resin. The resin skin layer 3 may contain a plasticizer, a stabilizer, a colorant and the like as the additive. The thickness of the resin skin layer 3 may be any thickness as long as the uneven structure 4 can be formed on the surface, and can be appropriately set depending on the use of the resin leather 1 or the like.

  As the resin material constituting the resin skin layer 3, it is preferable to use a material having a visible light transmittance of 10% or less measured by a predetermined method, and it is more preferable to use a material having 1% or less. Such visible light transmittance can be determined by measuring a total light transmittance according to JIS K 7375 using a resin sheet (thickness: 100 μm) made of a resin material as a sample.

  The color of the resin skin layer 3 is not particularly limited, but a pigment, a dye, or the like for coloring the resin skin layer 3 may be included in the resin skin layer 3, and a pigment is included. Is preferred. Examples of the pigment contained in the resin skin layer 3 include carbon black, perylene pigment, azo pigment, phthalocyanine pigment, iron oxide, and titanium white.

  The plurality of ridges 41 included in the concavo-convex structure 4 are formed by extending their longitudinal directions in a predetermined direction. In a cross-sectional view along the short direction (direction perpendicular to the longitudinal direction) of the ridge 41, the ridge 41 has a substantially isosceles triangle shape. The substantially isosceles triangular shape is formed by a normal line (perpendicular to the support layer) passing through the apex angle 41a of the ridge 41 in a cross-sectional view and a first side 41b constituting the ridge 41. When the angle is defined as the first angle θ1 and the angle formed by the normal line and the second side 41c constituting the convex portion 41 is defined as the second angle θ2, the first angle θ1 and the second angle θ2 It means that the difference is 0 ° or more and 30 ° or less, and preferably the difference is 0 ° or more and 15 ° or less.

  The angle (θ1 + θ2) of the apex angle 41a of the ridge 41 is 60 ° or less, preferably 30 ° or more and 60 ° or less, and more preferably 35 ° or more and 55 ° or less. If the angle of the apex angle 41a of the ridge 41 exceeds 60 °, the resin leather 1 cannot have a velvety appearance. Moreover, when the angle of the apex angle 41a of the ridge portion 41 is less than 30 °, it may be extremely difficult to manufacture the release sheet 10 (see FIG. 4) used for manufacturing the resin leather 1. The angle (θ1 + θ2), the first angle θ1, and the second angle θ2 of the ridge 41 are, for example, an electron microscope (for example, a field emission scanning electron microscope SU8000 manufactured by Hitachi High-Technologies Corporation). Can be calculated as an arithmetic average value of angles measured by observing the cut surfaces of the arbitrarily selected five ridges 41.

The interval P ₄₁ between adjacent ridges ₄₁ (the interval between apex angles 41a in a cross-sectional view) is preferably 20 μm or more and 80 μm or less, and more preferably 25 μm or more and 75 μm or less. If the distance P ₄₁ is less than 20 μm, the influence of the diffracted light on the surface of the resin skin layer 3 is increased, and there is a possibility that iridescent gloss is produced. If the distance P ₄₁ exceeds 80 μm, the height of the ridges 41 is inevitably increased, and the difficulty of manufacturing the resin leather 1 may increase. Note that the spacing P ₄₁ between the ridges ₄₁ is, for example, five ridges 41 arbitrarily selected using an electron microscope (for example, a field emission scanning electron microscope SU8000 manufactured by Hitachi High-Technologies Corporation). Can be calculated as an arithmetic average value of intervals measured by observing the above in a top view.

The dimension D ₄₁ of the ridge ₄₁ includes an apex angle 41 a, an interval P ₄₁ between adjacent ridges ₄₁ , a height T _{41 of the} ridge ₄₁ (the lowest end 42 a of the ridge 42 and the ridge 41. The length in the normal direction between the vertical angle 41a and the apex angle 41a can be set as appropriate. For example, the vertical angle 41a can be set to about 20 μm to 80 μm. If the dimension D ₄₁ of the ridge ₄₁ is less than 20 μm, it is difficult to control the dimension, and the velvet-like resin leather 1 may not be manufactured stably. If the dimension D ₄₁ of the ridge ₄₁ exceeds 80 μm, the height of the ridge 41 is inevitably increased, and the difficulty of manufacturing the resin leather 1 may increase. In addition, the dimension of the protruding item | line part 41 shall mean the length between the lowest ends 42a of the adjacent recessed item part 42 along the transversal direction of the protruding item | line part 41. As shown in FIG.

