WO2015063841A1 - Method for producing decorative sheet - Google Patents

Abstract

This method for producing a decorative sheet comprises: a printing step wherein an ink containing a crosslinkable resin material, which contains a curable resin and is capable of forming a three-dimensional crosslinked structure, is printed on a first surface of a base layer that is formed of a resin, and then a print part is formed by curing the curable resin; a coating step wherein a coating material containing an active energy ray-curable resin material, which contains a curable resin and is cured by irradiation of an active energy ray, is applied over the first surface of the base layer and the print part, thereby forming a coating film on the first surface; and a curing step wherein the coating film is cured by being irradiated with an active energy ray. A decorative sheet having improved scratch resistance can be easily produced by this method for producing a decorative sheet.

Description

Manufacturing method of decorative sheet

The present invention relates to a method for manufacturing a decorative sheet.

Improved design for building exteriors such as exterior walls of buildings, exterior doors of houses, exteriors or interiors of automobiles, exteriors or interiors of vehicles, exteriors or interiors of ships, surface layers of electrical appliances, signboards or sign surfaces And for protection of the surface, a decorative sheet is used.
Generally as a decorative sheet, the lamination sheet provided with the base material layer which has the designability, and the surface layer formed in the surface of this base material layer is used widely.
By the way, in a decorative sheet, a mat part with reduced gloss may be formed on a part of its surface.
Conventionally, as a method for forming a mat portion on a part of the surface of a decorative sheet, the following method (1) or (2) has been known.
(1) A surface layer forming coating containing an active energy ray-curable resin is applied to the surface of a substrate layer having design properties, and then cured by irradiation with active energy rays to form a surface layer. A mat portion forming coating containing an active energy ray-curable resin and particles is partially applied to the surface of the surface layer, and then cured by irradiation with active energy rays to form a mat portion (Patent Document 1). .
(2) A liquid containing melamine resin particles is printed on one surface of a polyethylene terephthalate substrate to obtain a mat-shaped film having an uneven surface. An uncured coating film is formed by applying a surface layer-forming coating material containing an active energy ray-curable resin to the surface of the substrate layer having design properties. The uneven surface of the mat shaping film is brought into close contact with the uncured coating film to transfer the unevenness. The surface layer is formed by curing the uncured coating film by irradiating an active energy ray while keeping the uneven surface of the mat shaping film in close contact with the uncured coating film. The mat forming film is peeled off from the surface layer (Patent Document 2).

However, in the above method (1), when the surface is rubbed, the mat portion protruding from the surface layer is easily cut and damaged, and the intended designability may not be obtained.
In the method (2), the production of the decorative sheet becomes complicated, and the productivity of the decorative sheet tends to be low.

Japanese Patent Laid-Open No. 9-156064 JP-A-1-320156

The problem to be solved by the present invention is to easily manufacture a decorative sheet having improved scratch resistance in a method for manufacturing a decorative sheet having a mat portion.

The method for producing a decorative sheet according to the first aspect of the present invention includes an ink containing a crosslinkable resin material containing a curable resin and capable of forming a three-dimensional crosslinked structure on a first surface of a resin base layer. A printing step of printing and curing the curable resin to form a printed portion, and the first surface of the base material layer and the printed portion contain a curable resin and are cured by irradiation with active energy rays. Applying a coating material containing an active energy ray-curable resin material, forming a coating film on the first surface, and irradiating the coating film with an active energy ray to cure the coating film A curing step.
In the method for producing a decorative sheet according to the second aspect of the present invention, printing is performed by printing an ink containing a curable resin and a curing agent on the first surface of a resin base layer, and curing the curable resin. A coating process including an active energy ray-curable resin material that contains a curable resin and is cured by irradiation with active energy rays on the first surface of the base material layer and the printed portion. And a coating process for forming a coating film on the first surface, and a curing process for irradiating the coating film with an active energy ray to cure the coating film.
In the method for producing a decorative sheet of the present invention, the viscosity of the ink at 25 ° C. is preferably 10 to 100 mPa · s.
In the method for producing a decorative sheet of the present invention, it is preferable that the integrated irradiation amount of active energy rays in the curing step is 50 to 500 mJ / cm ² .
In the method for producing a decorative sheet of the present invention, the resin constituting the base material is preferably polyethylene terephthalate or polyvinyl chloride.
In the method for producing a decorative sheet of the present invention, it is preferable that both the curable resin contained in the ink and the curable resin contained in the paint are acrylic compounds.

