JP6870418B2 - Resin articles and mold release sheets - Google Patents

Description

The present disclosure relates to resin articles and mold release sheets used to manufacture them.

Resin leather, which is also called artificial leather or synthetic leather, includes, for example, clothing, bags, shoes, wallets, smartphone cover skin materials, interior materials, instrument panel materials, car seat skin materials, steering wheel skin materials, and other vehicles. It is used as an article such as interior materials for leather and seat materials for motorcycles. Resin leather is produced by applying a resin composition such as polyurethane resin or vinyl chloride resin on a release sheet having a peelable surface, curing the resin composition, and then peeling the release sheet. The resin leather has a texture and color similar to that of natural leather due to the skin layer composed of the resin composition.

In recent years, resin leather is required to have various appearances. For example, it is required to have a velvety appearance that has a smooth surface, a deep luster, and a glossy feeling, and various measures have been taken to obtain such an appearance on 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 base material, the specular reflectance of the resin layer with respect to visible light is set within a predetermined range, and a velvety surface is provided. Resin leather has been proposed (see Patent Document 1).

Further, as a decorative board used for the surface of various articles such as furniture, a thermosetting resin decorative board using a thermosetting resin such as a melamine resin, a diallyl phthalate (DAP) resin, or a polyester resin is widely used. There is. These thermosetting resin decorative boards are excellent in surface characteristics such as impact resistance, stain resistance, and pencil hardness, and are widely used for table tops, sinks, desk top plates, and the like. A thermosetting resin decorative board generally has a pattern layer or is colored in a single color, and is coated or impregnated with a thermosetting resin such as a melamine resin, a diallyl phthalate (DAP) resin, or a polyester resin, and is further required. It is produced by stacking overlay paper and core paper impregnated with a thermosetting resin, sandwiching them between metal plates, and performing pressure molding or heat pressure molding. Similar to resin leather, thermosetting resin decorative boards are also required to have various appearances.

Japanese Unexamined Patent Publication No. 2015-206154

The resin leather described in Patent Document 1 can have a velvety surface by setting the specular reflectance of the resin layer with respect to visible light within a predetermined range. In order to set the specular 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 pyramidal in size and arrangement (conical, pyramidal, etc.), there is a high possibility that the fine irregularities will be deformed when the release sheet is peeled off, and the specular reflectance within a predetermined range. There is a problem that the difficulty of forming the resin layer showing the above is extremely high.

In view of the above problems, the present invention provides a resin article having a velvety surface and 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, a support layer and a resin layer provided on the support layer are provided, and the resin layer has irregularities including a plurality of ridges extending in one longitudinal direction. structure is formed, the in a cross-sectional view along the widthwise direction of each ridge, the angle of each convex portion has a substantially isosceles triangular, the apex angle of each convex portion 60 ° Ri der hereinafter interval of the vertical angle between the convex portions adjacent to each, 20Myuemu～80myuemu der Ru resin article is provided.

Wherein the angle of the apex angle of each convex portion can be 30 ° to 60 °, in a cross-sectional view along said widthwise direction of each ridge, through the apex angle of each of the ridges When the angle formed by the vertical line with respect to the support layer and the first side forming the apex angle is defined as the first angle, and the angle formed by the vertical line and the second side forming the apex angle is defined as the second angle. , The difference between the first angle and the second angle can be set to 0 ° or more and 30 ° or less.

As long than 10% visible light transmittance of the resin material constituting the resin layer, before the cross-sectional view along the widthwise direction of the Kitotsu ridges, recessed located between the convex portions adjacent The strip can have a substantially V-shape with rounded corners.

As one embodiment of the present invention, the release sheet used for producing the resin article described above includes 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 uneven structure corresponding to the uneven structure of the resin layer is formed on the first surface side.

According to the present invention, it is possible to provide a resin article having a velvety surface and being easily and stably produced, and a release sheet used for producing the resin article.