The height T ₄₁ of the ridge ₄₁ can be set to, for example, about 17 μm or more and 150 μm or less. If the height T ₄₁ of the ridge ₄₁ is less than 17 μm, unevenness may be conspicuous, and if it exceeds 150 μm, the difficulty of manufacturing the resin leather 1 may increase.

  The shape of the concave strip portion 42 positioned between the adjacent convex strip portions 41 may be, for example, a substantially V shape with rounded corners 42a positioned at the lowermost end. Since the shape of the concave portion 42 is substantially V-shaped with rounded corners 42a, the resin leather 1 can be manufactured stably and with high accuracy.

  The curvature radius R of the substantially V-shaped corner 42a of the concave strip portion 42 is preferably 15 μm or less, and more preferably 1 μm or more and 10 μm or less. If the radius of curvature R of the substantially V-shaped corner 42a of the concave portion 42 exceeds 15 μm, the reflectance of the light beam having a small incident angle increases, and therefore the velvety appearance may not be easily achieved in the resin leather 1. is there. When the radius of curvature R of the substantially V-shaped corner 42a of the concave portion 42 is smaller than 1 μm, the resin leather 1 (resin skin layer 3) is removed from the release sheet 10 (see FIG. 4) used for manufacturing the resin leather 1. It becomes difficult to peel off, and the release sheet 10 may be destroyed and may not be used repeatedly.

  Examples of the use of the resin leather 1 in the present embodiment include general uses of resin leather (synthetic leather, artificial leather). Applications of the resin leather 1 include, for example, vehicle interior materials such as clothing, bags, shoes, wallets, smartphone cover skin materials, interior materials, instrument panel materials, car seat skin materials, steering wheel skin materials, and motorcycles. Sheet material and the like.

  According to the resin leather 1 in the present embodiment, the rugged structure 4 (the ridge portions 41 and the ridge portions 42) formed on the surface of the resin skin layer 3 with high accuracy can provide a velvety appearance.

[Production method of resin leather]
The manufacturing method of the resin leather in this embodiment is demonstrated. FIG. 4 is a cross-sectional view illustrating a schematic configuration of a release sheet used for manufacturing the resin leather in the present embodiment, and FIGS. 5A to 5D are methods for manufacturing the resin leather in the present embodiment. It is a process flowchart which shows this by sectional drawing.

  In the manufacturing method of the resin leather in the present embodiment, as shown in FIG. 5A, first, a separation having a concavo-convex structure 14 corresponding to the concavo-convex structure 4 formed on the surface of the resin skin layer 3 of the resin leather 1. A mold sheet 10 is prepared.

  As shown in FIG. 4, the release sheet 10 is provided on the base 11 having the first surface 11 </ b> A and the second surface 11 </ b> B facing the first surface 11 </ b> A, and the first surface 11 </ b> A of the base 11, and on the base 11 side. A release layer 12 including a second surface 12B positioned and a first surface 12A opposite to the second surface 12B and having a concavo-convex structure 14 formed on the first surface 12A side is provided.

  The base material 11 is not particularly limited as long as the release layer 12 can be formed, and a base material of a conventionally known material generally used for a release sheet for manufacturing resin leather or process paper can be used. . Specifically, as the base material 11, a paper base material such as kraft paper, high-quality paper, cast coated paper; a polyester base material such as polyethylene terephthalate or polyethylene naphthalate; a polyamide film such as various nylons; a resin film such as polypropylene; Synthetic paper, metal foil, woven fabric, non-woven fabric and the like can be used. These may be used alone or in combination of two or more as the substrate 11. In producing resin leather using the release sheet 10, it is preferable to use a paper base material as the base material 11 from the viewpoint of hardly causing thermal deterioration and high adhesion to the release layer 12.

  The thickness of the base material 11 is not particularly limited, and can be appropriately set according to the material of the base material 11, but is preferably set to, for example, about 50 μm to 200 μm.