The decorative sheet of the present invention comprises a resin base layer and a surface layer formed on the first surface of the base layer, and the surface layer has a glossiness of 2 to 18% measured according to ISO2813. The mat portion includes a gloss portion having a glossiness of 80 to 100% measured according to ISO 2813, and the mat portion has a three-dimensional cross-linking structure.
In the decorative sheet of the present invention, the arithmetic average surface roughness measured according to ISO 4287: 1997 of the mat portion is 0.05 to 2.0 μm, and the arithmetic average surface roughness measured according to ISO 4287: 1997 of the gloss portion is The value is preferably smaller than the arithmetic average surface roughness of the mat portion and is 0.01 to 1.0 μm.
In the decorative sheet of the present invention, the resin constituting the base material is preferably polyethylene terephthalate or polyvinyl chloride.
In the decorative sheet of the present invention, it is preferable that both the mat portion and the gloss portion are formed of an acrylic resin.

According to the method for producing a decorative sheet of the present invention, a decorative sheet having improved scratch resistance can be easily produced.

It is sectional drawing which shows the decorative sheet manufactured by one Embodiment of the manufacturing method of the decorative sheet of this invention. It is sectional drawing explaining the printing process which comprises one Embodiment of the manufacturing method of the decorative sheet of this invention. It is sectional drawing explaining the coating process which comprises one Embodiment of the manufacturing method of the decorative sheet of this invention.

Hereinafter, an embodiment of the present invention will be described.
The decorative sheet manufactured by the manufacturing method of the decorative sheet of this embodiment is demonstrated.
In FIG. 1, the decorative sheet manufactured by the manufacturing method of the decorative sheet of this embodiment is shown. The decorative sheet 1 in this embodiment includes a base material layer 10 and a surface layer 20 formed on the first surface 10 a of the base material layer 10.

The base material layer 10 is a resin layer, and for example, a resin film is used.
In order to improve the designability, the base material layer 10 may be subjected to printing, may be colored, or may be subjected to both printing and coloring.
The base material layer 10 may be composed of a plurality of layers. In that case, the printing film to which printing was given may be provided, the coloring film to which coloring was given may be provided, and both a printing film and a coloring film may be provided.
There is no restriction | limiting in particular in the pattern formed in the base material layer 10 by printing.
As a colorant used when the base material layer 10 is colored, various inorganic color pigments, organic color pigments, and glitter pigments can be used.
A primer layer may be formed on the resin film in order to improve adhesion with the surface layer 20.

When a resin film is used as the base material layer 10, examples of the resin constituting the resin film include polyethylene terephthalate and polyvinyl chloride.
The thickness of the resin film is preferably 20 to 700 μm, more preferably 50 to 500 μm. If the thickness of the resin film is not less than the lower limit, the mechanical strength can be sufficiently increased, and if it is not more than the upper limit, sufficient flexibility can be ensured.

The base material layer 10 may contain additives such as an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a storage stabilizer, a plasticizer, a lubricant, and a filler as necessary.

The surface layer 20 includes a mat portion 21 and a gloss portion 22 having a glossiness higher than that of the mat portion 21. Here, the glossiness is a glossiness (%) measured according to ISO2813 (JIS Z8741). The glossiness is obtained by obtaining the reflectance of the sample based on the reflectance of the black standard plate at an incident angle of 60 degrees and a reflection angle of 60 degrees, and is measured by, for example, Gloss Checker IG-320 (manufactured by Horiba Seisakusho). Can do.
The glossiness of the mat portion 21 is 2 to 18%, and preferably 3 to 15%.
The glossiness of the gloss part 22 is 80 to 100%, preferably 85 to 95%.
If the glossiness of the mat portion 21 and the glossiness of the gloss portion 22 are within the above ranges, a sufficient difference in gloss occurs, and it becomes easy to obtain a high-quality design.
The arithmetic average surface roughness of the mat portion 21 is preferably 0.05 to 2.0 μm, and more preferably 0.2 to 2.0 μm.
The arithmetic average surface roughness of the gloss part 22 is smaller than the arithmetic average surface roughness of the mat part 21, and is preferably 0.01 to 1.0 μm, more preferably 0.02 to 0.5 μm. preferable.
The arithmetic average surface roughness is a value measured according to ISO 4287: 1997 (JIS B 0601-2001). The arithmetic average surface roughness can be measured by, for example, a color 3D laser microscope VK-9710 (manufactured by Keyence). Specifically, the surface is observed at each magnification using the attached standard objective lenses CF IC EPI Plan 10X, CF IC EPI Plan 20X, CF IC EPI Plan Apo 50X, and CF IC EPI Plan Apo 150XA (all manufactured by Nikon). The image data can be measured by image analysis using an observation application (VK-HV1 manufactured by Keyence).
In the present embodiment, the mat portion 21 and the gloss portion 22 are formed with a pattern.