FIG. 1 is a cross-sectional view showing a schematic configuration of 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 a resin leather according to an embodiment of the present invention. FIG. 3 is a perspective view showing a schematic configuration of a resin leather according to an embodiment of the present invention. FIG. 4 is a cross-sectional view showing a schematic configuration of a release sheet according to an embodiment of the present invention. 5 (A) to 5 (D) are process flow charts showing a method for producing resin leather according to an embodiment of the present invention in a cross-sectional view. FIG. 6 is a schematic view showing an example of a method for producing a release sheet according to an 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 charts showing a method for manufacturing a thermosetting resin decorative board according to an embodiment of the present invention in a cross-sectional view.

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

In the present specification and the like, terms such as "film", "sheet", and "board" are not distinguished from each other based on the difference in designation. For example, "board" is a concept that includes members that can be generally called "sheet" or "film".

[Resin leather]
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 the present embodiment, and FIG. 2 is a partially enlarged view showing a schematic configuration of a resin skin layer of the resin leather according to the present embodiment. It is a cross-sectional view, and FIG. 3 is a perspective view which shows the schematic structure of the resin leather in this embodiment.

As shown in FIGS. 1 to 3, the resin leather 1 in the present 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.

The support layer 2 is a woven fabric made of, for example, natural fibers such as cotton, hemp, and wool; regenerated or semi-synthetic fibers such as rayon and acetate; synthetic fibers such as polyamide, polyester, polyacrylonitrile, polyvinyl alcohol, and polyolefin. From cloth, non-woven fabric, net cloth, paper, resin film such as polyester and polyolefin, metal plate, glass plate, etc., which are generally used for resin leather (synthetic leather, artificial leather), depending on the type and application of resin leather. It can be selected as appropriate. 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 if desired. Examples of the resin material include resin materials generally used for producing 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 it can form the uneven structure 4 on the surface, and can be appropriately set according to the use of the resin leather 1 and 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, and more preferably a material having a visible light transmittance of 1% or less, which is measured by a predetermined method. Such visible light transmittance can be obtained by measuring the 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 contained in the resin skin layer 3, and the pigment is contained. Is preferable. Examples of the pigment contained in the resin skin layer 3 include carbon black, perylene pigment, azo pigment, phthalocyanine pigment, iron oxide, titanium white and the like.

The plurality of ridges 41 included in the concave-convex structure 4 extend their longitudinal directions in a predetermined one direction. The convex portion 41 has a substantially isosceles right triangle shape in a cross-sectional view along the lateral direction (direction orthogonal to the longitudinal direction) of the convex portion 41. The substantially isosceles triangle shape is formed by a normal line (perpendicular line with respect to the support layer) passing through the apex angle 41a of the ridge portion 41 in a cross-sectional view and a first side 41b constituting the ridge portion 41. When the angle is the first angle θ1 and the angle formed by the normal and the second side 41c forming the convex portion 41 is 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 convex portion 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 portion 41 exceeds 60 °, the resin leather 1 cannot obtain a velvety appearance. Further, if 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) of the apex angle 41a of the ridge portion 41, the first angle θ1 and the second angle θ2 are, for example, an electron microscope (for example, a field emission scanning electron microscope SU8000 manufactured by Hitachi High-Technologies Co., Ltd.) and the like. Can be calculated as an arithmetic average value of the angles measured by observing the cut surfaces of the five ridges 41 arbitrarily selected using the above.

The distance P ₄₁ (distance of the apex angle 41a in the cross-sectional view) of the adjacent ridges 41 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 interval P ₄₁ is less than 20 μm, the influence of the diffracted light on the surface of the resin skin layer 3 becomes large, and there is a possibility that iridescent luster is exhibited. If the interval P ₄₁ exceeds 80 μm, the height of the ridge portion 41 must be increased inevitably, which may increase the difficulty of manufacturing the resin leather 1. The spacing P ₄₁ between the ridges 41 is 5 ridges 41 arbitrarily selected by using, for example, an electron microscope (for example, Hitachi High-Technologies Corporation, field emission scanning electron microscope SU8000, etc.). Can be calculated as the arithmetic mean value of the intervals measured by observing from above.