  The first surface 11A of the substrate 11 is subjected to easy adhesion treatment such as corona discharge treatment and ozone treatment, surface treatment such as primer coating, etc. for the purpose of improving the adhesion to the release layer 12. It may be.

  As a material constituting the release layer 12, the uneven structure 14 can be formed on the first surface 12A, and the resin leather can be easily peeled when the resin leather is manufactured using the release sheet. The material is not particularly limited as long as it is a simple material. Examples of the material constituting the release layer 12 include a thermoplastic resin, a thermosetting resin, and an active energy ray curable resin (such as an ultraviolet curable resin and an electron beam curable resin).

  Examples of the thermoplastic resin include acrylic resins such as polymethyl methacrylate; polyolefin resins such as polyethylene, polypropylene, and polymethylpentene; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; styrene resins such as polystyrene; Conventional resins such as vinyl resins such as vinyl chloride; polycarbonate resins; Examples of the thermosetting resin include unsaturated polyester, melamine, epoxy, polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine ( Examples include meth) acrylate, triazine acrylate, and silicone resin. Examples of the active energy ray-curable resin include urethane resins, epoxy resins, ester resins, acrylic resins, acrylic ester copolymers, and the like.

  The release layer 12 preferably contains the thermoplastic resin, and particularly preferably contains polypropylene. When the release layer 12 contains a thermoplastic resin, particularly polypropylene, the concavo-convex structure 14 can be formed on the first surface 12A side of the release layer 12 with high accuracy. When manufacturing the resin leather, the resin leather can be easily peeled off. The release layer 12 may be transparent (visible light transmittance is about 80% or more), and may be translucent or opaque. Moreover, the release layer 12 may be colored.

  The thickness of the mold release layer 12 should just be the thickness which can form the uneven structure 14 in the 1st surface 12A side, for example, can be set to 5 micrometers or more and 200 micrometers or less, Preferably they are 10 micrometers or more and 100 micrometers or less.

  A release layer (not shown) that can be formed by applying and drying a silicone resin, a fluorine resin, or the like may be provided on the first surface 12A of the release layer 12. By providing the release layer, the peelability of the release sheet 10 can be further improved when the resin leather is manufactured. When a release layer is provided, the thickness of the release layer may be a thickness that does not impair the function of the concavo-convex structure 14 formed on the first surface 12A side of the release layer 12. It can be set to about 01 μm or more and 0.5 μm or less.

  The shape of the concavo-convex structure 14 formed on the surface of the release layer 12 is a shape corresponding to the concavo-convex structure 4 of the resin leather 1, and the concave strip 141 and the concave strip portion corresponding to the convex strip portion 41 of the resin leather 1. 42 corresponding to 42 is included.

  The concavo-convex structure 14 formed on the first surface 12A of the release layer 12 is transferred to the resin leather 1 (resin skin layer 3) when the resin leather 1 is manufactured. The structure etc. which can provide the external appearance. For example, the angle of the lower end in the cross-sectional view of the concave stripe 141 of the concavo-convex structure 14 is set to, for example, about 60 ° or less, and the interval between adjacent concave stripes 141 is set to about 20 μm or more and 80 μm or less. Moreover, the dimension of the concave strip 141 (the length between the apex angles of adjacent convex strips 142) can be set to, for example, about 20 μm to 80 μm, and the depth can be set to, for example, about 17 μm to 150 μm.

  Subsequently, as shown in FIG. 5 (B), a resin skin layer forming composition is applied to the first surface 12A of the release layer 12 of the release sheet 10 by a conventionally known method, and dried to form a resin skin. Layer 3 is formed. As the resin skin layer forming composition, a composition having a desired visible light transmittance is preferably used, but is appropriately selected depending on the type of the resin leather 1. For example, when the resin leather 1 is polyurethane leather, a polyurethane paste having a solid content of about 20% by mass or more and 50% by mass or less containing polyurethane and an optional additive may be used as the resin skin layer forming composition. When the resin leather is polyvinyl chloride leather, a sol or the like containing polyvinyl chloride and any additive can be used as the resin skin layer forming composition.