The area ratio between the mat portion 21 and the gloss portion 22 in the surface layer 20 is appropriately selected according to the target design. In order to obtain a sufficient design property, the area of the mat portion 21 / the area of the gloss portion 22 is preferably 1/100 to 3/1, and more preferably 1/10 to 1/1.

The surface layer 20 may contain a colorant, a light stabilizer, an antioxidant, an antistatic agent, a storage stabilizer, a plasticizer, a lubricant, a filler, and the like.

The thickness of the surface layer 20 is preferably 1 to 20 μm, and more preferably 3 to 15 μm. If the thickness of the surface layer 20 is not less than the lower limit value, sufficiently high scratch resistance and design can be obtained, and if it is not more than the upper limit value, the occurrence of cracks in the surface layer 20 can be prevented.
The mat portion 21 and the gloss portion 22 constituting the surface layer 20 have the same thickness.

The decorative sheet 1 as described above is excellent in design, and is a building material such as an outer wall of a building, an entrance door of a house, an exterior or interior of an automobile, an exterior or interior of a vehicle, an exterior or interior of a ship, and a surface material of an electrical appliance. Used for signboards or sign surfaces.

Next, a method for manufacturing a decorative sheet for manufacturing the decorative sheet will be described.
The manufacturing method of the decorative sheet 1 of this embodiment has a printing process, a coating process, and a hardening process.

As shown in FIG. 2, the printing process is a process in which ink containing a curable resin is printed on the first surface 10 a of the base material layer 10, and the curable resin is cured to form a printing portion 21 a. . As the ink, an ink containing a crosslinkable resin material containing a curable resin and capable of forming a three-dimensional crosslinked structure can be used. The ink may be an ink that contains a curable resin and cannot form a three-dimensional crosslinked structure. An ink containing a curable resin and a curing agent may not have a three-dimensional crosslinked structure.
As a printing method, gravure printing, screen printing, flexographic printing, inkjet printing, or the like can be applied.
Examples of patterns for printing include, for example, wood, stone, fabric, sand, tiled patterns, brickwork patterns, leather pattern, geometric patterns, conduit patterns, character combinations, symbol combinations, stripe patterns, etc. Is mentioned.

Examples of the crosslinkable resin material contained in the ink include the following (a) to (c).
(A) A two-component curable resin material containing a curable resin and a curing agent.
(B) A thermosetting resin material that contains a curable resin and a cross-linking agent such as a polyfunctional monomer and is cured by heat.
(C) An active energy ray-curable resin material that contains a curable resin and a cross-linking agent such as a polyfunctional monomer and is cured by irradiation with active energy rays such as ultraviolet rays and electron beams.
When the two-component curable resin material (a) is used as the crosslinkable resin material, the mat portion 21 with reduced glossiness can be easily formed.

Examples of the curable resin include an acrylic compound, an epoxy compound, and a phenol compound, but an acrylic compound is preferable in terms of obtaining high hardness.

Examples of the acrylic compound include polyfunctional (meth) acrylates having two or more (meth) acryloyl groups in the molecule and monofunctional (meth) acrylates having one (meth) acryloyl group in the molecule. The polyfunctional (meth) acrylate and the monofunctional (meth) acrylate may be used alone or in combination.