Dimension D ₄₁ of convex portion 41, the angle of the apex angle 41a, the lowermost end 42a and the ridge portion 41 of the height T ₄₁ (concave portions 42 of the adjacent spacing P ₄₁ of the convex portion 41, convex portion 41 The length in the normal direction with the apex angle 41a) and the like can be appropriately set, but for example, it can be set to about 20 μm or more and 80 μm or less. If the dimension D ₄₁ of the ridge portion 41 is less than 20 μm, it is difficult to control the dimension, and it may be difficult to stably manufacture the velvety resin leather 1. If the dimension D ₄₁ of the ridge portion 41 exceeds 80 μm, the height of the ridge portion 41 must be increased inevitably, and the difficulty of manufacturing the resin leather 1 may increase. The dimension of the ridge portion 41 means the length between the lowermost ends 42a of the adjacent ridge portions 42 along the lateral direction of the ridge portion 41.

The height T ₄₁ of the ridge portion 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 portion 41 is less than 17 μm, unevenness may become noticeable, and if it exceeds 150 μm, the difficulty of manufacturing the resin leather 1 may increase.

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

The radius of curvature R of the substantially V-shaped corner 42a of the concave 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 light rays having a small incident angle increases, so that the resin leather 1 may not have a velvety appearance. 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 so that it cannot be used repeatedly.

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

According to the resin leather 1 in the present embodiment, a velvety appearance can be exhibited by the uneven structure 4 (convex portion 41 and concave portion 42) formed on the surface of the resin skin layer 3 with high accuracy.

[Manufacturing method of resin leather]
The method for producing the resin leather in the present embodiment will be described. FIG. 4 is a cross-sectional view showing a schematic configuration of a release sheet used for producing the resin leather in the present embodiment, and FIGS. 5 (A) to 5 (D) are methods for producing the resin leather in the present embodiment. Is a process flow chart showing a cross-sectional view.

In the method for producing resin leather in the present embodiment, as shown in FIG. 5A, first, a release 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. Prepare the mold sheet 10.

As shown in FIG. 4, the release sheet 10 is provided on the base material 11 having the first surface 11A and the second surface 11B facing the first surface 11A and the first surface 11A of the base material 11, and is provided on the base material 11 side. It has a release layer 12 including a second surface 12B located and a first surface 12A facing the second surface 12B, and a concave-convex structure 14 is formed on the first surface 12A side.

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 mold release sheet for producing resin leather or process paper can be used. .. Specifically, as the base material 11, paper base materials such as kraft paper, high-quality paper, and cast-coated paper; polyester base materials such as polyethylene terephthalate and polyethylene naphthalate; polyamides such as various nylons, resin films such as polypropylene; Synthetic paper, metal foil, woven fabric, non-woven fabric and the like can be used. These can be used alone or by laminating two or more kinds as the base material 11. When the resin leather is produced using the release sheet 10, it is preferable to use a paper base material as the base material 11 from the viewpoint that heat deterioration is unlikely to occur and the adhesion to the release layer 12 is high.

The thickness of the base material 11 is not particularly limited and may be appropriately set depending on the material of the base material 11 and the like, but is preferably set to, for example, about 50 μm or more and 200 μm or less.

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

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

Examples of the thermoplastic resin include acrylic resins such as polymethylmethacrylate; polyolefin resins such as polyethylene, polypropylene and polymethylpentene; polyester resins such as polyethylene terephthalate and polybutylene terephthalate; styrene resins such as polystyrene; poly. Examples thereof include vinyl-based resins such as vinyl chloride; polycarbonate resins; conventionally known resins such as polyvinyl alcohol. 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, and melamine ( Examples thereof include meta) acrylates, triazine-based acrylates, and silicone resins. Examples of the active energy ray-curable resin include urethane-based resins, epoxy-based resins, ester-based resins, acrylic resins, and acrylic acid ester copolymers.