  Next, as shown in FIGS. 5C and 5D, the support layer 2 is laminated on the resin skin layer 3 via an adhesive layer (not shown), dried and aged, and then the release sheet 10 is attached. Peel off. Thereby, the resin leather 1 which has a velvety appearance can be manufactured. As the adhesive layer, a conventionally known adhesive layer used for the production of resin leather (synthetic leather, artificial leather) can be used.

  According to the resin leather manufacturing method of the present embodiment, the resin leather 1 having a velvety appearance can be stably manufactured.

[Method for producing release sheet]
An example of a method for producing the release sheet 10 used in the method for producing the resin leather 1 in the present embodiment will be described. FIG. 6 is a schematic view showing an example of a method for producing a release sheet in the present embodiment.

  A transfer plate 20 having a concavo-convex structure corresponding to the concavo-convex structure 14 of the release sheet 10 (a concavo-convex structure including ridges and recesses) formed on one surface is prepared. This is transferred to the resin material film 12 ′ formed on the first surface 11A. Preferably, as shown in FIG. 6, a transfer roll 22 in which a transfer plate 20 is wound around a roll body 21 is prepared, and a resin material film 12 ′ is formed on the first surface 11 </ b> A of the substrate 11. The concave-convex structure 14 is formed on the first surface 12 </ b> A of the release layer 12 by pressing the transfer roll 22 while conveying the original fabric. In this way, the release sheet 10 can be produced.

[Thermosetting resin decorative board]
FIG. 7 is a cross-sectional view showing a schematic configuration of a thermosetting resin decorative board which is an aspect of the resin article according to the present embodiment.

  As shown in FIG. 7, the thermosetting resin decorative board 1 ′ in this embodiment includes a support layer 2 ′ and a thermosetting resin layer 3 ′ laminated on the support layer 2 ′. On the surface of the thermosetting resin layer 3 ′, a concavo-convex structure 4 ′ including a plurality of ridges 41 ′ and recesses 42 ′ is formed. Examples of the thermosetting resin decorative board 1 ′ include a high-pressure melamine resin decorative board, a low-pressure melamine resin decorative board, a diallyl phthalate (DAP) resin decorative board, a polyester decorative board, a guanamine resin decorative board, and a phenol resin decorative board. And a high-pressure melamine resin decorative board is preferable. The high-pressure melamine resin decorative board has excellent pencil hardness, heat resistance, stain resistance, chemical resistance, etc., so that it can be used as interior or exterior materials for buildings such as walls, ceilings, and floors; window frames, doors, It can be suitably used as a decorative sheet for furniture such as handrails, skirting boards, edges, and malls; decorative panel for cabinets such as kitchens, furniture, light electrical appliances, office automation equipment, etc .;

The support layer 2 ′ has a core layer 2a ′ and a pattern printing layer 2b ′ formed on the core layer 2a ′.
The core layer 2a ′ is provided for imparting the necessary thickness and strength to the thermosetting resin decorative board 1 ′. For example, phenol resin, melamine resin, diallyl phthalate (DAP) resin, polyester resin, Examples thereof include a fibrous base material impregnated with a thermosetting resin such as a guanamine resin, preferably a phenol resin, a melamine resin or the like at an impregnation rate of 45% by mass to 60% by mass. In addition, the impregnation rate (mass%) of the thermosetting resin is “the mass of the impregnated thermosetting resin relative to the“ mass of the base material (fibrous base material) ”(the mass of the base material after impregnation with the thermosetting resin) The difference between the difference from the mass of the substrate before impregnation) ”can be calculated.

Examples of the fibrous base material constituting the core layer 2a ′ include craft paper and non-woven fabric, and those having a basis weight of about 150 g / m ² or more and 250 g / m ² or less are suitable. The core layer 2a ′ may be formed by laminating a plurality of fibrous base materials impregnated with a thermosetting resin. The number of laminated fibrous base materials is determined by the thermosetting resin decorative board 1 ′. Can be set as appropriate according to the required thickness.