Examples of the polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the molecule include neopentyl glycol di (meth) acrylate, 1,6-hexanediol diacrylate, trimethylolpropane tri (meth) acrylate, Polyol poly (meth) acrylates such as ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Bisphenol A diglycidyl ether di (meth) acrylate, di (meth) acrylate of neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl Epoxy (meth) acrylate such as di (meth) acrylate of polyester, polyester (meth) acrylate obtained by esterifying polyhydric alcohol with polyhydric carboxylic acid and / or anhydride thereof and (meth) acrylic acid, Examples thereof include urethane (meth) acrylate and polysiloxane poly (meth) acrylate obtained by reacting polyhydric alcohol, polyvalent isocyanate and hydroxyl group-containing (meth) acrylate.
Monofunctional (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (Meth) acrylate etc. are mentioned.
These may be used individually by 1 type, and may mix and use 2 or more types.

When the crosslinkable resin material is (a) a two-component curable resin material, a diisocyanate compound, an epoxy compound, or the like can be used as a curing agent contained together with the curable resin.
The addition amount of the curing agent is preferably 0.1 to 20 parts by mass and more preferably 5 to 15 parts by mass with respect to 100 parts by mass of the curable resin. If the addition amount of the curing agent is not less than the lower limit, sufficient hardness can be obtained. However, when the addition amount of the curing agent exceeds the upper limit, the amount of the curing agent that does not participate in the curing increases and waste increases.

When the crosslinkable resin material is (b) a thermosetting resin material, a thermopolymerization initiator is included together with the curable resin, thereby becoming thermosetting. Examples of the thermal polymerization initiator include peroxides.
The blending amount of the thermal polymerization initiator is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the curable resin. If the content of the thermal polymerization initiator is not less than the lower limit, thermal polymerization can be easily performed. However, even if a thermal polymerization initiator is blended in excess of the upper limit, the effect of improving thermal polymerization reaches a peak and is useless.

When the crosslinkable resin material is (c) an active energy ray curable resin material, the photopolymerization initiator is contained together with the curable resin, and the active energy ray curable is obtained. Examples of the photopolymerization initiator include acetophenone, benzophenone, benzoin ether, anthraquinone, thiol and the like.
The blending amount of the photopolymerization initiator is preferably 0.01 to 10 parts by mass based on 100 parts by mass of the curable resin. If the content of the photopolymerization initiator is not less than the lower limit, photopolymerization can be easily performed. However, even if a photopolymerization initiator is blended in excess of the above upper limit, the effect of improving photopolymerization reaches its peak and is useless.

The ink may contain a diluting solvent. Examples of the dilution solvent include ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; esters such as ethyl acetate, butyl acetate, isobutyl acetate, and propyl acetate; alcohols such as ethanol and isopropyl alcohol; Examples thereof include hydrocarbons such as toluene, xylene, and cyclohexane.

The ink may contain a colorant. As the colorant, inorganic pigments, organic pigments, glitter pigments and the like can be used.
Examples of the inorganic pigment include titanium white, zinc white, carbon black, iron black, dial, chrome vermilion, cadmium red, ultramarine, cobalt blue, yellow lead, titanium yellow, and the like.
Examples of the organic pigment include phthalocyanine blue, indanthrene blue, isoindolinone yellow, benzylidine yellow, quinacridone red, polyazo red, berylene red, and aniline black. Examples of the luster pigment include aluminum pieces and brass pieces.
The colorants can be used alone or in combination of two or more.

The viscosity of the ink is preferably 10 to 100 mPa · s, and more preferably 50 to 80 mPa · s. The viscosity of the ink is a value measured using a B-type viscometer at 25 ° C.
If the viscosity of the ink is within the above range, the printability is good.

The ink may contain a light stabilizer, an antioxidant, an antistatic agent, a storage stabilizer, a plasticizer, a lubricant, a filler and the like as required.

The coating step is a step of coating the first surface 10a of the base material layer 10 and the printing portion 21a with a paint containing an active energy ray-curable resin that contains a curable resin and is cured by irradiation with active energy rays. It is.
As shown in FIG. 3, the coating material applied to the first surface 10a of the base material layer 10 becomes a coating film 22a formed on the first surface 10a. The coating film 22a is an uncured film of a paint containing an active energy ray curable resin material.
The paint applied to the printing unit 21a is absorbed into the printing unit 21a.

The active energy ray-curable resin material contained in the paint contains a photopolymerization initiator together with the curable resin. As the curable resin and the photopolymerization initiator, the same curable resin and photopolymerization initiator as those contained in the ink can be used.
However, the curable resin contained in the paint and the curable resin contained in the ink need not be the same and may be different. The photopolymerization initiator contained in the paint and the photopolymerization initiator contained in the ink need not be the same and may be different.

