JP2017185773A - Decorative sheet and molded article using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet having excellent workability and good mirror surface performance after winding, and to provide a molded article using the same.SOLUTION: There is provided a decorative sheet in which a primer layer and a surface protective layer are laminated in this order on a base material sheet, where ten-point average roughness (R) of a rear face of the decorative sheet measured according to JIS B0601:2001 is 15 μm or less, the base material sheet is formed of a polyolefin resin, the surface protective layer is a cured product of an ionizing radiation-curable resin composition, elongation at which cracks appear measured by a predetermined method is 20-130%, and 20° gloss of a surface of the surface protective layer is 40 or more.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet and a molded article using the decorative sheet.

  A member having a curved surface, such as interior and exterior parts for automobiles, home appliances, etc., is attached with a decorative sheet that gives a beautiful appearance by applying a color, pattern, unevenness, etc. to a plastic sheet as a base material. Polyvinyl chloride (PVC) is mainly used as a raw material for the substrate. However, in recent years, in order to reduce the processing cost related to waste processing, an alternative to a material having a small environmental load has been demanded, and the use of a polyolefin-based resin has been studied. Further, these members are required to have specularity due to the recent trend toward high-end products by consumers, and in particular, those having specularity maintained even after processing are required.

A cosmetic sheet comprising a polyolefin resin sheet as a base material, and having a mirror surface and processability, and comprising a base material sheet made of polypropylene resin and a surface protective layer that is a cured product of an ionizing radiation curable resin composition A sheet has been proposed (for example, Patent Document 1). In Patent Document 1, the thickness of the substrate sheet is 150 to 500 μm, the surface ten-point average roughness (R _zJIS ) is 5 μm or less, the thickness of the surface protective layer is 7 to 17 μm, and cracks It is described that a decorative sheet having specularity and workability can be obtained when the generated elongation is 10 to 20%.

  Moreover, in order to make it hard to produce an abrasion and a wrinkle after winding up a roll, it is proposed to give a roughening process to the back surface of a decorating sheet (decorative sheet) (for example, patent document 2).

International Publication No. 2015/141781 Japanese Patent No. 5625548

  However, the decorative sheet described in Patent Document 1 can be used for 2R bending, but it is difficult to use for a molded product having a more severe curved surface. Further, according to the method described in Patent Document 2, it is difficult to cause dents and scratches on the surface due to the inclusion of foreign matters when winding the roll, and scratches and wrinkles due to the close contact between the front surface and the back surface. Although a decorative sheet is obtained, when the top coat is high gloss and a soft sheet composed of polyolefin resin or the like is used as the base material, the back surface irregularities are picked up and the specularity is lowered.

  Under such circumstances, an object of the present invention is to provide a decorative sheet having excellent processability and good specularity even after winding, and a molded product using the decorative sheet.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the problem can be solved by the following invention. That is, the present invention provides the following decorative sheet and a molded product using the same.

That is, the present invention relates to a decorative sheet and a molded article shown in the following items 1 to 10.
1. A decorative sheet in which a primer layer and a surface protective layer are laminated in this order on a base sheet,
The decorative sheet has a back surface ten-point average roughness (R _zJIS ) measured in accordance with JIS B0601: 2001 of 15 μm or less,
The base sheet is made of a polyolefin resin;
The surface protective layer is a cured product of an ionizing radiation curable resin composition, the crack generation elongation measured by the following method is 20 to 130%, and the 20 ° gloss of the surface of the surface protective layer is 40. That's it,
Makeup sheet.
(Measurement of crack elongation)
A strip-shaped test piece conforming to JIS K7127 is prepared using a decorative sheet, and the test piece is arbitrarily selected in a room temperature environment using a tensile tester at a tensile speed of 200 mm / min and a distance between chucks of 100 mm. After pulling at the elongation, the inside of the chuck is colored with a whiteboard marker, and the colored portion is wiped off with a cloth. .
2. Item 2. The decorative sheet according to Item 1, wherein the surface protective layer has a crack generation elongation of 20 to 80%.
3. Item 3. The decorative sheet according to Item 1 or 2, wherein the surface protective layer has a thickness of 6 to 20 µm. 4). Item 4. The decorative sheet according to any one of Items 1 to 3, wherein the surface protective layer further contains a silicone component.
5. The cosmetic sheet according to any one of Items 1 to 4, wherein the silicone component is 0.5 to 2 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin contained in the ionizing radiation curable resin composition. .
6). The decorative sheet according to any one of Items 1 to 5, wherein a ten-point average roughness (R _zJIS ) of the surface of the primer layer measured in accordance with JIS B0601: 2001 is 5 μm or less.
7). Item 7. The decorative sheet according to any one of Items 1 to 6, further comprising a back primer layer on a surface opposite to the surface having the primer layer of the base sheet.
8). The decorative sheet with a masking film, comprising a masking film on the surface of the decorative sheet according to any one of Items 1 to 7.
9. The decorative sheet with an adhesive layer, comprising an adhesive layer on the back surface of the decorative sheet according to any one of Items 1 to 8.
10. Item 8. A molded article having the decorative sheet according to any one of Items 1 to 7 or the decorative sheet with a masking film according to Item 8 on an adherend.