  Examples of the pattern print layer 2b 'include a porous substrate on which a pattern is printed. The porous substrate is not particularly limited as long as the pattern can be printed. For example, thin paper, kraft paper, titanium paper, art paper, sulfate paper, glassine paper, linter paper, paperboard, gypsum board paper Examples thereof include a vinyl wallpaper original fabric obtained by sol or dry laminating a polyvinyl chloride resin on paper, paper such as fine paper, coated paper, parchment paper, paraffin paper, and Japanese paper.

  The method for printing the pattern on the porous substrate is not particularly limited, and can be obtained, for example, by dissolving or dispersing a known colorant (pigment or dye) together with a binder resin in a solvent or dispersion medium. For example, a printing method using ink may be used. More specifically, for example, a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, an inkjet printing method and the like can be mentioned. Further, when printing a solid pattern on the entire surface of the porous substrate, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow Various coating methods such as a coating method and a dip coating method can be employed. In addition, the hand-drawn method, the ink-sink method, the photographic method, the transfer method, the laser beam drawing method, the electron beam drawing method, the metal partial evaporation method, the etching method, etc. may be used, or may be used in combination with other printing methods. May be.

  As the ink used in the printing method, an aqueous composition may be used from the viewpoint of reducing VOC of the porous substrate. When printing a pattern on a porous substrate, a solid print layer may be formed on the porous substrate as a pretreatment.

  Examples of the colorant contained in the ink include inorganic pigments such as carbon black, titanium white, zinc white, petal, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, and isoindolinones. Examples thereof include organic pigments such as pigments and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants may be used alone or in a combination of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  As binder resin, in addition to polyester urethane resin treated with hydrophilicity, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative Alcohol adducts of styrene-maleic anhydride copolymers, cellulose resins, casein resins, and the like can also be used in combination. More specifically, for example, polyacrylamide resins, poly (meth) acrylic resins, polyethylene oxide resins, poly N-vinyl pyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino acids. Resin, water-soluble phenolic resin, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides and the like can also be used. Also, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin modified, natural rubber mixture, and other resins May be used. The binder resin can be used alone or in combination of two or more.

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

  Examples of the thermosetting resin layer 3 ′ include unsaturated polyester resin, polyurethane resin (including two-component curable polyurethane), epoxy resin, amino alkyd resin, phenol resin, urea resin, diallyl phthalate (DAP) resin, melamine A resin, guanamine resin, melamine-urea cocondensation resin, silicon resin, polysiloxane resin, or other thermosetting resin is impregnated at an impregnation ratio of 30% by mass to 200% by mass, preferably 50% by mass to 150% by mass. And porous substrates.

  The thermosetting resin may contain a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, and the like. As a hardening | curing agent, the isocyanate which can be contained in the unsaturated polyester resin as a thermosetting resin, a polyurethane resin, etc., an organic sulfonate; The organic amine etc. which can be contained in an epoxy resin etc. are mentioned, for example. Examples of the polymerization initiator (radical initiator) include peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, and the like that can be included in an unsaturated polyester resin as a thermosetting resin.

  The porous substrate is not particularly limited as long as the thermosetting resin can be impregnated, and examples thereof include a fibrous substrate having permeability of the thermosetting resin. Examples of such fibrous base materials include thin paper, craft paper, titanium paper, art paper, sulfate paper, glassine paper, linter paper, paperboard, gypsum board paper, vinyl wallpaper in which a polyvinyl chloride resin is sol or dry laminated on paper. Paper such as raw fabric, high-quality paper, coated paper, parchment paper, paraffin paper, and Japanese paper; inorganic fibers such as glass fiber, asbestos, potassium titanate fiber, alumina fiber, silica fiber, and carbon fiber are formed into a sheet. Paper-like sheet: Nonwoven fabric or woven fabric made of synthetic resin fibers such as polyester, vinylon, polyethylene, polypropylene and the like. From the viewpoint of impregnation of thermosetting resin, titanium paper, thin paper, kraft paper, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, and Japanese paper are preferable, and titanium paper is particularly preferable. .

  The porous base material may be colored, and if the porous base material is made of paper, if the porous base material is paper, it is made porous by blending a colorant (pigment, dye, etc.) at the paper making stage. As the colorant, for example, inorganic pigments such as titanium dioxide, carbon black and iron oxide, organic pigments such as phthalocyanine blue, and various dyes can be used. It is sufficient that at least one kind is contained, and when two or more kinds are contained, the blending amount of the colorant can be appropriately set according to a desired color tone, etc. Depending on the type, various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers may be included.