The paint may contain a curing agent. As the curing agent, the same ones as those contained in the ink can be used. However, the curing agent contained in the paint and the curing agent contained in the ink need not be the same and may be different.
The paint may contain a diluting solvent. As the diluting solvent, the same solvents as those contained in the ink can be used. However, the diluting solvent contained in the paint and the diluting solvent contained in the ink need not be the same and may be different.
The paint may contain a colorant, a light stabilizer, an antioxidant, an antistatic agent, a storage stabilizer, a plasticizer, a lubricant, a filler, and the like as necessary.

The viscosity of the paint is preferably 1 to 100 mPa · s, and more preferably 5 to 50 mPa · s. The viscosity of the paint is a value measured using a B-type viscometer at 25 ° C.
When the viscosity of the paint is in the above range, the coating property is improved and the paint is more easily absorbed by the printing unit 21a.
The solid content concentration of the paint is preferably 5 to 50% by mass, and more preferably 20 to 30% by mass.
When the solid content concentration of the paint is in the above range, the coating property is improved and the paint is more easily absorbed by the printing unit 21a.

Examples of paint coating methods include gravure coating methods (including micro gravure reverse coating methods), roll knife coating methods, die coating methods, reverse roll coating methods, roll coating methods, and cast coating methods.
The coating amount of the paint is set so that the thickness of the coating film 22a is the same as the thickness of the printing portion 21a.

The coating film may be dried or may not be dried.
As a drying method for drying the coating film, a heat drying method, a vacuum drying method, or a combination of these methods can be applied.

The curing step is a step of curing the coating film 22a by irradiating the coating film 22a with active energy rays. When the coating film 22a is cured, the gloss portion 22 is obtained.
The gloss portion 22 may have a three-dimensional crosslinked structure or may not have a three-dimensional crosslinked structure.

Examples of the irradiation method of the active energy ray include a method of irradiating the coating film 22a with ultraviolet rays using an ultraviolet lamp, and a method of irradiating the coating film 22a with electron beams using an electron beam generator.
The cumulative dose of active energy rays is preferably 50 to 500 mJ / cm ^2, and preferably 100 to 300 mJ / cm ² . If the integrated irradiation amount of the active energy ray is set to the lower limit value or more, the coating film 22a can be sufficiently cured. On the other hand, if the integrated irradiation amount of the active energy ray is set to the upper limit value or less, useless consumption of energy can be prevented in curing the coating film 22a.

In the manufacturing method of the decorative sheet 1, the printing portion 21 a formed in the printing process becomes the mat portion 21. In the printing part 21a, irregularities are easily formed on the surface, and the light is diffusely reflected.
In the coating process, even if the coating is applied from above the printing unit 21a, the coating is absorbed by the printing unit 21a, so that the unevenness of the surface of the printing unit 21a is maintained. On the other hand, when a paint is applied to the first surface 10a of the base material layer 10, a coating film 22a having a small surface irregularity can be formed. Therefore, when the coating film 22a is cured, the gloss portion 22 having high glossiness is obtained.
The mat portion 21 and the gloss portion 22 have the same surface because they are absorbed even when a coating is applied to the printing portion 21a. Therefore, since the mat portion 21 does not protrude from the gloss portion 22, it is difficult to chip even if the surface is rubbed. Moreover, since both the mat portion 21 and the gloss portion 22 are made of a cured resin, the surface layer 20 has high scratch resistance.
In the manufacturing method of said decorative sheet 1, there are few processes at the time of forming the mat | matte part 21 and the gloss part 22. FIG. Therefore, the decorative sheet 1 can be easily manufactured.

Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other changes of the configuration can be made without departing from the spirit of the present invention. The present invention is not limited to the above embodiment, and is limited only by the scope of the claims.

