JP2014210368A - High sharpness decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyester decorative sheet with a design having a feeling of depth and excellent in sharpness.SOLUTION: Fine embossment of a specific shape is applied on a surface of a transparent hard coat. Gloss of a surface of the fine embossment on the transparent hard coat and gloss of a surface of a transparent polyester resin film as a transparent resin layer or a hard coat laminate surface of a transparent polyester resin film laminate body is set at a constant relation.

Description

The present invention relates to a decorative sheet. More specifically, the present invention relates to a polyester-based decorative sheet having a sense of depth and having a sharp design.

Traditionally, furniture such as display cabinets, storage cabinets, cupboards, desks, etc .; household appliances such as refrigerators, washing machines, air conditioners, mobile phones, personal computers; or wood, plywood, laminated wood as building components such as floors, walls, bathrooms Decorative decoration made by adhering a decorative sheet made of resin on the surface of a base material made of a wood-based material such as particle board or hard board; or on the surface of a base material made of a metal-based material such as iron or aluminum Things are used. Polyester-based resin films have high transparency, gloss, good impact resistance, and are excellent in pasting workability on the surface of a substrate, and are therefore frequently used in such decorative sheets. However, the polyester-based resin film has a design problem that only a low sharpness can be obtained by laminating it as a transparent resin layer on the decorative layer and adding a depth to the decorative sheet design. was there.

Therefore, as a technique for obtaining a “laminating film having a low reflectance and a low wavelength dependency of the reflectance”, “a laminating film having a fine concavo-convex structure on the surface, wherein the fine concavo-convex structure has a plurality of convex portions. And an average interval between the convex portions is 400 nm or less. ”(Patent Document 1) has been proposed.

However, when a polyester resin is used as the transparent resin layer on the decorative layer, the sharpness improving effect can be obtained even if the same shape of fine embossing is applied to the hard coat surface of the decorative sheet. However, there is no description or suggestion regarding this point.

JP 2009-269237 A

The subject of this invention is providing the polyester-type decorating sheet which has a design which has a deep feeling and was excellent also in sharpness.

As a result of diligent research, the present inventor has made a fine emboss of a specific shape on the surface of the transparent hard coat, and the gloss of the fine embossed surface of the transparent hard coat, and a transparent polyester resin film or transparent polyester as a transparent resin layer It has been found that the above problem can be achieved by making the surface gloss of the hard coat laminate surface of the resin film laminate a certain relationship.

That is, the present invention
A decorative sheet having a transparent hard coat (A), a transparent polyester resin layer (B), and a decorative layer (C) in order from the surface side,
(1) The transparent hard coat (A) and the transparent polyester resin layer (B) are directly laminated;
(2) The transparent polyester resin layer (B) and the decorative layer (C) are laminated directly or via a transparent adhesive (E);
(3) The transparent hard coat (A) is the outermost layer;
(4) The surface of the transparent hard coat (A) is finely embossed;
(5) The shape of the fine embossing has a plurality of convex portions, an average interval between the convex portions is 100 to 500 nm, and an average height of the convex portions is 80 to 500 nm;
(6) 60 ° gloss (Ga) of the fine embossed surface of the transparent hard coat (A) and 60 ° gloss (Gb) of the hard coat laminated surface of the transparent polyester resin layer (B) satisfy the following formula (α). about;
Is a decorative sheet characterized by
Gb-Ga ≧ 35 (α)
A decorative sheet having a transparent hard coat (A), a transparent polyester resin layer (B), and a decorative layer (C) in order from the surface side,
(1) The transparent hard coat (A) and the transparent polyester resin layer (B) are laminated via the transparent anchor coat (D);
(2) The transparent polyester resin layer (B) and the decorative layer (C) are laminated directly or via a transparent adhesive (E);
(3) The transparent hard coat (A) is the outermost layer;
(4) The surface of the transparent hard coat (A) is finely embossed;
(5) The shape of the fine embossing has a plurality of convex portions, an average interval between the convex portions is 100 to 500 nm, and an average height of the convex portions is 80 to 500 nm;
(6) The 60 ° gloss (Ga) of the fine embossed surface of the transparent hard coat (A) and the 60 ° gloss (Gd) of the hard coat laminated surface of the transparent anchor coat (D) satisfy the following formula (β);
Is a decorative sheet characterized by
Gd-Ga ≧ 35 (β)

The design of the decorative sheet of the present invention has a sense of depth and is excellent in sharpness. Therefore, it can be suitably used for decorative makeup of articles, particularly for decorative makeup of articles such as refrigerator doors and kitchen doors.