  ADVANTAGE OF THE INVENTION According to this invention, while having the outstanding workability, the decorative sheet which has a favorable mirror surface property after processing, especially after winding-up, and a molded board using the same can be obtained.

It is a schematic diagram which shows the cross section of one aspect of the decorative sheet of this invention. It is a schematic diagram which shows the cross section of another aspect of the decorative sheet of this invention.

1. The decorative sheet of the present invention is a decorative sheet in which a primer layer and a surface protective layer are laminated in this order on a base sheet, and the back surface of the decorative sheet measured in accordance with JIS B0601: 2001. The ten-point average roughness ( _RzJIS ) is 15 μm or less, the base sheet is made of a polyolefin resin, the surface protective layer is a cured product of an ionizing radiation curable resin composition, and a predetermined method The crack generation elongation measured in (1) is 20 to 130%, and the 20 ° gloss on the surface of the surface protective layer is 40 or more. The decorative sheet of the present invention having the above-described configuration has a crack generation elongation of the surface protective layer of 20 to 130%, and the ten-point average roughness (R _zJIS ) of the back surface of the decorative sheet is 15 μm or less. In addition to excellent properties, the 20 ° gloss is 40 or more and excellent in specularity. In particular, since unevenness on the back surface of the decorative sheet can be prevented from being formed on the surface protective layer during winding, good mirror surface properties can be maintained even after winding.

  The decorative sheet of the present invention will be described with reference to FIGS. In the decorative sheet of the present invention, the surface is a so-called “front surface”, and when the decorative sheet of the present invention is used by being laminated on an adherend or the like, a surface in contact with the adherend Is a surface on the opposite side and is a surface visually recognized after lamination. In the present specification, the direction of the surface of the decorative sheet of the present invention may be referred to as “front” or “up”, and the opposite side may be referred to as “back” or “down”.

  The layer configuration of the decorative sheet of the present invention is not particularly limited as long as it has at least a primer layer and a surface protective layer in this order on the base sheet. 1 and 2 are schematic views showing a cross section of one embodiment of the decorative sheet of the present invention. A decorative sheet 10 shown in FIG. 1 has a base sheet 1, a primer layer 2, and a surface protective layer 3 in this order. Moreover, the decorative sheet shown in FIG. 2 has the base material sheet 1, the primer layer 2, the surface protective layer 3, and the masking film 5 in this order, and the side having the primer layer and the surface protective layer of the base material sheet. The back side primer layer 4 is provided on the opposite side (hereinafter sometimes simply referred to as the back side).

  Hereinafter, the decorative sheet of the present invention will be described, and each layer will be specifically described with the decorative sheet having such a layer configuration as a representative example.