The basis weight of the porous substrate is not particularly limited, and is preferably 40 g / m ² or more and 150 g / m ² or less, for example. Moreover, although the thickness of a porous base material can be suitably set according to the use, usage method, etc. of thermosetting resin decorative board 1 ', it is about 50 micrometers or more and 170 micrometers or less, for example.

  Note that a surface treatment for the purpose of improving adhesion may be performed on one surface of the thermosetting resin layer 3 ′ (the surface that comes into contact with the pattern print layer 2 b ′). Examples of the surface treatment include corona discharge treatment.

  For example, the thermosetting resin layer 3 ′ is a method of immersing a porous substrate in a thermosetting resin; a method of applying a thermosetting resin to a porous substrate using a coater such as a kiss coater or a comma coater, spray Impregnating the porous substrate with the thermosetting resin by a method such as spraying the thermosetting resin onto the porous substrate with an apparatus, a shower device, etc., and heating the porous substrate to cure the thermosetting resin Can be made. The heating temperature and heating time of the porous substrate can be appropriately set according to the type of the thermosetting resin. For example, when an isocyanate curable unsaturated polyester resin or urethane curable polyurethane resin is used as the thermosetting resin, it may be heated at a temperature of 40 ° C. to 60 ° C. for about 1 day to 5 days. When a polysiloxane resin is used as the thermosetting resin, it may be heated at a temperature of 80 ° C. to 150 ° C. for about 1 minute to 30 minutes. Furthermore, when a melamine resin is used as the thermosetting resin, it may be heated at a temperature of 90 ° C. to 160 ° C. for 30 seconds to 30 minutes. If necessary, the thermosetting resin may be cured by applying pressure and heating.

  The concavo-convex structure 4 ′ including the plurality of ridge portions 41 ′ and the concave ridge portions 42 ′ formed on the thermosetting resin layer 3 ′ is a ridge formed on the resin skin layer 3 of the resin leather 1 described above. Since it has the structure substantially the same as the strip part 41 and the concave strip part 42 (refer FIGS. 1-3), detailed description here shall be abbreviate | omitted.

  In the thermosetting resin decorative board 1 ′ described above, the concavo-convex structure 4 ′ (the ridge portions 41 ′ and the ridge portions 42 ′) is formed with high accuracy on the surface of the thermosetting resin layer 3 ′. A velvety appearance can be exhibited.

[Method for producing thermosetting resin decorative board]
FIG. 8 is a process flow diagram showing the manufacturing method of the thermosetting resin decorative board in the present embodiment in a cross-sectional view.

  As shown in FIG. 8A, the thermosetting resin layer 3 ′, the pattern printing layer 22 ′, and the core layer 21 ′ are stacked in this order, and the release sheet 10 is stacked on the thermosetting resin layer 3 ′. The laminated body is sandwiched between two metal plates 51 and 52, and is pressed at a pressure of 5.9 MPa to 9.8 MPa at a temperature of 110 ° C. to 160 ° C. for 10 minutes to 60 minutes. Heat for a period of time.

  As the release sheet 10 used for forming the concavo-convex structure 4 ′ (projection strip portion 41 ′ and recess strip portion 42 ′) on the surface of the thermosetting resin layer 3 ′, the above-described resin leather 1 (FIGS. 1 to 1). Although the thing similar to what is used in order to manufacture (refer FIG. 3) can be used, The polyester base materials 11, such as polyethylene terephthalate and polyethylene naphthalate which have heat resistance and smoothness, and heat resistance are suitable. And a release layer 12 made of an active energy ray curable resin or the like can be used.

  Next, as shown in FIG. 8 (B), the release sheet 10 is peeled from the laminated body that is sandwiched between the metal plates 51 and 52 and pressed and heated. Thereby, the thermosetting resin decorative board 1 ′ in which the concavo-convex structure 14 formed on the release layer 12 of the release sheet 10 is transferred to the thermosetting resin layer 3 ′ can be manufactured.

