JP4983515B2 - Decorative sheet, method for producing decorative sheet, decorative material - Google Patents

Description

  The present invention relates to a decorative sheet, a method for manufacturing the decorative sheet, and improvement of a decorative material using the decorative sheet.

  Conventionally, for use in surface makeup such as interior materials such as walls and floors in buildings such as houses, joinery, furniture, home appliances, etc. A decorative material attached to a substrate such as a board, a plywood board or a plastic member is used.

  Such cosmetic materials and cosmetic products using the same are usually used for several years to several decades, and may be damaged or surfaced by collision or friction with the human body or equipment during use. Sufficient scratch resistance and wear resistance are required so that the design properties are not likely to be damaged due to shaving.

  For this reason, in order to improve the scratch resistance and wear resistance, the protective layer is coated on the surface of the decorative sheet by adding an inorganic anti-wear agent such as alumina or silicon carbide in a synthetic resin paint. The forming method is widely used.

  However, the decorative material provided with the protective layer to which the inorganic antiwear agent is added as described above has a problem that the design expression on the surface is limited.

  That is, for example, in a decorative sheet using printing paper or printed film such as a wood grain pattern, the design is two-dimensional by printing, and the three-dimensional design feeling is insufficient. By embossing a conduit pattern or the like, a method of compensating a three-dimensional design feeling and achieving a design feeling comparable to a solid wood is widely performed.

  However, in the case of a decorative sheet provided with a protective layer to which an inorganic antiwear agent is added, in order to sufficiently obtain the effect of scratch resistance and wear resistance due to the blending of the inorganic antiwear agent, the particle size is from 10 μm to 10 μm. In many cases, it is necessary to use an inorganic antifriction agent having a large particle diameter of several tens of μm, and accordingly, the thickness of the protective layer is inevitably about several tens of μm.

  Then, after embossing the base material of the unpainted decorative sheet first, when trying to paint a paint blended with an inorganic anti-wear agent, a highly viscous paint for thick coating has unevenness due to embossing. There are problems that uneven coating occurs without being well adapted to the surface of the base material, or that the embossed concave portions are clogged with an inorganic antiwear agent, thereby reducing the three-dimensional effect of the emboss. In addition, due to the clogged inorganic anti-wear agent, the embossed recesses may be whitened or colored, or the inorganic anti-wear agent clogged in the embossed recesses may cause unevenness during painting. Occurs.

  On the other hand, in order to avoid the above problem, when a protective layer is first formed by applying a paint containing an inorganic antifriction agent on the surface of the base material and then embossing is applied to the surface, the inorganic antiwear agent becomes an obstacle. The embossing does not work well, or the protective layer is cracked due to the interface peeling between the inorganic antifriction agent and the paint resin due to the embossing pressure, or the embossing plate is scratched by the inorganic antiwear agent. There are problems such as being unable to continue.

  Further, as another problem of the decorative sheet provided with a protective layer to which an inorganic antiwear agent is added, the inorganic antiwear agent protrudes from the average surface of the protective layer because the inorganic antiwear agent having a large particle diameter as described above is used. The surface of the decorative sheet is likely to be damaged by the separation of the protruding inorganic anti-wear agent from the abrasion-resistant resin layer by external force and the surface of the decorative sheet is rubbed. There is a problem that the agent may scrape the article in contact with the surface of the decorative material.

  Further, in terms of manufacturing, there is a problem that productivity is low such that a heat curing process after printing is necessary and a processing time is long, and a lot of energy is required, so that a great production cost is required.

  Therefore, in order to solve the above problems, Patent Document 1, Patent Document 2 and Patent Document 3 disclose a decorative sheet 11 having a structure as shown in FIG. 3, for example. In the decorative sheet 11, a printing layer 13 composed of a uniform colored layer 13a and a pattern ink 13b is formed on a base material 12, and an emulsifying process is performed on the printing layer 13 in place of embossing. One protective layer 14 is formed by full surface printing, and a second protective layer 15 is formed on the first protective layer 14 by pattern printing.