The release layer 12 preferably contains the above-mentioned thermoplastic resin, and particularly preferably polypropylene. Since the release layer 12 contains a thermoplastic resin, particularly polypropylene, the uneven structure 14 can be formed on the first surface 12A side of the release layer 12 with high accuracy, and the release sheet 10 is used to form the resin leather. The resin leather can be easily peeled off during the production of. The release layer 12 may be transparent (the transmittance of visible light is about 80% or more), or may be translucent or opaque. Further, the release layer 12 may be colored.

The thickness of the release layer 12 may be such that the concave-convex structure 14 can be formed on the first surface 12A side, and can be set to, for example, 5 μm or more and 200 μm or less, preferably 10 μm or more and 100 μm or less.

A release layer (not shown) that can be formed by applying and drying a silicone-based resin, a fluororesin, or the like may be provided on the first surface 12A of the release layer 12. By providing the release layer, the release property of the release sheet 10 can be further improved when the resin leather is manufactured. When the release layer is provided, the thickness of the release layer may be such that the function of the uneven structure 14 formed on the first surface 12A side of the release layer 12 is not impaired. For example, 0. It can be set to about 01 μm or more and 0.5 μm or less.

The shape of the concave-convex structure 14 formed on the surface of the release layer 12 is a shape corresponding to the concave-convex structure 4 of the resin leather 1, and the concave portions 141 and the concave portions corresponding to the convex portions 41 of the resin leather 1. Includes ridges 142 corresponding to 42.

The uneven 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, so that the resin leather 1 has a velvety tone. It has a structure and the like that can give the appearance of. For example, the angle of the lower end portion of the concave-convex structure 14 in cross-sectional view is set to, for example, about 60 ° or less, and the distance between adjacent concave grooves 141 is set to about 20 μm or more and 80 μm or less. Further, the dimension of the recess 141 (the length between the apex angles of the adjacent protrusions 142) can be set to, for example, about 20 μm or more and 80 μm or less, and the depth can be set to, for example, about 17 μm or more and 150 μm or less.

Subsequently, as shown in FIG. 5B, a composition for forming a resin skin layer is applied to the first surface 12A of the release layer 12 of the release sheet 10 by a conventionally known method, dried, and the resin skin is dried. Form layer 3. As the composition for forming the resin skin layer, it is preferable to use a composition having a desired visible light transmittance, but it 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 containing polyurethane and an arbitrary additive and having a solid content of about 20% by mass or more and 50% by mass or less can be used as the composition for forming the resin skin layer. When the resin leather is polyvinyl chloride leather, a sol containing polyvinyl chloride and an arbitrary additive can be used as the composition for forming the resin skin layer.

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 released. Peel off. Thereby, the resin leather 1 having a velvety appearance can be produced. As the adhesive layer, a conventionally known adhesive layer used for producing resin leather (synthetic leather, artificial leather) can be used.

According to the method for producing resin leather in the present embodiment, resin leather 1 having a velvety appearance can be stably produced.

[Manufacturing method of 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 according to the present embodiment.

A transfer plate 20 having a concavo-convex structure (concave and convex structure including ridges and recesses) corresponding to the concavo-convex structure 14 of the release sheet 10 is prepared on one surface, and the concavo-convex structure of the transfer plate 20 is applied to the base material 11. Transfer to the resin material film 12'formed on the first surface 11A of the above. Preferably, as shown in FIG. 6, a transfer roll 22 in which the transfer plate 20 is wound around the roll body 21 is prepared, and a resin material film 12'is formed on the first surface 11A of the base material 11. By pressing the transfer roll 22 while transporting the raw fabric, the uneven structure 14 is formed on the first surface 12A of the release layer 12. In this way, the release sheet 10 can be produced.