  According to the manufacturing method of the thermosetting resin decorative board in the present embodiment, the thermosetting resin decorative board 1 ′ having a velvety appearance can be stably manufactured.

  The embodiment described above is described for facilitating understanding of the present invention, and is not described for limiting the present invention. Therefore, each element disclosed in the above embodiment is intended to include all design changes and equivalents belonging to the technical scope of the present invention.

  In the said embodiment, although demonstrated taking the example of the method of manufacturing the resin leather 1 and the thermosetting resin decorative board 1 'using the release sheet 10 provided with the base material 11, it is not limited to this aspect. For example, the release sheet 10 may include only the release layer 12 and may not include the substrate 11.

  In the said embodiment, although the resin skin layer 3 of the resin leather 1 demonstrated and demonstrated the example comprised by a single layer, it is not limited to this aspect, For example, the resin leather 1 is on the support layer 2 You may provide the resin skin layer 3 comprised by two layers of the 1st resin skin layer and the 2nd resin skin layer laminated | stacked in order, In this case, the uneven structure 4 is on the surface of the 2nd resin skin layer. It only has to be formed. Similarly, in the thermosetting resin decorative board 1 ′, the thermosetting resin layer 3 ′ may be composed of a plurality of thermosetting resin layers.

  In the said embodiment, although the uneven | corrugated structure 4 was described taking the example of the aspect currently formed in the surface of the resin skin layer 3, it is not limited to this aspect, It is uneven | corrugated to the support layer 2 and the resin skin layer 3 Structure 4 may be formed. The resin leather 1 of this aspect can be manufactured, for example, by forming a resin film constituting the resin skin layer 3 on the support layer 2 and subjecting the resin film to a heat pressing process (heat embossing process). Similarly, in the thermosetting resin decorative board 1 ′, the concavo-convex structure 4 ′ may be formed on the pattern printing layer 2b ′ and the thermosetting resin layer 3 ′, or the core layer 2a ′ and the pattern printing layer. 2b ′ and thermosetting resin layer 3 ′ may be formed.

  EXAMPLES Hereinafter, although an Example etc. are given and this invention is demonstrated further in detail, this invention is not limited to the following Example etc. at all.

[Example 1]
(1) Preparation of transfer plate An uneven structure was formed on the surface of a copper plate (210 mm x 297 mm) by mechanical cutting to prepare a transfer plate 20. The shape of the ridges of the concavo-convex structure formed on the transfer plate 20 is an isosceles triangle, the apex angle of the ridges is 30 °, the interval is 50 μm, and the curvature radius R of the substantially V-shaped corner of the concavo-convex structure Was 2 μm.

(2) Production of release sheet Polypropylene is applied on the first surface 11A of a paper substrate 11 (thickness: 150 μm) to form a release layer 12 (thickness: 50 μm), and release is performed under the following conditions. The release plate 20 is heated and pressed to the first surface 12A of the mold layer 12 to transfer the concavo-convex structure, and is provided with a substrate 11 and a release layer 12 in which the concavo-convex structure 14 is formed on the first surface 12A. A mold sheet 10 was produced.
(Transfer conditions)
・ Cylinder temperature: 120 ℃
・ Pressing force: 150 kgf / cm

(3) Production of resin leather On the first surface 12A of the release layer 12 of the release sheet 10, a resin skin layer forming composition (polyurethane composition for a resin skin layer having the composition shown below) is bar-coated. And the resin skin layer 3 was formed by heating and drying within a range of 100 ° C. or higher and 120 ° C. or lower for 2 minutes. Thereafter, the support layer 2 was bonded onto the resin skin layer 3 using an adhesive, and after drying and aging, the release sheet 10 was peeled off to produce a resin leather 1.
(Resin skin layer forming composition)
・ Polyurethane (Resamine NE-8811, manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 parts by mass. Colorant (Seika Seven NET-5794 Black, manufactured by Dainichi Seika Kogyo Co., Ltd.) 15 parts by mass. Toluene 25 parts by mass. Isopropyl alcohol 25 parts by mass.

[Example 2]
A transfer plate 20 was prepared in the same manner as in Example 1 except that the apex angle of the ridges of the concavo-convex structure formed on the transfer plate 20 was changed to 50 °, and a release sheet 10 and a resin leather 1 were produced.