  In the disclosed decorative sheet 11, since the first protective layer 14 contains an inorganic antiwear agent, it has excellent scratch resistance and wear resistance. In addition, since the second protective layer 15 is pattern-printed on the first protective layer 14, the decorative sheet 11 is provided with a three-dimensional effect to improve the design, and an article that comes into contact with the inorganic antiwear agent. Injury can be prevented.

Further, Patent Document 1, Patent Document 2 and Patent Document 3 disclose using an electron beam curable resin for the first protective layer 14 and the second protective layer 15. When an electron beam curable resin is used, the protective layer can be cured at room temperature and in a short time by electron beam irradiation, so that productivity is greatly improved.
JP 2001-138469 A JP 2001-315286 A JP 2006-281931 A

  However, when the second protective layer is pattern-printed on the first protective layer, recoat (repainting) property becomes a problem. That is, in order for the second protective layer to be disposed on the first protective layer, it is necessary to ensure adhesion with the first protective layer. There was a problem that the protective layer 2 was peeled off. For this reason, the material selection of the 2nd protective layer was restricted.

  The present invention has been made to solve the above-described problems, and provides a decorative sheet capable of expressing a three-dimensional design without peeling off a pattern, a manufacturing method thereof, and a decorative material to which these are applied. With the goal.

In order to achieve the above object, the present invention employs the following configuration.
The decorative sheet of the present invention includes a base material, a printing layer comprising a base printing layer and a patterned printing layer sequentially laminated on the base material, and a first protection patterned so as to cover the patterned printing layer. And a second protective layer formed on the base print layer exposed from the non-formation region of the first protective layer, and the film surface height of the second protective layer from the base print layer is the first. The protective layer is characterized in that it is higher than the film surface height from the base printed layer.

In the decorative sheet of the present invention, one or both of the first protective layer and the second protective layer is preferably made of an ionizing radiation curable resin, the first protective layer contains an inorganic antiwear agent, The protective layer 2 preferably contains no inorganic antiwear agent.
Furthermore, in the decorative sheet of the present invention, the base material is preferably paper, and the pattern of the printed layer is preferably woodgrain.

The decorative sheet manufacturing method of the present invention includes a step of sequentially forming a base printing layer and a patterned printing layer on a substrate to form a printing layer, and a first protective layer so as to cover the patterned printing layer. Forming a second protective layer higher than the film surface height of the first protective layer from the base print layer on the base print layer exposed from the non-formation region of the first protective layer; and And a step of simultaneously curing the first protective layer and the second protective layer with radiation.
In addition, the decorative material of the present invention is characterized in that the decorative sheet described above is adhered to a substrate.

  As described above, the decorative sheet of the present invention has the second protective layer formed on the base printed layer exposed from the non-formation region of the first protective layer. Even when a material having poor recoatability (repaintability) is used for the protective layer, the second protective layer does not peel from the decorative sheet. In addition, the decorative sheet of the present invention is formed such that the film surface height of the second protective layer from the base print layer is higher than the film surface height of the first protective layer from the base print layer. Stereological properties can be imparted by the two protective layers. Therefore, it is possible to provide a decorative sheet capable of expressing a three-dimensional design without peeling off the pattern.

The decorative sheet of the present invention can cure the protective layer at room temperature and in a short time when one or both of the first protective layer and the second protective layer are made of an ionizing radiation curable resin. Therefore, productivity can be improved.
Furthermore, in the decorative sheet of the present invention, when the first protective layer contains an inorganic antiwear agent and the second protective layer does not contain an inorganic antiwear agent, the patterned printed layer becomes the first protective layer. Since it is coated, it can have excellent scratch resistance and abrasion resistance. On the other hand, since the second protective layer containing no inorganic antiwear agent has a higher film surface height from the base print layer than the first protective layer, it is possible to prevent the surface of the contacting article from being scraped. Furthermore, high designability can be expressed by setting the first protective layer containing an inorganic antiwear agent to a matte state and setting the second protective layer not containing an inorganic antiwear agent to a glossy state.

  In the method for producing a decorative sheet according to the present invention, the first protective layer and the second protective layer are simultaneously cured by radiation, so that the protective layer can be cured at room temperature in a short time. For this reason, productivity can be improved.