The ten-point average roughness (R _zJIS ) of the back surface measured according to JIS B0601: 2001 of the decorative sheet is 15 μm or less. The ten-point average roughness (R _zJIS ) of the back surface of the decorative sheet is 15 μm or less, that is, by smoothing the back surface of the decorative sheet, the surface (surface protective layer) of the decorative sheet is in contact with the smooth back surface after winding. As a result, it is possible to prevent the surface protective layer from being shaped and maintain the specularity. When the ten-point average roughness (R _zJIS ) of the back surface of the decorative sheet is larger than 15 μm, the surface protective layer shapes the unevenness of the back surface of the decorative sheet, and the mirror surface property after winding is lowered. From the viewpoint of obtaining excellent specularity and suppressing the occurrence of blocking when the decorative sheet is wound, the 10-point average roughness (R _zJIS ) is preferably 3 to 15 μm, and preferably 5 to 13 μm. It is more preferable. The ten-point average roughness (R _zJIS ) of the decorative sheet can be adjusted, for example, by adjusting the ten-point average roughness (R _zJIS ) of the base sheet according to the material of the roll used during film _formation. is there. Moreover, ten-point average roughness ( _RzJIS ) is measured based on JIS B0601: 2001, and can be measured using a contact-type surface roughness meter. In addition, the back surface of a decorative sheet is the back surface of the lowest layer of a decorative sheet. For example, when the base sheet is the lowermost layer of the decorative sheet, the back surface of the base sheet corresponds to the back surface of the decorative sheet, and the back surface primer layer described later is provided on the back surface of the base sheet. The back surface of the back primer layer corresponds to the back surface of the decorative sheet.

(Substrate sheet)
As the base sheet, a sheet made of polyolefin resin is used. Usually, a film made of polyolefin resin may be used.

  It does not specifically limit as polyolefin-type resin, What is normally used in the field | area of a decorative sheet can be used. Examples of such polyolefin resins include polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-propylene-butene copolymer. Examples thereof include a coalescence and a polyolefin-based thermoplastic elastomer. Among these, polypropylene resins, polyolefin-based thermoplastic elastomers and the like are preferable.

  By adopting polypropylene resin, even if the base sheet is thin, uneven application of glue (adhesive) or unevenness of the adherend surface is difficult to pick up so-called duck, and excellent specularity is obtained. Excellent production efficiency can be obtained, and an increase in material costs or transportation costs can be suppressed.

  The polypropylene resin is preferably a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, a polypropylene resin having a polypropylene crystal part, or an α-olefin copolymer having 2 to 20 carbon atoms other than the polypropylene resin having a polypropylene crystal part. Can be mentioned. Other propylene-α-olefin copolymers containing 15 mol% or more of ethylene, 1-butene, 1-hexene, 1-octene, 3-methyl-1-butene, 4-methyl-1-pentene, etc. Propylene copolymers, ethylene-propylene-butene copolymers and the like are also preferred.

  As the polypropylene resin, a crystalline resin having a glass transition point (Tg) of −50 to 70 ° C. and a melting point (Tm) of 130 to 220 ° C. is preferably used. If the polypropylene resin constituting the base sheet is a crystalline resin, it has a stable crystal structure as long as it is below the melting point (Tm) even in a temperature range higher than the glass transition temperature (Tg), so flexibility due to temperature changes. Change, that is, the temperature dependency of flexibility is low. For example, when a decorative sheet is heated (50-120 ° C.) while being wrapped on an adherend, uneven application of glue (adhesive) or Without picking up so-called duck such as irregularities on the surface of the adherend, the mirror finish does not deteriorate after sticking to the adherend, and excellent specularity even if there is uneven temperature due to local heating Can be maintained.

  The glass transition point (Tg) of the polypropylene resin as the crystalline resin is preferably −50 to 70 ° C. If the glass transition point (Tg) is lower than −50 ° C., there is a possibility that excellent specularity may not be obtained, and if it exceeds 70 ° C., specularity may not be obtained or heat resistance may not be obtained. From the viewpoint of obtaining excellent specularity and heat resistance, it is more preferably -20 to 50 ° C.

  Here, the glass transition point (Tg) is a value measured according to JIS K7121-1987. Specifically, using the base sheet as a test piece, the test piece is heated from room temperature at a rate of 20 ° C./min, the calorific value is measured with a differential scanning calorimeter (DSC), and an endothermic curve diagram or exotherm. A curve diagram is created, and an extension line is drawn on each of the straight lines before and after the inflection point, and the intersection of the 1/2 straight line between the two extension lines and the endothermic curve or exothermic curve is defined as Tg.