The decorative sheet of the present invention is a decorative sheet having a transparent hard coat (A), a transparent polyester resin layer (B), and a decorative layer (C) in this order from the surface layer side, and (1) a transparent hard coat (A ) And the transparent polyester resin layer (B) are laminated directly or via the transparent anchor coat (D), and (2) the transparent polyester resin layer (B) and the decorative layer (C) are directly Alternatively, they are laminated via a transparent adhesive (E). By having such a layer structure, a sense of depth is imparted to the design of the decorative sheet.

Said transparent hard-coat (A) is located in the outermost layer of a decorating sheet | seat, and the fine emboss is given to the surface. The fine embossed shape has a plurality of convex portions in order to obtain high sharpness, and the average interval between the convex portions is 100 to 500 nm, preferably 150 to 450 nm, more preferably 200 to 400 nm or less. In addition, the average height of the convex portions is 80 nm or more, preferably 120 nm or more, more preferably 150 nm or more. Further, from the viewpoint of moldability of fine embossing, the average height of the convex portions is 500 nm or less, preferably 400 nm or less, more preferably 300 nm or less.

As the structure of the convex portion, for example, a so-called moth-eye structure in which a plurality of projections such as a substantially conical shape and a substantially pyramid shape are arranged; a so-called pillar structure in which a plurality of projections such as a substantially cylindrical shape and a substantially prismatic shape are arranged.

The transparent hard coat (A) having the fine embossed surface on the surface has a 60 ° gloss (Ga) of the fine embossed surface of usually 70% or less, preferably 50% or less, more preferably 40% or less. The feeling is suppressed.

In addition, in this specification, the average distance between convex parts uses an atomic force microscope, measures the distance from the center of a convex part to the center of an adjacent convex part in each of five visual fields, and gives a total of 25 points. The average value was obtained. The average height of the protrusions is measured using an atomic force microscope, and the height difference between the highest point of the protrusion and the lowest point of the adjacent recess is measured at 5 points each in 5 fields of view, and the average value of 25 points is averaged. And asked.

The thickness of the transparent hard coat (A) is preferably 0.5 μm or more in order to obtain fine sharpness on the surface to obtain high sharpness. There is no particular upper limit on the thickness of the transparent hard coat (A). However, since an unnecessarily thick hard coat only increases the cost, the thickness is 60 μm at most.

The method for forming the transparent hard coat (A) with fine embossing on the surface is not limited, and can be formed by any method. For example, a method of pressing an uncured coating film of an arbitrary curable resin material such as an active energy ray-curable resin composition with a mold having a fine embossed structure on the surface; An arbitrary curable resin material such as an energy ray curable resin composition may be poured and cured, and then transferred.

The active energy ray-curable resin composition can be polymerized and cured by active energy rays such as ultraviolet rays and electron beams to form a hard coat. Examples of the composition include a compound having two or more isocyanate groups (—N═C═O) and / or a photopolymerization initiator.