  Since the decorative material of the present invention uses the above-described decorative sheet, it has excellent scratch resistance and abrasion resistance by using an inorganic anti-wear agent, and can express a three-dimensional design, and the surface of an article to be contacted can be obtained. It is possible to provide a large amount of cosmetic materials that are not shaved at low cost.

Hereinafter, a decorative sheet to which the present invention is applied will be described in detail with reference to the drawings.
As an embodiment of the present invention, the configuration of the decorative sheet 1 shown in FIG. 1 will be described. In addition, the following figures are for demonstrating the structure of the decorative sheet of this embodiment, and the magnitude | size of each part shown, thickness, a dimension, etc. may differ from the dimensional relationship of an actual decorative sheet.

  As shown in FIG. 1, the decorative sheet 1 of the present embodiment includes a base material 2, a colored layer (underprint layer) 3 a formed on the base material 2, and a conduit ink layer (patterned print layer) 3 b. The printed layer 3, the first protective layer 4 formed so as to cover the conduit ink layer 3b, and the second layer formed on the colored layer 3a exposed from the non-formation region W of the first protective layer 4. The protective layer 5 is schematically configured.

<Base material>
The base material 2 is not particularly limited, and can be arbitrarily selected from those generally used widely as a base material for conventional decorative sheets. In the present embodiment, the substrate 2 is preferably paper.

  Specifically, for example, thin paper, titanium paper, resin-impregnated paper, inter-paper reinforced paper, resin-coated paper, resin-laminated paper, transparent paper, bleached or unbleached kraft paper, fine paper, paperboard, flame retardant paper, inorganic paper, etc. Paper, woven fabrics or nonwoven fabrics made of natural fibers or synthetic fibers can be used.

  Also, for example, it is made of thermoplastic resin such as polyolefin resin, polyester resin, acrylic resin, styrene resin, ABS resin, polyamide resin, polyvinyl chloride resin, polyvinylidene chloride resin, fluorine resin, and fiber derivative. A film or the like can also be used.

  In addition, the above-described various thermoplastic resins, for example, plate-like bodies or molded articles made of thermosetting resins such as unsaturated polyester resins, polyurethane resins, melamine resins, urea resins, alkyd resins, etc. It can also be used.

  Also, for example, wood base materials such as wood veneer, veneer, plywood, laminated wood, particle board, medium density fiber board, and inorganic base materials such as gypsum board, cement board, calcium silicate board, glass board, ceramic board, etc. Metal base materials such as materials, iron, copper, brass, aluminum, and stainless steel may be used.

  Moreover, the base material which mixed, combined or laminated | stacked the some material chosen from the various materials enumerated above may be sufficient.

<Print layer>
The print layer 3 is formed on the substrate 2 and is composed of a base print layer and a patterned print layer. The base printing layer is, for example, a uniform colored layer 3a, and the patterned printing layer is composed of, for example, a conduit ink layer 3b. Thereby, for example, the printing layer 3 has a wood grain pattern.
Although the material of the ink used for the colored layer 3a and the conduit ink layer 3b constituting the printing layer 3 is not particularly limited, the adhesiveness with the base material 2 is good, and the required picture can be configured. It is preferable that In addition, it is preferable that the decorative sheet 1 of this embodiment has the pattern of the printing layer 3 as a wood grain.
When the substrate 2 is paper, acrylic nitrified cotton-based ink is preferable. Moreover, when the base material 2 is an olefin resin, urethane type ink is preferable. When the substrate 2 is a vinyl chloride resin, a vinyl chloride / vinyl acetate copolymer ink is preferable.

  The acrylic nitrified cotton-based ink is a mixture of an acrylic resin and nitrified cotton, and both can be mixed and used at an arbitrary ratio. Acrylic resins include poly (meth) butyl acrylate, poly (meth) ethyl acrylate, poly (meth) propyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate and butyl (meth) acrylate. Copolymer, (Meth) acrylic such as ethyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, styrene / methyl (meth) acrylate copolymer Examples thereof include acrylic resins composed of a single or copolymer containing an acid ester (wherein (meth) acryl means acryl or methacryl, and the same shall apply hereinafter). It is preferable that at least one selected from these acrylic resins and nitrified cotton are mixed and used as ink for the printing layer 3.