Example 3
A transfer plate 20 was prepared in the same manner as in Example 1 except that the apex angle of the ridges of the concavo-convex structure formed on the transfer plate 20 was changed to 60 °, and a release sheet 10 and a resin leather 1 were produced.

[Comparative Example 1]
A transfer plate 20 was prepared in the same manner as in Example 1 except that the apex angle of the ridges of the concavo-convex structure formed on the transfer plate 20 was changed to 70 °, and a release sheet 10 and a resin leather 1 were produced.

[Comparative Example 2]
A transfer plate 20 was prepared in the same manner as in Example 1 except that the apex angle of the ridges of the concavo-convex structure formed on the transfer plate 20 was changed to 90 °, and a release sheet 10 and a resin leather 1 were produced.

[Comparative Example 3]
A release sheet and resin leather were produced in the same manner as in Example 1 except that the uneven structure 4 was not formed on the resin skin layer 3.

[Test Example 1] Appearance evaluation test Using the resin leather 1 of Examples 1 to 3 and Comparative Examples 1 to 3 as test samples, each test sample was placed on a desk and in an illuminance of 400 lux (equivalent to a bright office). Each subject evaluated the appearance of each test sample according to the following evaluation criteria. The results are shown in Table 1. In addition, the appearance evaluation in Table 1 is “◎” when the average score of all subjects is 2.5 or more, “◯” when 2.0 or more and less than 2.5, and 2.0 Those less than “△” were assigned.
<Evaluation criteria>
Looks velvety: 3 points Cannot say either: 2 points Not velvety: 1 point

  From the results shown in Table 1, it is possible to impart a velvety appearance to the resin leather 1 when the apex angle of the ridges 41 of the concavo-convex structure 4 formed in the resin skin layer 3 is 60 ° or less. It was confirmed that there was.

[Test Example 2] Visible light transmittance measurement test A resin sheet having a thickness of 0.1 mm was prepared using the resin skin layer forming composition used in Examples 1 to 3 and Comparative Examples 1 to 3, and The visible light transmittance was measured using a transmittance measuring device (Murakami Color Research Laboratory, product name: HR-100). As a result, the visible light transmittance was 0.8%.

DESCRIPTION OF SYMBOLS 1 ... Resin leather 2 ... Support layer 3 ... Resin skin layer (resin layer)
DESCRIPTION OF SYMBOLS 4 ... Uneven structure 41 ... Convex part 42 ... Convex part 10 ... Release sheet 11 ... Base material 12 ... Release layer 14 ... Uneven structure

Claims (7)

A support layer, and a resin layer provided on the support layer,
In the resin layer, a concavo-convex structure including a plurality of ridges whose longitudinal direction extends in one direction is formed,
The cross-sectional view along the transversal direction of the said protruding item | line part WHEREIN: The said protruding item | line part has a substantially isosceles triangle shape, and the angle of the vertex angle of the said protruding item | line part is 60 degrees or less.   The resin article according to claim 1, wherein an angle of a vertex angle of the ridge portion is 30 ° or more and 60 ° or less.   In a cross-sectional view along the short direction of the ridge portion, an angle formed by a perpendicular to the support layer passing through the apex angle of the ridge portion and a first side constituting the apex angle is defined as a first angle. The difference between the first angle and the second angle is not less than 0 ° and not more than 30 °, where an angle formed by the perpendicular and the second side constituting the apex angle is a second angle. Or the resin-made article of 2.   The resin article according to any one of claims 1 to 3, wherein a visible light transmittance of a resin material constituting the resin layer is 10% or less.   The resin article according to any one of claims 1 to 4, wherein an interval between the apex angles between the adjacent ridge portions is 20 µm to 80 µm.   The cross-sectional view along the transversal direction of the said convex strip part WHEREIN: The concave strip part located between the said adjacent convex strip part has the substantially V shape in which the corner | round was rounded. The resin article described in 1. A release sheet used for producing the resin article according to any one of claims 1 to 6,
Including a release layer having a first surface and a second surface facing the first surface;
A release sheet in which a corresponding uneven structure corresponding to the uneven structure of the resin layer is formed on the first surface side of the release layer.

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