Examples of the active energy ray-curable resin include polyurethane (meth) acrylate, polyester (meth) acrylate, polyacryl (meth) acrylate, epoxy (meth) acrylate, polyalkylene glycol poly (meth) acrylate, and polyether. (Meth) acryloyl group-containing prepolymer or oligomer such as (meth) acrylate; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenyl (meth) acrylate, Enylcellosolve (meth) acrylate, 2-methoxyethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-acryloyloxyethyl hydrogen phthalate, dimethylaminoethyl (meth) acrylate, trifluoroethyl ( (Meth) acrylate and (meth) acryloyl group-containing monofunctional reactive monomers such as trimethylsiloxyethyl methacrylate; monofunctional reactive monomers such as N-vinylpyrrolidone and styrene; diethylene glycol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 2,2′-bis (4- (meth) acryloyl (Meth) acryloyl group-containing bifunctional reactive monomers such as oxypolyethyleneoxyphenyl) propane and 2,2′-bis (4- (meth) acryloyloxypolypropyleneoxyphenyl) propane; trimethylolpropane tri (meth) acrylate (Meth) acryloyl group-containing trifunctional reactive monomers such as trimethylolethane tri (meth) acrylate; (meth) acryloyl group-containing tetrafunctional reactive monomers such as pentaerythritol tetra (meth) acrylate; and dipentaerythritol hexa Examples thereof include one or more resins selected from (meth) acryloyl group-containing hexafunctional reactive monomers such as acrylate, or resins having one or more of the above as constituent monomers.

In the present specification, (meth) acrylate means acrylate or methacrylate.

Examples of the compound having two or more isocyanate groups in one molecule include methylene bis-4-cyclohexyl isocyanate; trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylol of isophorone diisocyanate. Polyisocyanates such as propane adduct, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurate of isophorone diisocyanate, biuret of hexamethylene diisocyanate; and urethanes such as block isocyanates of the above polyisocyanates A crosslinking agent can be used. These can be used alone or in combination of two or more. Further, at the time of crosslinking, a catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be added as necessary.

Examples of the photopolymerization initiator include benzophenone, methyl-o-benzoylbenzoate, 4-methylbenzophenone, 4,4′-bis (diethylamino) benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl. Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; benzoin, benzoin methyl ether, benzoin Benzoin compounds such as ethyl ether, benzoin isopropyl ether and benzyl methyl ketal; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, etc. Acetophenone compounds; anthraquinone compounds such as methylanthraquinone, 2-ethylanthraquinone, 2-amylanthraquinone; thioxanthone compounds such as thioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; alkylphenones such as acetophenone dimethyl ketal Compounds; triazine compounds; biimidazole compounds; acyl phosphine oxide compounds; titanocene compounds; oxime ester compounds; oxime phenylacetate compounds; hydroxy ketone compounds; and aminobenzoate compounds. it can. These can be used alone or in combination of two or more.

In addition, the active energy ray-curable resin composition includes an antistatic agent, a surfactant, a leveling agent, a thixotropic agent, a stain prevention agent, a printability improving agent, an antioxidant, and a weather resistance stabilizer as necessary. In addition, one or more additives such as a light resistance stabilizer, an ultraviolet absorber, a heat stabilizer, a colorant, and a filler may be contained.

Moreover, since the said active energy ray curable resin composition is diluted to the density | concentration which is easy to apply, it may contain the solvent as needed. The solvent is not particularly limited as long as it does not react with the components of the curable resin composition and other optional components or does not catalyze (promote) the self-reaction (including deterioration reaction) of these components. For example, 1-methoxy-2-propanol, ethyl acetate, nbutyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol, acetone and the like can be mentioned.

The active energy ray-curable resin composition can be obtained by mixing and stirring these components.

The method for applying the paint is not particularly limited, and a known web application method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The mold having a fine embossed structure on the surface is not limited as long as the fine emboss having the above shape can be applied to the surface of the transparent hard coat (A), and any mold can be used. Such molds are commercially available, and examples thereof include “Fill Feel (trade name)” by Soken Chemical Co., Ltd. NTT Advanced Technology Co., Ltd., Dai Nippon Printing Co., Ltd., Canon Marketing Japan Co., Ltd., etc. also sell molds.

The said transparent polyester-type resin layer (B) is a layer of transparent polyester-type resin, and consists of a transparent polyester-type resin film normally. The layer (B) preferably has a thickness of 50 μm or more, more preferably 75 μm or more in order to give the decorative sheet a feeling of depth. The thickness is preferably 1000 μm or less so that a known web coating method and apparatus can be applied.

Examples of the transparent polyester-based resin include aromatic polyvalent carboxylic acid components such as terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, ethylene glycol, diethylene glycol, neopentyl glycol, 1,2-butanediol, , 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 1,4-cyclohexanedimethanol, etc. One type or a mixture of two or more types of polyester-based (co) polymers with a polyhydric alcohol component can be used.