  The melting point (Tm) of the polypropylene resin as the crystalline resin is preferably 130 to 220 ° C. When the melting point (Tm) is less than 130 ° C., there is a possibility that excellent specularity cannot be obtained. On the other hand, when the temperature exceeds 220 ° C., a spring back may occur particularly when the adherend having a curved surface is processed, and thus excellent processing characteristics may not be obtained. From the viewpoint of obtaining excellent specularity and processing characteristics, it is more preferably 130 to 200 ° C.

  Here, the melting point (Tm) is a value measured in accordance with JIS K7121-1987. Specifically, using the base sheet as a test piece, the test piece was heated from room temperature at a rate of 10 ° C./min, heated to a temperature 30 ° C. higher than the end of the melting peak, held for 10 minutes, and then 10 In the DSC curve obtained by cooling at 40 ° C./min to 40 ° C. and repeating the same heating and cooling again, the temperature at the top of the melting peak was defined as the melting point (Tm). When there are a plurality of endothermic peaks in the DSC curve, the apex temperature of the endothermic peak with the maximum area is adopted.

  In consideration of the flexibility of the base sheet, it is preferable to blend an elastomer with the polyolefin resin. By blending the elastomer with the polyolefin-based resin, it is possible to prevent the base sheet from being deformed, for example, the base sheet is stretched and thinned or rapidly contracted during processing of the decorative sheet. Examples of the elastomer include polyolefin elastomers, styrene elastomers, polyester elastomers, polyurethane elastomers, and the like. Of these, polyolefin-based thermoplastic elastomers are preferred. As a compounding quantity of the said elastomer, about 10-60 mass% is preferable with respect to the said polyolefin resin whole quantity, and about 30 mass% is more preferable.

  50-250 micrometers is preferable and, as for the thickness of a base material sheet, 90-150 micrometers is more preferable. When the thickness of the base sheet is within the above range, a decorative sheet excellent in specularity and workability can be obtained.

When the base material sheet is the lowermost layer of the decorative sheet, the 10-point average roughness (R _zJIS ) of the back surface measured according to JIS B0601: 2001 of the base material sheet is set to 15 μm or less. The 10-point average roughness (R _zJIS ) of the back surface of the base sheet is 15 μm or less, that is, the back surface of the decorative sheet (surface protective layer) is smooth after winding by smoothing the back surface of the decorative sheet ( It will be in contact with the base material sheet), and the surface protective layer can be prevented from shaping and the mirror surface property can be maintained. From the viewpoint of obtaining excellent specularity and suppressing the occurrence of blocking when the decorative sheet is wound up, the ten-point average roughness (R _zJIS ) of the base sheet is preferably 3 to 15 μm. More preferably, it is ˜13 μm. The ten-point average roughness (R _zJIS ) of the base sheet can be adjusted by the material of the roll used during film _formation . Moreover, ten-point average roughness ( _RzJIS ) is measured based on JIS B0601: 2001, and can be measured using a contact-type surface roughness meter.

  The substrate sheet is preferably colored with a colorant. By being colored, the base of an adherend such as a substrate on which a decorative sheet is provided can be concealed, and at the same time, excellent design properties can be obtained.

  Colorants that can be used for the base sheet include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, Organic pigments such as isoindolinone yellow and phthalocyanine blue, or pearly luster consisting of scaly foils such as dyes, metallic pigments made of scaly foils such as aluminum and brass, titanium dioxide-coated mica, and basic lead carbonate (pearl) ) Pigments are preferred.

  The amount of the colorant to be used is not particularly limited as long as it does not lower the film formability and mechanical strength when the substrate sheet is obtained by extrusion molding.

  An additive may be blended in the resin material used for forming the base sheet, if necessary. Examples of the additive include a filler, a flame retardant, an antioxidant, a lubricant, a foaming agent, and a weathering agent.