<Protective layer>
The protective layer is composed of a first protective layer 4 and a second protective layer 5. The first protective layer 4 is formed so as to cover the patterned printing layer (conduit ink layer) 3b. The second protective layer 5 is formed on the base print layer (colored layer) 3 a exposed from the non-formation region W of the first protective layer 4. The second protective layer 5 may be formed so as to provide an overlap portion so as to slightly overlap the film surface of the first protective layer 4. Thereby, the airtightness of the interface of the 2nd protective layer 5 and the 1st protective layer 4 becomes high, and the colored layer 3a can be protected effectively.

  The film surface height of the second protective layer 5 from the colored layer 3a is higher than the film surface height of the first protective layer 4 from the colored layer 3a. Further, the film surface of the second protective layer 5 is not limited to a smooth surface, and the lowest film surface height from the colored layer 3 a of the second protective layer 5 is the color of the first protective layer 4. In the case where it is formed higher than the highest film surface height from the layer 3a, it may be a surface in which the central portion is recessed.

  These first protective layer 4 and second protective layer 5 have a composition curable with ionizing radiation, in which prepolymers, oligomers and monomers having a polymerizable unsaturated bond or epoxy group are appropriately mixed in the molecule. An object (ionizing radiation curable resin) can be used. In the present embodiment, it is preferable to use an electron beam curable resin as the ionizing radiation curable resin. The electron beam curable resin is a resin that is cured with high hardness by irradiation with an electron beam.

  As the above-mentioned prepolymers and oligomers, unsaturated polyesters such as unsaturated dicarboxylic acid and polyhydric alcohol condensates, polyester methacrylates, polyether methacrylates, polyol methacrylates, methacrylates such as melamine methacrylates, polyester acrylates, epoxy acrylates, Examples thereof include acrylates such as urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds.

Examples of the urethane acrylate include polyether-based urethane (meth) acrylates represented by the following general formula obtained by reacting polyether diol and diisocyanate.
_{CH 2 = C (R1) -COOCH} 2 CH 2 -OCONH-X-NHCOO - _{[- CH (R2) - (CH} 2) n -O- ] _{m -CONH-X-NHCOO-CH} 2 CH 2 OCOC (R1 ) = CH2
(In the formula, R1 and R2 are each hydrogen or a methyl group, X is a diisocyanate residue, n is an integer of 1 to 3, and m is an integer of 6 to 60.)

Examples of the diisocyanate used in the polyether-based urethane (meth) acrylate include isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and tolylene diisocyanate.
Examples of the polyether diol include polyoxypropylene glycol, polyoxyethylene glycol, and polyoxytetramethylene glycol.

As monomers used for electron beam curable resins, styrene monomers such as styrene and α-methylstyrene,
Acrylic esters such as methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, phenyl acrylate,
Methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate,
Acrylic acid-2- (N, N-diethylamino) ethyl, methacrylic acid-2- (N, N-dimethylamino) ethyl, acrylic acid-2- (N, N-dibenzylamino) methyl, acrylic acid-2- Substituted amino alcohol esters of unsaturated substituted acids such as (N, N-diethylamino) propyl;
Unsaturated carboxylic acid amides such as acrylamide and methacrylamide;
Compounds such as ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6 hexanediol diacrylate, triethylene glycol diacrylate,
Polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate,
Examples include polythiol compounds having two or more thiol groups in the branch, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, pentaerythritol tetrathioglycol and the like.

  Spherical particles may be mixed and dispersed in the first protective layer 4 for the purpose of adding scratch resistance. The material of the spherical particles may be higher than that of the cross-linking curable resin, and both inorganic particles and organic resin particles can be used, but inorganic particles are recommended in terms of wear resistance and hardness. In addition, the surface of the 1st protective layer 4 can be made into a matte state by including an inorganic abrasion-resistant material in the 1st protective layer 4. On the other hand, the second protective layer 5 does not contain an inorganic abrasion resistant material, and can be in a glossy state as compared with the surface of the first protective layer 4 in a matte state.