In the present specification, the polyester (co) polymer means a polyester polymer or a polyester copolymer. The term “polyester resin” is used as a term that includes not only one or a mixture of two or more polyesters but also a resin composition with components other than polyester.

Among the above, from the viewpoint of transparency, an amorphous or low-crystalline aromatic polyester-based resin is preferable. Specifically, the total amount of monomers is 100 mol%, and terephthalic acid 50 mol% and ethylene glycol 30-40. Glycol-modified polyethylene terephthalate (PETG) comprising 10% to 20% by mole of 1,4-cyclohexanedimethanol; 50% by mole of terephthalic acid, 16 to 21% by mole of ethylene glycol, and 29 to 34% of 1,4-cyclohexanedimethanol Glycol-modified polycyclohexylene dimethylene terephthalate (PCTG) comprising 25% acid-modified poly consisting of 25 to 44.5 mol% terephthalic acid, 0.5 to 25 mol% isophthalic acid and 50 mol% 1,4-cyclohexanedimethanol Cyclohexylene dimethylene terephthalate (PCTA); from 30 to 45 mol% terephthalic acid, 5 to 20 mol% isophthalic acid and 35 to 48 mol% ethylene glycol, 2 to 15 mol% neopentyl glycol, less than 1 mol% diethylene glycol, and less than 1 mol% bisphenol A And acid-modified and glycol-modified polyethylene terephthalate.

In this specification, using a Diamond DSC type differential scanning calorimeter of Perkin Elmer Japan Co., Ltd., holding the sample at 320 ° C. for 5 minutes, then cooling to −50 ° C. at a temperature decreasing rate of 20 ° C./min, A polyester having a heat of fusion of 10 J / g or less in the melting curve obtained by performing DSC measurement with a temperature program of holding at 50 ° C. for 5 minutes and then heating to 320 ° C. at a temperature increase rate of 20 ° C./min. A polyester having a property of more than 10 J / g and not more than 60 J / g was defined as low crystallinity.

The transparent polyester resin can contain components other than the transparent polyester resin as necessary. Optional components that can be included include thermoplastic resins other than transparent polyester resins; pigments, inorganic fillers, organic fillers, resin fillers; lubricants, antioxidants, weathering stabilizers, thermal stabilizers, mold release agents, antistatic agents And additives such as surfactants; and the like. The compounding amount of these optional components is usually about 0.1 to 10 parts by mass when the polyester resin is 100 parts by mass.

As a preferred optional component, core-shell rubber can be used, and by using this, it is possible to improve the bonding processability of the decorative sheet to the article, particularly to the article having a three-dimensional decorative surface. Can do. Examples of the core-shell rubber include methacrylate ester / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / butadiene rubber graft copolymer, acrylonitrile / styrene / ethylene / propylene rubber graft copolymer, and acrylonitrile / styrene / acrylic acid. Mention of one or a mixture of two or more core-shell rubbers such as ester graft copolymers, methacrylate ester / acrylate rubber graft copolymers, methacrylate ester / acrylonitrile / acrylate rubber graft copolymers Can do.

The amount of the core-shell rubber is preferably 0.5 parts by mass or more and maintains transparency when the transparent polyester-based resin is 100 parts by mass in order to improve the bonding processability of the decorative sheet to the article. Therefore, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

The transparent polyester-based resin film can be obtained by forming the transparent polyester-based resin into a film using, for example, a calendar processing machine; or using an extruder and a T-die. Any calendar processing machine can be used, for example, an upright type 3 roll, an upright type 4 roll, an L type 4 roll, an inverted L type 4 roll, and a Z type roll. it can. Any extruder can be used, and examples thereof include a single-screw extruder, a same-direction rotating twin-screw extruder, and a different-direction rotating twin-screw extruder. Any T-die can be used, and examples thereof include a manifold die, a fishtail die, and a coat hanger die. Moreover, you may further uniaxially stretch or biaxially stretch the obtained polyester-type resin film.