  Among the above additives, from the viewpoint of obtaining excellent processing characteristics, inorganic fillers such as calcium carbonate, barium sulfate, clay and talc; ultraviolet absorbers (UVA) and hindered amine light stabilizers for improving weather resistance It is preferable to contain a weathering agent such as (HALS). The content of these inorganic fillers is preferably in the range of 1 to 60% by mass with respect to the resin material.

(Primer layer)
The primer layer is a layer provided between the base sheet and the surface protective layer, and is provided to improve the adhesion of these layers, improve workability, and prevent blocking in the production process. .

  A primer layer is comprised by the resin composition containing binder resin and a mat agent, for example. The binder resin is not particularly limited, but preferred examples include urethane resins, acrylic resins, urethane / acrylic copolymers, polyester resins, vinyl chloride / vinyl acetate copolymers, chlorinated polypropylene resins, chlorinated polyethylene resins, and the like. It is done. In addition, from the viewpoint of obtaining excellent adhesion and specularity, a two-component curable resin containing the above resin as a main component and isocyanate or the like as a curing agent is preferable.

  As the isocyanate curing agent, a conventionally known compound may be appropriately used. For example, aromatic compounds such as 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and 4,4′-diphenylmethane diisocyanate. Isocyanate or poly (such as aliphatic (or cycloaliphatic) isocyanate such as 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate Isocyanates are used. Further, adducts or multimers of these various isocyanates, for example, adducts of tolylene diisocyanate, tolylene diisocyanate trimers and the like are also used.

  In order to prevent blocking in the production process, the primer layer preferably contains a matting agent. By including a matting agent in the primer layer, it is possible to prevent blocking from occurring when the primer layer is once wound up in a roll shape after forming the primer layer on the base sheet. Preferred examples of the matting agent include inorganic particles such as alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide, and organic particles such as acrylic resin, urethane resin, nylon resin, polypropylene resin, and urea resin. Any one type may be used, or two or more types may be used in combination.

  Examples of the shape of the matting agent include a sphere, an ellipsoid, a polyhedron, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable in terms of obtaining specularity.

  The average particle size of the matting agent is preferably 0.5 to 8 μm, and more preferably 1 to 5 μm. When the average particle diameter is within the above range, excellent specularity can be obtained. Here, the average particle size is a volume-based particle size measured by laser diffraction type or laser scattering type particle size distribution measurement.

  The content of the matting agent is preferably 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass, and further preferably 3 to 20 parts by mass with respect to 100 parts by mass of the binder resin. preferable. When the content is within the above range, excellent adhesion can be obtained.

  In the primer layer, additives other than the matting agent may be blended as necessary. Examples of the additive include a filler, a flame retardant, an antioxidant, a lubricant, a foaming agent, and a weathering agent. Among the additives, it is preferable to contain a weathering agent such as an ultraviolet absorber (UVA) or a hindered amine light stabilizer (HALS) in order to improve weatherability.

  The thickness of a primer layer is about 0.5-20 micrometers normally, and 1-10 micrometers is preferable. When the thickness of the primer layer is within the above range, excellent adhesion and specularity can be obtained.

Moreover, the 10-point average roughness ( _RzJIS ) of the surface measured based on JIS B0601: 2001 of a primer layer is 5 _micrometers or less. When it is larger than 5 μm, mirror surface properties cannot be obtained. From the viewpoint of obtaining excellent specularity and obtaining excellent workability, the ten-point average roughness (R _zJIS ) is preferably 1 to 5 μm, and preferably 2.5 to 4.5 μm. The ten-point average roughness (R _zJIS ) of the primer layer can be adjusted by changing the average particle size, content, etc. of the matting agent. Moreover, ten-point average roughness ( _RzJIS ) is measured based on JIS B0601: 2001, and can be measured using a contact-type surface roughness meter.

(Surface protective layer)
The surface protective layer is an ionizing radiation curable resin that imparts surface characteristics such as weather resistance, stain resistance, scratch resistance, solvent resistance, and heat resistance to the decorative sheet of the present invention, and also provides excellent specularity. It is a layer composed of a cured product of the composition.