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

As shown in FIG. 7, the thermosetting resin decorative plate 1'in the present 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 convex portions 41'and concave portions 42'is formed. Examples of the thermosetting resin veneer 1'include a high-pressure melamine resin veneer, a low-pressure melamine resin veneer, a diallyl phthalate (DAP) resin veneer, a polyester veneer, a guanamine resin veneer, a phenol resin veneer, and the like. Therefore, a high-pressure melamine resin decorative board is suitable. High-pressure melamine resin veneer has excellent pencil hardness, heat resistance, stain resistance, chemical resistance, etc., so interior or exterior materials for buildings such as walls, ceilings, and floors; window frames, doors, etc. It can be suitably used as a surface decorative board for fittings such as handrails, skirting boards, peripheral edges, and moldings; a surface decorative board for cabinets such as kitchens, furniture, light electric appliances, and OA equipment; as interior or exterior materials for vehicles.

The support layer 2'has a core layer 2a'and a pattern printing layer 2b' laminated on the core layer 2a'.
The core layer 2a'is provided to impart the thickness and strength required for the thermosetting resin decorative plate 1', and is, for example, a phenol resin, a melamine resin, a diallyl phthalate (DAP) resin, a polyester resin, and the like. Examples thereof include a thermosetting resin such as a guanamine resin, preferably a fibrous base material impregnated with a phenol resin, a melamine resin or the like at an impregnation rate of 45% by mass or more and 60% by mass or less. The impregnation rate (mass%) of the thermosetting resin is the mass of the impregnated thermosetting resin (the mass of the base material after impregnation with the thermosetting resin) with respect to the "mass of the base material (fibrous base material)". It can be calculated as a percentage of "difference from the mass of the base material before impregnation)".

Examples of the fibrous base material constituting the core layer 2a' include kraft paper, non-woven fabric, and the like, and those having a basis weight of 150 g / m ² or more and 250 g / m ² or less are preferable. The core layer 2a'may be formed by laminating a plurality of fibrous base materials impregnated with a thermosetting resin, and the number of laminated fibrous base materials is the thermosetting resin decorative plate 1'. It can be appropriately set according to the thickness required for.

Examples of the pattern printing layer 2b' include a porous base material on which a pattern is printed. The porous base material is not particularly limited as long as the pattern can be printed. For example, thin leaf paper, kraft paper, titanium paper, art paper, sulfate paper, glassin paper, linter paper, board paper, and gypsum board paper. Examples thereof include vinyl wallpaper raw fabric obtained by sol or dry-laminating a polyvinyl chloride resin on paper, high-quality paper, coated paper, parchment paper, paraffin paper, Japanese paper and the like.

The method for printing a pattern on a porous substrate is not particularly limited, and is obtained, for example, by dissolving or dispersing a known colorant (pigment or dye) in a solvent or a dispersion medium together with a binder resin. Examples include a printing method using ink. 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. 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 adopted. In addition, the hand-painting method, suminagashi method, photographic method, transfer method, laser beam drawing method, electron beam drawing method, partial vapor deposition method for metals, etching method, etc. are used, or they are used in combination with other printing methods. You may.

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

Colorants contained in the ink include, for example, inorganic pigments such as carbon black, titanium white, zinc flower, petal pattern, dark blue, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, and isoindolinones. Organic pigments such as pigments and dioxazine pigments; metal powder pigments such as aluminum powder and bronze powder; pearl luster pigments such as titanium oxide-coated mica and bismuth oxide; fluorescent pigments; luminous pigments and the like. These colorants may be used alone or in combination of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizers, surfactants and the like.