Furthermore, before forming a hard coat (A) on the hard coat lamination surface of the said transparent polyester-type resin film, a transparent anchor coat (D) can be formed previously. By forming the transparent anchor coat (D), the interlayer strength between the transparent hard coat (A) and the transparent polyester resin layer (B) can be improved.

As the anchor coating agent, known ones such as polyester, acrylic, polyurethane, acrylic urethane, and polyester urethane can be used.

The method for applying the anchor coating agent to the hard coat laminated surface of the transparent polyester resin film is not particularly limited, and a known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used.

The thickness of the transparent anchor coat (D) is usually about 0.1 to 5 μm, preferably 0.5 to 2 μm.

When the transparent hard coat (A) and the transparent polyester resin layer (B) are directly laminated, the decorative sheet of the present invention has a 60 ° gloss (Ga) on the fine embossed surface of the transparent hard coat (A). ) And 60 ° gloss (Gb) on the hard coat laminated surface of the transparent polyester resin layer (B) satisfy the following formula (α).
Gb-Ga ≧ 35 (α)
Preferably, the following formula (α2) is satisfied.
Gb-Ga ≧ 40 (α2)

Here, Ga is a value obtained by measuring the fine embossed surface of the transparent hard coat (A) according to JIS-K7105-1981. Gb is a value obtained by measuring the hard coat laminate surface of the transparent polyester resin film according to JIS-K7105-1981.

In addition, the decorative sheet of the present invention has a transparent hard coat (A) in the case where the transparent hard coat (A) and the transparent polyester resin layer (B) are laminated via the transparent anchor coat (D). The 60 ° gloss (Ga) on the fine embossed surface and the 60 ° gloss (Gd) on the hard coat lamination surface of the transparent anchor coat (D) satisfy the following formula (β).
Gd-Ga ≧ 35 (β)
The format (β2) is preferably satisfied.
Gd-Ga ≧ 40 (β2)

Here, Ga is a value obtained in the same manner as described above. Gd is a value obtained by measuring the anchor coat side surface of the laminate of the transparent polyester resin film and the anchor coat (D) according to JIS-K7105-1981.

Gb and Gd are common or correspond to each other in that the hard coat lamination surface of the layer directly laminated on the back side of the transparent hard coat (A) is 60 ° gloss. It is surprising that not only Ga but also Gb and Gd are related to the sharpness of the decorative sheet, and the mechanism is unknown, but the human eye simply looks at the surface reflection of light. There may be hypotheses such as feeling sharpness by looking at reflections of light that has entered deeply.

On the other hand, in the embodiment in which the transparent polyester resin layer (B) and the decoration layer (C) are laminated via the transparent adhesive (E), the surface of the transparent polyester resin layer (B) on the decoration layer (C) side Even if the 60 ° gloss is low, for example, it has a matte tone, the sharpness is not affected. Although this is also surprising, it is thought that the transparent adhesive (E) completely fills the surface irregularities.

The method of laminating the transparent hard coat (A) and the transparent polyester-based resin layer (B) directly or via the transparent anchor coat (D) is not limited, and can be laminated by any method. For example, a method in which a hard coat forming paint is directly applied to a transparent polyester resin film or a transparent polyester resin film previously provided with an anchor coat; and a hard coat formed by pouring a hard coat forming paint into a mold to form a transparent polyester resin It can be obtained by a method of transferring to a film or a transparent polyester resin film provided with an anchor coat beforehand.

The decorative layer (C) imparts design properties to the decorative sheet, and can be formed, for example, by printing an arbitrary pattern using an arbitrary ink and an arbitrary printing machine. For printing, a thermoplastic resin layer (F) may be further provided under the decorative layer (C), and may be applied on the (F). What is the hard coat laminated surface of the transparent polyester resin layer (B)? It may be applied to the opposite side.

Examples of patterns include wood grain patterns, stone patterns simulating the surface of rocks such as marble, fabric patterns simulating cloth or cloth patterns, tiled patterns, brickwork patterns, parquet patterns, patchwork, etc. it can.