  The material constituting the surface protective layer is constituted by a cured product of an ionizing radiation curable resin composition containing an ionizing radiation curable resin. Here, the ionizing radiation curable resin composition is a resin composition that is cured by irradiating with ionizing radiation, and the ionizing radiation has an energy quantum capable of polymerizing or crosslinking molecules among electromagnetic waves or charged particle beams. In addition to ultraviolet rays (UV) or electron beams (EB), electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays are also used.

  The ionizing radiation curable resin contained in the ionizing radiation curable resin composition is appropriately selected from polymerizable monomers and polymerizable oligomers (or prepolymers) conventionally used as ionizing radiation curable resins. be able to.

  For example, polymerizable monomers such as monofunctional (meth) acrylate and polyfunctional (meth) acrylate, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer Polymerizable oligomers such as acrylic (meth) acrylate oligomers, or prepolymers can be used alone or in combination of two or more.

  In the present invention, a polymerizable oligomer is preferably used as the ionizing radiation curable resin, and a polyfunctional polymerizable oligomer having 2 or more functional groups is preferable.

  Further, from the viewpoint of adjusting the viscosity of the ionizing radiation curable resin composition and improving the coating suitability, a polymerizable oligomer and a polymerizable monomer can be used in combination.

  When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the resin. The initiator for photopolymerization can be appropriately selected from those conventionally used, and is not particularly limited. For example, the initiator for photopolymerization such as benzoin, acetophenone, phenylketone, benzophenone, and anthraquinone An agent is preferably mentioned.

  Moreover, as a photosensitizer, p-dimethylbenzoic acid ester, tertiary amines, a thiol type sensitizer, etc. can be used, for example.

  The ionizing radiation curable resin used in the present invention is preferably an electron beam curable resin. In the case of an electron beam curable resin, solvent-free is possible, which is more preferable from the viewpoint of environment and health, and does not require a photopolymerization initiator, provides stable curing characteristics, and excellent surface characteristics. This is because

  In the ionizing radiation curable resin composition, various additives such as silicone components, wear-resistant fillers, mat-forming fillers, fillers such as scratch-resistant fillers, UV absorbers, and light stabilizers are used to improve weather resistance. Weathering agents such as agents can be included.

  The silicone component refers to a component having in its molecule a structure formed by alternately bonding silicon having an organic group and oxygen. As a silicone component, specifically, a silicone oil having a polysiloxane skeleton as a main component, an organic group having reactivity such as an amino group, a vinyl group, an epoxy group, a carboxyl group, an acrylic group, and a methacryl group at the side chain or terminal. Reactive silicone introduced with a group; non-reactive silicone introduced with a non-reactive organic group such as an alkyl group, an ether group or a higher fatty acid at the side chain or terminal; side of an organic resin, ionizing radiation curable resin, etc. Examples thereof include a silicone-modified resin whose chain or terminal is modified with silicone. By adding the silicone component, the leveling property when coating the ionizing radiation curable resin composition is improved and a uniform coating film can be formed. In addition, the silicone component floats on the surface of the coating film. Due to the rising action, a decrease in planar smoothness caused by the ionizing radiation curable resin composition soaking into the primer layer is suppressed, so that the specularity can be improved. Of these, reactive silicone is preferred.

  Among these, the reactive silicone reacts and integrates with the ionizing radiation curable resin when the ionizing radiation curable resin composition is cured, and it is difficult to cause poor appearance due to bleeding out. It is preferable at the point which can hold | maintain.

  The types of reactive silicone include modified silicone oil side chain type, modified silicone oil both end type, and modified silicone oil side chain both end type, depending on the organic group to be introduced, amino-modified, epoxy-modified, mercapto-modified. , Carboxyl modification, carbinol modification, phenol modification, methacryl modification, heterogeneous functional group modification, and the like.

  It is preferable that content of a silicone component is 0.1-2 mass% with respect to the ionizing radiation curable resin contained in an ionizing radiation curable resin composition. By setting it as the above range, sufficient lubricity can be imparted to the surface, no repelling occurs at the time of coating, the coating surface is not roughened, and stability can be improved. . The content is more preferably 0.2 to 1% by mass.