Specific examples of the material of the spherical particles include inorganic particles such as α-alumina, silica, chromium oxide, iron oxide, diamond, and graphite, and organic resin particles such as synthetic resin beads such as crosslinked acrylic.
The spherical particles preferably have a shape with a smooth surface and no concave portions on the particle surface, such as a spherical shape or a spheroid with a flat sphere. Spherical particles greatly improve the wear resistance of the surface resin layer itself, compared to amorphous particles of the same material, and do not wear the coating device, and other materials that come into contact with the coating film after curing. It is possible to prevent the object from being worn.

  In addition, an electron beam non-curable resin can be added to the first protective layer 4 and the second protective layer 5 as long as the stain resistance is not impaired. As the electron beam non-curable resin, thermoplastic resins such as urethane-based, fiber-based, polyester-based, acrylic-based, butyral-based, polyvinyl chloride, and polyvinyl acetate can be used. The butyral system is preferable from the viewpoint of flexibility.

The coating composition of the first protective layer 4 includes, in addition to the above components, colorants such as dyes and pigments and other CaCO ₂ as long as the transparency and wear resistance as the surface resin layer are not impaired. Additives usually added to paints and inks such as fillers such as known matting modifiers and extenders such as BaSO ₄ , defoaming agents, leveling agents, thixotropic agents, and the like can be added.

  The second protective layer 5 needs to be printed after the formation of the first protective layer 4 and formed so that the film surface height from the colored layer 3 a is higher than that of the first protective layer 4. . Therefore, it is desirable that the second protective layer 5 has a high viscosity so as to be higher than the first protective layer 4. Further, it is desirable that the solid content is as high as possible in order to eliminate volume shrinkage due to evaporation of the solvent in drying before curing. Furthermore, since the second protective layer 5 fills the recesses where the first protective layer 4 is not formed, it is preferable that the ink has fluidity until the electron beam is irradiated. As the ink component of the second protective layer 5, a composition curable by ionizing radiation used for curing the first protective layer 4 can be used.

  In the coating composition of the second protective layer 5, it is possible to dilute the resin component in order to adjust the viscosity, and use a solvent having a boiling point in the range of 70 ° C. to 150 ° C. at normal pressure. it can. In addition, although what is normally used for a coating material, ink, etc. can be applied as said solvent, It is preferable to use water from a viewpoint of environmental response in recent years.

  The second protective layer 5 is formed on the colored layer 3 a exposed from the non-formation region W of the first protective layer 4. Thereby, when selecting the coating composition of the second protective layer 5, a wide range of materials can be selected without taking into account the recoatability (repaintability) with the first protective layer 4.

  Next, the manufacturing method of the decorative sheet 1 described above will be described. The manufacturing method of the decorative sheet 1 according to the present embodiment includes a step of sequentially forming the base printing layer 3a and the patterned printing layer 3b on the base material 2 to form the printing layer 3, and covering the patterned printing layer 3b. The step of forming the first protective layer 4 and the film surface height of the first protective layer 4 from the base print layer 3a on the base print layer 3a exposed from the non-formation region W of the first protective layer 4 It is roughly comprised from the process of forming the 2nd protective layer 5 higher than this, and the process of hardening the 1st protective layer 4 and the 2nd protective layer 5 with a radiation simultaneously. Each step will be described in detail below.

<Print layer formation process>
In the step of forming the printing layer 3, first, for example, a uniform colored layer 3 a is formed as a base printing layer on the substrate 1. Gravure printing can be used as a method for forming the colored layer 3a. Further, letterpress, gravure offset, flexo, offset, and screen printing can be used.
Next, for example, a conduit ink layer 3b is formed as a patterned printing layer on the colored layer 3a. Gravure printing can be used as a method for forming the conduit ink layer 3b. Further, letterpress, gravure offset, flexo, offset, and screen printing can be used. In this way, the printing layer 3 (colored layer 3a and conduit ink layer 3b) is formed.