As the binder resin, in addition to the hydrophilic treated polyester-based urethane resin, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, and rosin derivative. , Alcohol adduct of styrene-maleic anhydride copolymer, cellulose-based resin, casein resin and the like can also be used in combination. More specifically, for example, polyacrylamide resin, poly (meth) acrylic acid resin, polyethylene oxide resin, poly N-vinylpyrrolidone resin, water-soluble polyester resin, water-soluble polyamide resin, water-soluble amino. Water-soluble resins, water-soluble phenolic resins, and other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, and polysaccharides can also be used. Further, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin and the like are modified, a mixture of natural rubber and the like, and other resins. May be used. The binder resin may 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-ethoxy acetate. Ester-based organic solvents such as ethyl; Alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol; Ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Solvents; ether-based organic solvents such as diethyl ether, dioxane, tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene; inorganic solvents such as water and the like. These solvents or dispersion media may 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, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate (DAP) resin, and melamine. A thermosetting resin such as a resin, a guanamine resin, a melamine-urea cocondensate resin, a silicon resin, or a polysiloxane resin is impregnated with an impregnation rate of 30% by mass or more and 200% by mass or less, preferably 50% by mass or more and 150% by mass or less. Examples include a porous base material.

The thermosetting resin may contain a curing agent such as a cross-linking agent and a polymerization initiator, a polymerization accelerator and the like. Examples of the curing agent include unsaturated polyester resin as a thermosetting resin, isocyanate which can be contained in polyurethane resin and the like, organic sulfonate; organic amine which can be contained in epoxy resin and the like. Examples of the polymerization initiator (radical initiator) include peroxides such as methyl ethyl ketone peroxide and azoisobutylnitrile that can be contained in unsaturated polyester resins as thermosetting resins.

The porous base material is not particularly limited as long as it can be impregnated with the thermosetting resin, and examples thereof include a fibrous base material having the permeability of the thermosetting resin. Examples of such fibrous base material include thin leaf paper, kraft paper, titanium paper, art paper, sulfate paper, glassin paper, linter paper, paperboard, gypsum board paper, and vinyl wallpaper obtained by sol or dry laminating a polyvinyl chloride resin on paper. Papers 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 sheets; examples thereof include non-woven fabrics or woven fabrics made of synthetic resin fibers such as polyester, vinylon, polyethylene and polypropylene. From the viewpoint of impregnation property of the thermosetting resin, titanium paper, thin leaf paper, kraft paper, coated paper, art paper, sulfate paper, glassin paper, parchment paper, paraffin paper, and Japanese paper are preferable, and titanium paper is particularly preferable. ..

The porous base material may be colored, and by blending a colorant (pigment, dye, etc.) at the manufacturing stage of the porous base material (if the porous base material is paper, the papermaking stage), the porous base material is porous. The quality substrate can be colored. As the colorant, for example, an inorganic pigment such as titanium dioxide, carbon black, iron oxide; an organic pigment such as phthalocyanine blue; various dyes and the like can be used. , At least one type may be contained, and when two or more types are contained, the blending amount of the colorant can be appropriately set according to the desired color and the like. Further, it is necessary for the porous base material. Various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers may be contained depending on the conditions.

The basis weight of the porous base material is not particularly limited, and is preferably ^{40 g / m 2} or more and 150 g / m ^{2 or less, for example.} The thickness of the porous base material can be appropriately set according to the use, usage, etc. of the thermosetting resin decorative board 1', and is, for example, about 50 μm or more and 170 μm or less.

One surface of the thermosetting resin layer 3'(the surface that comes into contact with the pattern printing layer 2b') may be surface-treated for the purpose of improving adhesion. Examples of the surface treatment include corona discharge treatment and the like.

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

The concave-convex structure 4'including the plurality of convex portions 41'and the concave portion 42'formed in the thermosetting resin layer 3'is the convex formed in the resin skin layer 3 of the resin leather 1 described above. Since it has substantially the same configuration as the strip 41 and the recess 42 (see FIGS. 1 to 3), detailed description here will be omitted.

In the thermosetting resin decorative plate 1'described above, the uneven structure 4'(convex portion 41'and the concave portion 42') is formed on the surface of the thermosetting resin layer 3'with high accuracy. , Can exhibit a velvety appearance.