As printing ink, what mixed the pigment, the solvent, the stabilizer, the plasticizer, the catalyst, the hardening | curing agent, etc. in the binder suitably can be used. Examples of the binder include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamides. Resins such as resin, butyral resin, polystyrene resin, nitrocellulose resin, and cellulose acetate resin, and these resin compositions can be used.

As another embodiment of the decoration layer (C), an embodiment in which the film of the colored resin composition is used as both the thermoplastic resin layer (F) and the decoration layer (C) can be mentioned.

Examples of the film that can be used for the thermoplastic resin layer (F) include polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1, chlorinated polyethylene, ethylene / α-olefin copolymer, and ethylene / vinyl acetate. Polyolefin resins such as copolymers and ethylene / acrylic acid ester copolymers; Polyvinyl chloride resins such as polyvinyl chloride and vinyl chloride / vinyl acetate copolymers; Non-crystalline, low crystalline or crystalline polyesters Acrylonitrile / butadiene / styrene copolymer (ABS resin); hydrogenated styrene elastomer such as hydrogenated styrene / conjugated diene copolymer; polyamide resin such as nylon 6, nylon 66, nylon 12; polycarbonate Resin; polyurethane resin; acrylic resin; Film of one or a mixture of two or more can be mentioned. The thermoplastic resin used as the raw material of the film includes pigments, inorganic fillers, organic fillers, resin fillers; plasticizers; lubricants, antioxidants, weathering stabilizers, thermal stabilizers, mold release agents, antistatic agents, interfaces. Additives such as activators and processing aids; and the like can be included. These films include unstretched films, uniaxially stretched films, and biaxially stretched films.

The thickness of the film that can be used for the thermoplastic resin layer (F) is not particularly limited, but is preferably 10 to 1000 μm so that known web coating methods and apparatuses can be applied.

When the decorative layer (C) is provided by printing on the thermoplastic resin layer (F); or when the colored resin composition film is used as both the thermoplastic resin layer (F) and the decorative layer (C), it is transparent. Lamination with the polyester resin layer (B) is usually performed via a transparent adhesive (E).

The transparent adhesive (E) is not particularly limited as long as it is transparent and can provide sufficient adhesive strength. For example, acrylic, ethylene vinyl acetate, vinyl acetate, polyester, polyurethane Conventional adhesives such as epoxy, epoxy resin, chloroprene rubber, and styrene butadiene rubber can be used.

The method in particular of providing the layer of transparent adhesive (E) is not restrict | limited, A well-known web coating method can be used. Specifically, methods such as roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, and die coating can be used. At this time, an arbitrary dilution solvent such as 1-methoxy-2-propanol, n-butyl acetate, toluene, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, and acetone can be used as necessary.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.

Measuring method
(I) Sharpness The decorative sheet (H) obtained in the same manner as in Example 1 except that the following (F-1) and a transparent hard coat were not formed as a reference sample. The appearance of the decoration on the decorative sheet (sharpness) was visually evaluated according to the following criteria.
A: Sharpness substantially equal to or greater than (F-1).
○: Sharpness is higher than that of the decorative sheet (H), but inferior to (F-1).
(Triangle | delta): It is the sharpness substantially equivalent to the sharpness of a decorating sheet (H).
X: The sharpness is inferior to the decorative sheet (H).

Raw materials and materials used
Paint for forming transparent hard coat (A) (A-1) Acrylic ultraviolet curable resin paint “PAK-02 (trade name)” manufactured by Toyo Gosei Co., Ltd.

Film (B-1) used as transparent polyester-based resin layer (B) Biaxially stretched polyethylene terephthalate film “Cosmo Shine A4100 (trade name)” with a thickness of 100 μm, hard coat laminated, with anchor coat laminated on one side of Toyobo Co., Ltd. 60% gloss 105% of the surface (anchor coat side surface). The 60 ° gloss on the surface on the decorative layer (C) side is 120%.
(B-2) Biaxially stretched polyethylene terephthalate film “Cosmo Shine A4100 (trade name)” with an anchor coat laminated on one side of Toyobo Co., Ltd., having a thickness of 188 μm. 60% gloss 105% of hard coat laminate surface (anchor coat side surface). The 60 ° gloss on the surface on the decorative layer (C) side is 130%.