<Formation process of 1st protective layer>
In the step of forming the first protective layer 4, first, the conduit ink layer 3b is coated with a coating composition containing the above-mentioned electron beam curable resin, spherical alumina, plastic beads, and other additives. Form. In order to express design properties, the first protective layer 4 may be patterned on the colored layer 3a where the conduit ink layer 3b is not formed.

  As the formation of the first protective layer 4, a direct method in which the coating composition is directly applied on the conduit ink layer 3b, or after the first protective layer 4 is formed in advance on the surface of another peelable substrate A transfer method of transferring the layer onto the conduit ink layer 3b can be used. For example, in the case where decorative paper is used as the base material 2 and the material of the decorative paper base paper that does not penetrate the coating composition is used, either the direct method or the transfer method can be used. In order to provide the first protective layer 4 and the second protective layer 5 with a three-dimensional visual appeal function, the direct method is preferably used.

  As the direct method, known methods such as letterpress, gravure offset, flexo, offset, screen printing, gravure offset coating, silk screen, and the like can be used, and gravure printing is more preferable.

  As the above transfer coating method, (a) injection molding simultaneous transfer method as disclosed in JP-B-2-42080, JP-B-4-19924 or the like or disclosed in JP-B-50-19132 Injection molding simultaneous lamination method, (b) Vacuum forming simultaneous transfer method as disclosed in JP-A-4-288214, JP-A-5-57786, or vacuum as disclosed in JP-B-56-45768. Molding simultaneous laminating method, (c) lapping simultaneous transfer method as disclosed in Japanese Patent Publication No. 59-51900, Japanese Patent Publication No. 61-5895, Japanese Patent Publication No. 3-2666, etc. A known method can be used.

  Next, the solvent is removed from the first protective layer 4 by thermal drying. The heat drying method is not particularly limited, and a known method can be applied under known conditions. Moreover, drying conditions can be suitably changed in relation to the solvent used in the coating composition. In this way, the first protective layer 4 is formed.

<Step of forming second protective layer>
In the step of forming the second protective layer 5, first, a coating product is formed on the underlying print layer exposed from the non-formation region W of the first protective layer 4, that is, on the colored layer 3 a. In addition, the formation method of the 2nd protective layer 5 can use the method similar to the above-mentioned 1st protective layer 4. FIG. In this way, the second protective layer 5 is formed.

<Curing process of protective layer>
After the formation of the second protective layer 5, the first protective layer and the second protective layer are simultaneously cured by radiation. The radiation for curing the ionizing radiation curable resin constituting the first protective layer 4 and the second protective layer 5 can be appropriately selected according to the cost of the apparatus and the physical properties required for the product. . For example, an electron beam, an ultraviolet ray, an α ray, a β ray, a γ ray, an X ray, a neutron ray, or the like can be used, but an electron beam or an ultraviolet ray is preferable in view of handling safety and safety. Moreover, if it is hardening by an electron beam, it is preferable to irradiate an electron beam with an acceleration voltage of 30-500 KV, and it is more preferable to irradiate an electron beam with 50-200 KV especially. The irradiation dose is preferably about 5 to 200 KGy, more preferably 10 to 100 KGy.
As described above, the decorative sheet 1 of the present embodiment is manufactured.

<Coating material>
Next, the decorative material 6 which is one embodiment of the present invention will be described with reference to FIG. As shown in FIG. 2, the decorative material 6 of the present embodiment is obtained by sticking a decorative sheet 1 to which the present invention is applied to a substrate 7. In addition, the decorative sheet 1 and the substrate 7 are bonded together by laminating the decorative sheet 1 and the substrate 7 so as to contact the adhesive 8 after the adhesive 8 is applied to the surface of the substrate 7. The adhesive 8 may be applied to the decorative sheet 6 side.

As described above, in the decorative sheet 1 to which the present invention is applied, the second protective layer 5 is formed on the base printed layer (colored layer 3 a) exposed from the non-formation region W of the first protective layer 4. Therefore, even when a material having poor recoatability (repaintability) with respect to the first protective layer 4 is used for the second protective layer 5, the second protective layer 5 does not peel from the decorative sheet 1. . Further, since the product can be designed without taking into account the recoating property with the first protective layer 4, the range of selection of the second protective layer is widened, and an inexpensive material can be used.
Moreover, since the film surface height from the colored layer 3a of the second protective layer 5 is formed higher than the film surface height from the colored layer 3a of the first protective layer 4, the second protective layer 5 is formed. The three-dimensionality can be imparted. Therefore, it is possible to provide the decorative sheet 1 capable of expressing a three-dimensional design without peeling off the pattern.