[Manufacturing method of thermosetting resin decorative board]
FIG. 8 is a process flow chart showing a method for manufacturing a 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 laminated in this order, and the release sheet 10 is laminated on the thermosetting resin layer 3'. The laminate is sandwiched between two metal plates 51 and 52 and pressed at a pressure of 5.9 MPa or more and 9.8 MPa or less at a temperature of 110 ° C or more and 160 ° C or less for 10 minutes or more and 60 minutes or less. Heat for the time.

As the release sheet 10 used for forming the concave-convex structure 4'(convex portion 41' and concave portion 42') on the surface of the thermosetting resin layer 3', the above-mentioned resin leather 1 (FIGS. 1 to 1) is used. The same ones used for producing (see FIG. 3) can be used, but preferably, a polyester base material 11 such as polyethylene terephthalate and polyethylene naphthalate having heat resistance and smoothness and heat resistance are used. A mold containing a release layer 12 made of a thermosetting resin, an active energy ray-curable resin, or the like can be used.

Next, as shown in FIG. 8B, the release sheet 10 is peeled off from the laminated body sandwiched between the metal plates 51 and 52 and pressed and heated. As a result, the thermosetting resin decorative plate 1'in which the uneven 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 method for producing a thermosetting resin veneer in the present embodiment, the thermosetting resin veneer 1'having a velvety appearance can be stably produced.

The embodiments described above are described for facilitating the understanding of the present invention, and are 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 above embodiment, a 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 has been described as an example, but the present invention is not limited to this embodiment. For example, the release sheet 10 may include only the release layer 12 and may not include the base material 11.

In the above embodiment, the example in which the resin skin layer 3 of the resin leather 1 is composed of a single layer has been described, but the present invention is not limited to this embodiment. For example, the resin leather 1 is placed on the support layer 2. A resin skin layer 3 composed of two layers, a first resin skin layer and a second resin skin layer, which are laminated in this order may be provided. In this case, the uneven structure 4 is formed on the surface of the second resin skin layer. It suffices if it is formed. Similarly, in the thermosetting resin decorative plate 1', the thermosetting resin layer 3'may be composed of a plurality of thermosetting resin layers.

In the above embodiment, the embodiment in which the uneven structure 4 is formed on the surface of the resin skin layer 3 has been described as an example, but the present invention is not limited to this embodiment, and the uneven structure 2 and the resin skin layer 3 are uneven. The structure 4 may be formed. The resin leather 1 of this embodiment can be produced, 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 treatment (heat embossing treatment). Similarly, in the thermosetting resin decorative board 1', the uneven structure 4'may be formed on the pattern printing layer 2b'and the thermosetting resin layer 3', and the core layer 2a'and the pattern printing layer may be formed. It may be formed on 2b'and a thermosetting resin layer 3'.

Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the present invention is not limited to the following Examples and the like.

[Example 1]
(1) Preparation of Transfer Plate A transfer plate 20 was produced by forming a concavo-convex structure on the surface of a copper plate (210 mm × 297 mm) by mechanical cutting. The shape of the ridges of the concave-convex structure formed on the transfer plate 20 is an isosceles triangle, the apex angle of the ridges is 30 °, the spacing is 50 μm, and the radius of curvature R of the substantially V-shaped corners of the concave ridges of the uneven structure Was 2 μm.

(2) Manufacture of release sheet Polypropylene is applied on the first surface 11A of the paper base material 11 (thickness: 150 μm) to form a release layer 12 (thickness: 50 μm), and the release layer 12 (thickness: 50 μm) is released under the following conditions. The transfer plate 20 is heated and pressed onto the first surface 12A of the mold layer 12 to transfer the concavo-convex structure, and the base material 11 and the release layer 12 having the concavo-convex structure 14 formed on the first surface 12A are provided. The mold sheet 10 was manufactured.
(Transfer conditions)
・ Cylinder temperature: 120 ° C
・ Pressing pressure: 150 kgf / cm