Example 1
Colored glycol-modified polyethylene terephthalate (hereinafter referred to as “PETG”) was molded using a calendar molding machine to obtain a PETG sheet having a thickness of 100 μm.
Ink was gravure-printed on the first surface of the PETG sheet to form a printing portion. The printed pattern at that time was a stripe pattern with a 5 mm width and an equal interval. The ink includes 100 parts by mass of a curable resin (CI medium 756 manufactured by DIC Graphics Corporation), 4 parts by mass of a diisocyanate curing agent (W-AH manufactured by DIC Graphics) and a solvent. Using.
The printed part was dried and allowed to stand at 25 ° C. for 3 days to be cured, and then a coating was applied to the first surface of the PETG sheet on which the printed part was formed, using a micro gravure reverse coater. As the paint, a urethane acrylate ultraviolet curable paint (RQ5360, manufactured by Mitsubishi Rayon Co., Ltd., solvent: methyl ethyl ketone, solid content concentration: 20% by mass, viscosity: 10 mPa · s) was used.
By the coating of the paint, a 20 μm coating film was formed on the portion of the PETG sheet where the printing part was not formed. The paint applied to the printing part penetrated into the printing part.
The coating film was dried by heating at 60 ° C. for 30 seconds, and then the dried coating film and the printed part were irradiated with ultraviolet rays to form a surface layer. At that time, the cumulative amount of UV irradiation was 300 mJ / cm ² .
Thereby, the said coating film was hardened and the decorative sheet was obtained. In this decorative sheet, the portion that was the printing portion became the mat portion, and the coating film formed on the portion where the printing portion was not formed became the gloss portion. No step was formed at the boundary between the mat portion and the gloss portion.
When the 60 ° glossiness and the arithmetic surface roughness of the mat part and the gloss part were measured, the values shown in Table 1 were obtained.

(Comparative Example 1)
A PETG sheet having a thickness of 100 μm was obtained by molding PETG using a calendar molding machine.
The printed part was formed by gravure printing the ink on the first surface of the PETG sheet. The ink includes 90% by mass of a urethane acrylate ultraviolet curable paint (RQ5360 manufactured by Mitsubishi Rayon Co., Ltd.) and 10% by mass of particles composed of melamine resin and silica (Opto Beads 2000M manufactured by Nissan Chemical Industries, Ltd.). Was used.
The printed part was dried by heating at 60 ° C. for 30 seconds, and then the dried printed part was irradiated with ultraviolet rays. At that time, the cumulative amount of UV irradiation was 300 mJ / cm ² .
Thereby, the said printing part was hardened and the decorative sheet was obtained. In this decorative sheet, the portion that was the printing portion became the mat portion. The mat portion protruded from the first surface of the PETG sheet, and large irregularities were formed on the surface of the decorative sheet.

(Comparative Example 2)
A PETG sheet having a thickness of 100 μm was obtained by molding PETG using a calendar molding machine.
A coating was applied to the first surface of the PETG sheet using a micro gravure reverse coater to form a coating film having a thickness of 10 μm. As the coating material, a urethane acrylate ultraviolet curable coating material (RQ5360 manufactured by Mitsubishi Rayon Co., Ltd.) was used.
The coating film was dried by heating at 60 ° C. for 30 seconds, and then the dried coating film was irradiated with ultraviolet rays to form a cured coating film. At that time, the cumulative amount of UV irradiation was 300 mJ / cm ² .
Gravure printing was performed on the surface of the cured coating film to form a printing portion. The printed pattern at that time was a stripe pattern with a 5 mm width and an equal interval. Moreover, as said ink, urethane acrylate type ultraviolet curable coating material (Mitsubishi Rayon Co., Ltd. RQ5360) 90 mass%, and the particle | grains (Nissan Chemical Chemical Co., Ltd. optobead 2000M) 10 mass% consisting of a melamine resin and silica. What was included was used.
The printed part was dried by heating at 60 ° C. for 30 seconds, and then the dried printed part was irradiated with ultraviolet rays. At that time, the cumulative amount of UV irradiation was 300 mJ / cm ² .
Thereby, the said printing part was hardened and the decorative sheet was obtained. In this decorative sheet, the portion that was the printing portion became the mat portion. The mat portion protruded from the cured coating film, and large irregularities were formed on the surface of the decorative sheet.