  As the ultraviolet absorber, either inorganic or organic can be used. As the inorganic ultraviolet absorber, titanium oxide, cerium oxide, zinc oxide or the like having an average particle diameter of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, a benzotriazole type, a triazine type, a benzophenone type, a salicylate type, an acrylonitrile type etc. can be mentioned preferably, for example. Of these, triazines are preferred because they have a high ability to absorb ultraviolet rays and do not easily deteriorate even with high energy such as ultraviolet rays. Further, as the ultraviolet absorber, an ultraviolet absorber having an electron beam reactive group in the molecule can be used.

  Preferred examples of the light stabilizer include hindered amine light stabilizers (HALS). Moreover, the light stabilizer which has the (meth) acryloyl group which is an electron beam reactive group in a molecule | numerator can also be used.

  By using the above ultraviolet absorber, light stabilizer and the like as a weathering agent, stable weatherability can be obtained without causing the weathering agent to bleed out.

  In addition, ionizing radiation curable resin compositions are used as various additive components for the purpose of improving the concealability of the surface protective layer in the resulting decorative sheet, preventing yellowing of the base material, and improving light resistance. Inorganic color pigments such as paste and carbon black can be appropriately added.

The surface protective layer has a crack generation elongation measured by the following method of 20 to 130%. (Measurement of crack elongation)
A strip-shaped test piece conforming to JIS K7127 is prepared using a decorative sheet, and the test piece is arbitrarily selected in a room temperature environment using a tensile tester at a tensile speed of 200 mm / min and a distance between chucks of 100 mm. After pulling at the elongation, the inside of the chuck is colored with a whiteboard marker, and the colored portion is wiped off with a cloth. . The decorative sheet of the present invention is implemented in the form of a decorative sheet with a masking film further having a masking film on the surface protective layer and / or in the form of a decorative sheet with an adhesive layer further having an adhesive layer on the back side. Although cracking elongation is obtained, it is a value measured in the state which does not have the masking film or adhesive bond layer mentioned later.

  In this specification, room temperature is 23 ° C. ± 5 ° C., and room temperature environment means a laboratory environment having a temperature of 23 ° C. ± 5 ° C.

  In the above method for measuring the crack occurrence elongation, Pentel knuckle whiteboard markers, blue, round core, and middle character were used as whiteboard markers. Further, the coloring between the chucks was colored throughout the chucks after being pulled.

  When the crack generation elongation of the surface protective layer is less than 20%, the surface of the decorative sheet is cracked. On the other hand, when the crack generation elongation exceeds 130%, the surface of the decorative sheet is too soft, and irregularities on the back surface of the decorative sheet are formed at the time of winding and the specularity is deteriorated. The crack generation elongation is preferably 20 to 80%.

  Adjustment of the crack generation elongation of the surface protective layer can be performed by adjusting the hardness of the surface protective layer. Specifically, for example, it can be carried out by adjusting the number of functional groups, molecular weight, etc. of the ionizing radiation curable resin contained in the ionizing radiation curable resin composition forming the surface protective layer. When the number of functional groups of the ionizing radiation curable resin is increased, the resin becomes hard and the crack generation elongation decreases, and when the number of functional groups is decreased, the resin becomes soft and the crack generation elongation tends to increase. When the molecular weight of the ionizing radiation curable resin is reduced, the resin becomes hard and crack generation elongation decreases, and when the molecular weight of the ionizing radiation curable resin is increased, the resin becomes soft and crack generation elongation tends to increase.

  Moreover, the crack generation elongation of the surface protective layer can be adjusted by adjusting the irradiation intensity of the ionizing radiation when forming the surface protective layer. When the irradiation intensity of ionizing radiation is increased, the surface protective layer is hardened and the crack generation elongation is reduced. On the other hand, when the irradiation intensity of ionizing radiation is weakened, the surface protective layer becomes soft and the crack generation elongation increases. Furthermore, the crack generation elongation of the surface protective layer can also be adjusted by mixing a plurality of ionizing radiation curable resins forming the surface protective layer and adjusting the blending ratio as appropriate to adjust the hardness of the surface protective layer. it can.