Moreover, since both the 1st protective layer 4 and the 2nd protective layer 5 are comprised from ionizing radiation curable resin, a protective layer can be hardened in normal temperature and a short time. Thereby, productivity can be improved.
Further, since the first protective layer 4 contains an inorganic antiwear agent, the patterned conduit ink layer 3b is coated on the first protective layer 4, thereby providing excellent scratch resistance and wear resistance. Can be provided. On the other hand, since the second protective layer 5 containing no inorganic antiwear agent has a higher film surface height from the colored layer 3a than the first protective layer 4, the surface of the contacting article can be prevented from being scraped. .
Furthermore, high designability can be expressed by setting the first protective layer 4 containing an inorganic antiwear agent to a matte state and setting the second protective layer 5 not containing an inorganic antiwear agent to a glossy state.

  In the manufacturing method of the decorative sheet 1 of the present embodiment, the first protective layer 4 and the second protective layer 5 are simultaneously cured by radiation, so that the protective layer can be cured at room temperature in a short time. For this reason, productivity can be improved.

  Since the decorative material 1 of the present embodiment uses the decorative sheet 1 described above, it has excellent scratch resistance and abrasion resistance due to the use of an inorganic anti-wear agent, and is capable of expressing a three-dimensional design and is an article in contact with it. It is possible to provide a large amount of a cosmetic material that does not cut the surface of the material at low cost.

Hereinafter, specific examples of the decorative sheet of the present invention will be given to describe the present invention in more detail.
(Example)
Using a six-color gravure printing machine as a base material with a reinforcing paper between building materials having a basis weight of 30 g / m ² , each printing ink and coating agent are sequentially printed or applied in the following order, as shown in FIG. A decorative sheet having the same configuration as the decorative sheet 1 to which the present invention was applied was produced (see FIG. 1).

<Print order>
As a printing order, first, as a first unit, a solid ink layer (underprint layer) is formed with nitrified cotton-based thin paper ink. Next, as a second unit to a fourth unit, a three-color wood grain pattern ink layer is formed with nitrified cotton-based thin paper ink. However, the fourth unit is a conduit pattern (patterned printing layer). Next, as the fifth unit, the first protective layer is formed with a coating amount of 5 (g / m ² dry). Finally, as the sixth unit, the second protective layer is formed with a coating amount of 8 (g / m ² dry).

<Coating agent composition of the first protective layer (fifth unit)>
Main agent (urethane acrylate resin) 100 parts by weight Slip agent (modified silicone type) 2 parts by weight Antiwear agent (spherical alumina, average particle size 30 μm) 10 parts by weight Anti-settling agent (urethane modified ether type) 2 parts by weight Dispersant ( Acrylic polymer) 2 parts by weight

<Coating agent composition of the second protective layer (sixth unit)>
Main agent (acrylic polyol resin) 100 parts by weight Release agent (silicone) 9 parts by weight

  In addition, as the radiation after the sixth unit, irradiation was performed using an electron beam at an acceleration voltage of 130 KV and an irradiation dose of 50 KGy.

(Comparative example)
Using a six-color gravure printing machine as a base material with a reinforcing paper between building materials having a basis weight of 30 g / m ² , each printing ink and coating agent are sequentially printed or applied in the following order, as shown in FIG. A decorative sheet having the same configuration as the conventional decorative sheet 11 was produced (see FIG. 3).

<Print order>
As a printing order, first, as a first unit, a solid ink layer (underprint layer) is formed with nitrified cotton-based thin paper ink. Next, as a second unit to a fourth unit, a three-color wood grain pattern ink layer is formed with nitrified cotton-based thin paper ink. However, the fourth unit is a conduit pattern (patterned printing layer). Next, as the fifth unit, the first protective layer is formed with a coating amount of 5 (g / m ² dry). Finally, as the sixth unit, the second protective layer is formed with a coating amount of 8 (g / m ² dry).