(3) Production of Resin Leather A resin skin layer forming composition (polyurethane composition for a resin skin layer having the composition shown below) is subjected to a bar coating method on the first surface 12A of the release layer 12 of the release sheet 10. The resin skin layer 3 was formed by heating and drying in the range of 100 ° C. or higher and 120 ° C. or lower for 2 minutes. Then, the support layer 2 was attached onto the resin skin layer 3 using an adhesive, dried and aged, and then the release sheet 10 was peeled off to produce the resin leather 1.
(Composition for forming resin epidermis layer)
-Polyurethane (Resamine NE-8811, manufactured by Dainichiseika Kogyo Co., Ltd.) 100 parts by mass-Colorant (Seika Seven NET-5794 Black, manufactured by Dainichiseika Kogyo Co., Ltd.) 15 parts by mass-Toluene 25 parts by mass-Isopropyl alcohol 25 parts by mass

[Example 2]
The transfer plate 20 was prepared in the same manner as in Example 1 except that the apex angle of the ridges having the uneven structure formed on the transfer plate 20 was changed to 50 °, and the release sheet 10 and the resin leather 1 were manufactured.

[Example 3]
The transfer plate 20 was prepared in the same manner as in Example 1 except that the apex angle of the uneven structure formed on the transfer plate 20 was changed to 60 °, and the release sheet 10 and the resin leather 1 were manufactured.

[Comparative Example 1]
The transfer plate 20 was prepared in the same manner as in Example 1 except that the apex angle of the ridges having the uneven structure formed on the transfer plate 20 was changed to 70 °, and the release sheet 10 and the resin leather 1 were manufactured.

[Comparative Example 2]
The transfer plate 20 was prepared in the same manner as in Example 1 except that the apex angle of the ridges having the uneven structure formed on the transfer plate 20 was changed to 90 °, and the release sheet 10 and the resin leather 1 were manufactured.

[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 is placed on a desk and placed in an environment with an illuminance of 400 lux (equivalent to a bright office). The appearance of each test sample was evaluated by each subject according to the following evaluation criteria. The results are shown in Table 1. As for the appearance evaluation in Table 1, those with an average score of 2.5 points or more by all subjects are "◎", those with 2.0 points or more and less than 2.5 points are "○", 2.0 points. Those less than are marked with "Δ".
<Evaluation criteria>
Looks velvety: 3 points Neither: 2 points Doesn't look velvety: 1 point

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

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

1 ... Resin leather 2 ... Support layer 3 ... Resin skin layer (resin layer)
4 ... Concavo-convex structure 41 ... Convex part 42 ... Concave part 10 ... Release sheet 11 ... Base material 12 ... Release layer 14 ... Concavo-convex structure

Claims (6)

A support layer and a resin layer provided on the support layer are provided.
The resin layer is formed with a concavo-convex structure including a plurality of ridges extending in one direction in the longitudinal direction.
In a cross-sectional view along said widthwise direction of each ridge, each ridge has a substantially isosceles triangular shape, and the Ri angle der than 60 ° apex angle of each ridge,
Distance between the vertical angle between the convex portions adjacent to each, 20Myuemu～80myuemu der Ru resin article. The resin article according to claim 1, wherein the angle of the apex angle of each convex portion is 30 ° or more and 60 ° or less. In a cross-sectional view along the widthwise direction of each ridge, the an angle first and first sides of the perpendicular line and the apex angle with respect to the supporting layer through said top angle of each convex portion When the angle formed by the vertical line and the second side constituting the apex angle is the second angle, the difference between the first angle and the second angle is 0 ° or more and 30 ° or less. Item 2. The resin article according to Item 1 or 2. The resin article according to any one of claims 1 to 3, wherein the resin material constituting the resin layer has a visible light transmittance of 10% or less. Any one of claims 1 to 4 in which the concave portion located between the adjacent convex portions has a substantially V-shape with rounded corners in a cross-sectional view along the lateral direction of the convex portion. The resin article described in. A release sheet used for producing the resin article according to any one of claims 1 to 5.
A mold release layer having a first surface and a second surface facing the first surface is included.
A release sheet on 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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