(B-3) Amorphous aromatic polyester “Sinopec FG702 (trade name)” of China Petrochemical Industry Chemical Fiber Co., Ltd. (monomer composition is 39.0 mol% terephthalic acid, 10.2 mol% isophthalic acid, ethylene glycol 42) .6 mol%, neopentyl glycol 7.1 mol%, diethylene glycol 0.6 mol% and bisphenol A 0.5 mol% No melting peak due to complete amorphousness (heat of fusion 0 J / g) Density 1330 Kg / m ³ ) And 100 parts by weight; Kaneka's methacrylic acid ester / acrylonitrile / butyl acrylate graft copolymer core-shell rubber “Kane Ace FM-40 (trade name)” with 1 part by weight of a polyester resin composition, T Equipped with a die and a nip-type take-up device for mirror metal roll and rubber roll Using the extrusion film forming apparatus, in terms of T-die outlet resin temperature 240 ° C., to obtain a transparent resin film having a thickness of 100 [mu] m. The 60 ° gloss of the hard coat laminated surface (no anchor coat used) was 91%. The surface on the decorative layer (C) side is matte (60 ° gloss is 12%).

(B-4) A transparent resin film was obtained in the same manner as in (B-3) except that the thickness was changed to 200 μm. The 60 ° gloss of the hard coat laminated surface (an anchor coat was not used) was 92%. The surface on the decorative layer (C) side is matte tone (14 ° for 60 ° gloss).

(B-5) A transparent resin film was obtained in the same manner as in (B-3) except that the T-die outlet resin temperature was changed to 200 ° C. The 60 ° gloss of the hard coat laminate surface (an anchor coat was not used) was 84%. The surface on the decorative layer (C) side is matte (60 ° gloss is 15%).

(B-6) A transparent resin film was obtained in the same manner as in (B-3) except that the T-die outlet resin temperature was changed to 200 ° C. and the thickness was changed to 200 μm. The 60 ° gloss of the hard coat laminate surface (an anchor coat was not used) was 84%. The surface on the decorative layer (C) side is matte (60 ° gloss is 16%).

(B-7) A gravure coating device is applied so that the anchor coating agent “Byron 24SS (trade name)” of Toyobo Co., Ltd. has a dry film thickness of 1 μm on the hard coat side of (B-5) above. Applied. The 60 ° gloss on the surface of the anchor coat (hard coat laminate surface) was 101%.

(B-8) A gravure type coating device is applied so that the anchor coating agent “Byron 24SS (trade name)” of Toyobo Co., Ltd. has a dry film thickness of 1 μm on the hard coating side of (B-6) above. Applied. The 60 ° gloss on the surface of the anchor coat (hard coat laminate surface) was 99%.

Transparent adhesive (E)
(E-1) 100 parts by mass of an ester resin solution-based adhesive “Seika Bond E-295 (trade name)” of Dainichi Seika Kogyo Co., Ltd., 10 parts by weight of Seika Bond C-75N (trade name) of the company, and a diluent solvent It was obtained by mixing and stirring 100 parts by mass of methyl ethyl ketone.

Thermoplastic resin film (F) provided with a decorative layer (C)
(F-1) Polyvinyl chloride resin film “S2338 FC92255 printing model number 1463 (Toyosina (printing model number) of Nippon Decor Co., Ltd.)” printed on one side of Riken Technos Co., Ltd., with a thickness of 80 μm.

Mold (M-1) A film mold “Fillfeel ARP250 (trade name)” by Soken Chemical Co., Ltd., a moth-eye pattern with a period of 250 nm and a height of 170 nm.
(M-2) Film mold “Fillfeel ARP350 (trade name)” by Soken Chemical Co., Ltd., moth eye pattern with a period of 350 nm and a height of 250 nm.
(M-3) A film mold “Fillfeel RIP140 (trade name)” by Soken Chemical Co., Ltd., a pillar pattern having a period of 250 nm, a height of 200 nm, and a convex diameter of 145 nm.
(M-4) A film mold “Fillfeel RIP1700 (trade name)” by Soken Chemical Co., Ltd., a pillar pattern with a period of 3000 nm, a height of 1700 nm, and a convex diameter of 1700 nm.