<Coating agent composition of the first protective layer (fifth unit)>
Main agent (acrylic polyol resin) 100 parts by weight Curing agent (hexamethylene diisocyanate) 30 parts by weight

<Coating agent composition of the second protective layer (sixth unit)>
Main agent (acrylic resin) 100 parts by weight Slip agent (silicone type) 1 part by weight Anti-wear agent (spherical alumina, average particle size 30 μm) 20 parts by weight

About these Examples and Comparative Examples, a cross-cut adhesive tape adhesion test, a stain resistance test, and an abrasion test were performed. Here, a cross-cut adhesive tape adhesion test is a test piece in which 11 grids of length and breadth are created at 1 mm intervals to create 100 squares of an area of 1 mm ² and then repeatedly peeled off four times with an adhesive tape. This is a method for evaluating the number of remaining cells after the operation. The stain resistance test is a test piece with a red crayon drawn at a width of 1 cm × 4 cm and left for 4 hours. The remaining half of the test piece is wiped off with methanol or ethanol, and the crayon falls. It is a test to check whether or not. The abrasion test is a method in which a wear wheel having a load of 1 kg is placed on a test piece, and the remaining area of the printed pattern after 200 rotations is evaluated using an abrasion tester (Taber Rotary Abraser 5135 manufactured by TABER). is there.

As a result of the cross-cut adhesive tape adhesion test, 100/100 squares remained in both Examples and Comparative Examples. Further, in all of the stain resistance tests, it was possible to remove the crayon drawing satisfactorily.
On the other hand, the results of the abrasion test showed that no change was observed in the degree of the printed pattern remaining area after the test in either the example or the comparative example, but it was relatively deep to the extent that it did not reach a uniform colored layer. In the worn part, both the polished surface and the matte surface were expressed in the example, whereas in the comparative example, the second protective layer was peeled off and the change in the gloss state was not seen. The difference was confirmed.

FIG. 1 is a schematic cross-sectional view showing a decorative sheet to which the present invention is applied. FIG. 2 is a schematic cross-sectional view showing a decorative material using a decorative sheet to which the present invention is applied. FIG. 3 is a schematic cross-sectional view showing a conventional decorative sheet.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Decorative sheet, 2 ... Base material, 3 ... Print layer, 3a ... Base print layer (colored layer), 3b ... Patterned print layer (conduit ink layer), 4. -1st protective layer, 5 ... 2nd protective layer, 6 ... Cosmetic material, 7 ... Substrate, 8 ... Adhesive, W ... Non-formation area | region of 1st protective layer

Claims (7)

  A substrate, a printing layer comprising a base printing layer and a patterned printing layer sequentially laminated on the substrate, a first protective layer patterned to cover the patterned printing layer, and the first A second protective layer formed on the base print layer exposed from the non-formation region of the first protective layer, and a film surface height of the second protective layer from the base print layer is the first protective layer. A decorative sheet, wherein the protective layer has a film surface height higher than that of the base printed layer.   The decorative sheet according to claim 1, wherein one or both of the first protective layer and the second protective layer is made of an ionizing radiation curable resin.   The decorative sheet according to claim 1 or 2, wherein the first protective layer contains an inorganic antiwear agent, and the second protective layer does not contain an inorganic antiwear agent.   The decorative sheet according to any one of claims 1 to 3, wherein the base material is paper.   The decorative sheet according to any one of claims 1 to 4, wherein the pattern of the printed layer has a wood grain tone. A method for producing a decorative sheet according to any one of claims 1 to 5,
Forming a printed layer by sequentially forming a base printed layer and a patterned printed layer on a substrate; forming a first protective layer so as to cover the patterned printed layer; and Forming a second protective layer higher than the film surface height of the first protective layer from the base print layer on the base print layer exposed from the non-formation region of the protective layer; and And a step of simultaneously curing the protective layer and the second protective layer with radiation.   A decorative material comprising the decorative sheet according to any one of claims 1 to 5 attached to a substrate.

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