(Comparative Example 3)
A PETG sheet having a thickness of 100 μm was obtained by molding PETG using a calendar molding machine.
On the first side of a biaxially stretched PET film (A4100 manufactured by Toyobo Co., Ltd., 50 μm thick), 50 parts by mass of melamine mat ink (melamine resin (EZ-3509-PR manufactured by DIC Corporation), silica (manufactured by Fuji Silysia Co., Ltd.) Silicia 350) 5 parts by mass and solvent (butyl acetate / butanol = 1/1) 45 parts by mass) were subjected to gravure printing to produce a film for shaping having an uneven surface.
A coating was applied to the PETG sheet using a micro gravure reverse coater and dried to form a coating film having a thickness of 10 μm. As the coating material, a urethane acrylate ultraviolet curable coating material (RQ5360 manufactured by Mitsubishi Rayon Co., Ltd.) was used.
The shaping film was bonded to the coating film so that the uneven surface of the shaping film was in close contact with the coating film, and ultraviolet rays were irradiated in that state. At that time, the cumulative amount of UV irradiation was 300 mJ / cm ² .
The shaping film was peeled off to obtain a decorative sheet.

<Evaluation>
The scratch resistance of the obtained decorative sheet was evaluated. Specifically, the surface of the decorative sheet was reciprocated 10 times while applying a load of 0.1 MPa to steel wool (# 0000). Thereafter, the surface was visually evaluated according to the following criteria.
1: No change or several minor scratches.
2: More than 10 scratches or a clear change in appearance was observed.
The evaluation results of the scratch resistance are shown in Table 2.
Table 2 also shows the number of steps and cost in the production of the decorative sheet.

The decorative sheet obtained in Example 1 was excellent in the scratch resistance of the mat portion. Manufacture of the decorative sheet of Example 1 was simple, low in cost, with few steps.
The decorative sheet obtained in Comparative Example 1 had low scratch resistance at the mat portion.
In the manufacture of the decorative sheets of Comparative Examples 2 and 3, the number of steps was large, complicated, and expensive.

DESCRIPTION OF SYMBOLS 1 Cosmetic sheet 10 Base material layer 10a 1st surface 20 Surface layer 21 Matte part 21a Printing part 22 Gloss part 22a Coating film

Claims (10)

On the first surface of the resin base material layer, an ink containing a crosslinkable resin material containing a curable resin and capable of forming a three-dimensional crosslinked structure is printed, and the curable resin is cured to form a printed portion. A printing process to be formed;
The first surface of the base material layer and the printing portion are coated with a paint containing an active energy ray-curable resin material that contains a curable resin and is cured by irradiation with active energy rays. A coating process for forming a coating film on the surface;
A curing step of irradiating the coating film with active energy rays to cure the coating film;
A method for producing a decorative sheet, comprising: A printing step of printing an ink containing a curable resin and a curing agent on the first surface of the resin base material layer, and curing the curable resin to form a printing portion;
The first surface of the base material layer and the printing portion are coated with a paint containing an active energy ray-curable resin material that contains a curable resin and is cured by irradiation with active energy rays. A coating process for forming a coating film on the surface;
A curing step of irradiating the coating film with active energy rays to cure the coating film;
A method for producing a decorative sheet, comprising: The method for producing a decorative sheet according to claim 1 or 2, wherein the ink has a viscosity of 10 to 100 mPa · s at 25 ° C. The method for producing a decorative sheet according to any one of claims 1 to 3, wherein an integrated irradiation amount of the active energy ray in the curing step is 50 to 500 mJ / cm ² . The method for producing a decorative sheet according to any one of claims 1 to 4, wherein the resin constituting the substrate is polyethylene terephthalate or polyvinyl chloride. The method for producing a decorative sheet according to any one of claims 1 to 5, wherein the curable resin contained in the ink and the curable resin contained in the paint are both acrylic compounds. A resin base layer, and a surface layer formed on the first surface of the base layer;
The surface layer includes a mat portion having a glossiness of 2 to 18% measured according to ISO2813 and a gloss portion having a glossiness of 80 to 100% measured according to ISO2813, and the mat portion has a three-dimensional cross-linking structure. A decorative sheet. The arithmetic average surface roughness of the mat portion measured according to ISO 4287: 1997 is 0.05 to 2.0 μm, and the arithmetic average surface roughness of the gloss portion measured according to ISO 4287: 1997 is the arithmetic average surface of the mat portion. The decorative sheet according to claim 7, wherein the decorative sheet has a value smaller than the roughness and 0.01 to 1.0 µm. The decorative sheet according to claim 7 or 8, wherein the resin constituting the substrate is polyethylene terephthalate or polyvinyl chloride. The decorative sheet according to any one of claims 7 to 9, wherein both the mat portion and the gloss portion are formed of an acrylic resin.

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