Example 1
The paint (A-1) is applied to the hard coat laminated surface of the transparent polyester resin film (B-1) using a Baker type applicator manufactured by Yasuda Seiki Co., Ltd. ) At a pressure of 0.25 MPa and a time of 20 seconds, and then using a 365 nm UV-LED light source irradiation device from the mold side, paint (A-1) under the conditions of 2.52 mmJ / cm ² and a time of 15 minutes. Was cured. Subsequently, the adhesive (E-1) was applied to the (B-1) side surface of the laminate obtained above using a baker type applicator manufactured by Yasuda Seiki Co., Ltd., and after preliminary drying Using a dielectric heating type laminator JD-DW manufactured by Tokuden Co., Ltd., it was bonded to the decorative surface of (F-1) under the conditions of a pressure of 0.3 MPa and a temperature of 120 ° C. Furthermore, the adhesive (E-1) was completely cured under conditions of a temperature of 120 ° C. and 24 hours to obtain a decorative sheet. The results are shown in Table 1.

Examples 2-12, Comparative Examples 1-4
The same procedure as in Example 1 was conducted except that the mold or / and the transparent polyester resin film used were changed to those shown in Table 1 or 2. The results are shown in Table 1 or Table 2.

The decorative sheet of the present invention expresses good sharpness. On the other hand, Comparative Examples 1 and 3 have Examples 1, 2, 10, and 11 and Comparative Example 2 has fine embossing of the same shape as Examples 3, 8, 9, and 12 applied to the transparent hard coat. Nevertheless, since the configuration does not satisfy the formula (α), the sharpness is inferior. Further, Comparative Example 4 is inferior in sharpness because the shape of the fine emboss applied to the transparent hard coat is inappropriate.

It is a scanning electron micrograph of the fine embossing given to the transparent hard coat (A) surface of the decorating sheet of Example 1.

Claims (3)

A decorative sheet having a transparent hard coat (A), a transparent polyester resin layer (B), and a decorative layer (C) in order from the surface side,
(1) The transparent hard coat (A) and the transparent polyester resin layer (B) are directly laminated;
(2) The transparent polyester resin layer (B) and the decorative layer (C) are laminated directly or via a transparent adhesive (E);
(3) The transparent hard coat (A) is the outermost layer;
(4) The surface of the transparent hard coat (A) is finely embossed;
(5) The shape of the fine embossing has a plurality of convex portions, an average interval between the convex portions is 100 to 500 nm, and an average height of the convex portions is 80 to 500 nm;
(6) 60 ° gloss (Ga) of the fine embossed surface of the transparent hard coat (A) and 60 ° gloss (Gb) of the hard coat laminated surface of the transparent polyester resin layer (B) satisfy the following formula (α). about;
Decorative sheet characterized by.
Gb-Ga ≧ 35 (α)
A decorative sheet having a transparent hard coat (A), a transparent polyester resin layer (B), and a decorative layer (C) in order from the surface side,
(1) The transparent hard coat (A) and the transparent polyester resin layer (B) are laminated via the transparent anchor coat (D);
(2) The transparent polyester resin layer (B) and the decorative layer (C) are laminated directly or via a transparent adhesive (E);
(3) The transparent hard coat (A) is the outermost layer;
(4) The surface of the transparent hard coat (A) is finely embossed;
(5) The shape of the fine embossing has a plurality of convex portions, an average interval between the convex portions is 100 to 500 nm, and an average height of the convex portions is 80 to 500 nm;
(6) The 60 ° gloss (Ga) of the fine embossed surface of the transparent hard coat (A) and the 60 ° gloss (Gd) of the hard coat laminated surface of the transparent anchor coat (D) satisfy the following formula (β);
Decorative sheet characterized by.
Gd-Ga ≧ 35 (β)
The decorative sheet according to claim 1 or 2, wherein the shape of the fine embossing is at least one selected from the group consisting of a moth-eye pattern and a pillar pattern.