  Further, the crack generation elongation can be adjusted by appropriately adjusting the coating amount of the ionizing radiation curable resin composition forming the surface protective layer. Increasing the coating amount decreases the cracking elongation, and decreasing the coating amount increases the cracking elongation.

  The thickness of the surface protective layer is preferably 6 to 20 μm. If the thickness of the surface protective layer is less than 6 μm, there is a possibility that excellent specularity cannot be obtained, and if it exceeds 20 μm, excellent processing characteristics may not be obtained.

  From the viewpoint of obtaining excellent specularity and excellent workability, the thickness of the surface protective layer is more preferably 7 to 18 μm, and further preferably 7 to 15 μm.

  The 20 ° gloss on the surface of the surface protective layer is 40 or more. In this specification, “gloss” means “Specular glossiness”. When evaluating the specularity, an angle of incident light of 60 ° is normally used. However, when the specularity is very good, the gloss value is saturated at 60 °, and the specular gloss sensation and the measured numerical value are based on vision. Correlation and significance are reduced, and there is no significant difference in numerical values. Therefore, in the present invention, the specularity was evaluated at an angle of 20 °. The 20 ° gloss is an average value of values measured at any five locations on the surface protective layer using a gloss measuring device (micro gloss manufactured by BYK Gardner) by a method based on JIS Z-8741.

  Since the 20 ° gloss of the surface protective layer is 40 or more, the decorative sheet of the present invention has excellent specularity. The 20 ° gloss of the surface protective layer is preferably 50 or more, more preferably 60 or more.

  The 20 ° gloss adjustment can be performed by adjusting the film thickness of the surface protective layer. Specifically, when the film thickness is reduced, the 20 ° gloss is reduced, and when the film thickness is increased, the 20 ° gloss is increased.

(Back primer layer)
The back primer layer is a layer preferably provided for the purpose of improving the adhesion between the substrate sheet and various adherends, and is on the side opposite to the surface of the substrate sheet on which the primer layer and the surface protective layer are provided. It is provided on the surface (back surface).

  A back surface primer layer is comprised by the resin composition containing binder resin and a mat agent, for example. As the binder resin, those described in the above section of the primer layer are preferably mentioned, and are appropriately selected according to the material of the adherend.

  Moreover, as a mat agent, what was described by the term of said primer layer is mentioned preferably, The average particle diameter and content are the same as the above.

  The thickness of the back primer layer is preferably about 0.5 to 5 μm, more preferably 1 to 3 μm. When the thickness is within the above range, excellent adhesion between the substrate sheet and various adherends can be obtained.

In addition, when the back surface primer layer is provided on the back surface of the base material sheet, the back surface of the back surface primer layer corresponds to the back surface of the decorative sheet. Roughness (R _zJIS ) is set to 15 μm or less.

(Decoration layer)
The decorative layer gives decorativeness to the decorative sheet, and may be a uniformly colored concealing layer (solid printing layer) or formed by printing various patterns using ink and a printing machine. The pattern layer may be a combination of a hiding layer and a pattern layer. The decoration layer is usually provided between the base material sheet and the primer layer.

  By providing a concealing layer, the surface of the adherend can be concealed, and when the base sheet is colored or uneven in color, the surface color can be adjusted by giving the intended color. .

  In addition, by providing a pattern layer, a grain pattern imitating the surface of a rock such as a wood grain pattern, marble pattern (for example, travertine marble pattern), a fabric pattern imitating a texture or cloth pattern, tiled pattern, brickwork A pattern such as a pattern or a combination of these, a parquet, a patchwork, or the like can be applied to the decorative sheet. These patterns are formed by multicolor printing with the usual yellow, red, blue and black process colors, as well as by multicolor printing with special colors prepared by preparing the individual color plates constituting the pattern. Is done.

As the ink composition used for the decorative layer, a binder resin in which a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used. The binder resin is not particularly limited. For example, urethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin. , Butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin and the like are preferable, and polyurethane resin is more preferable. Any of these binder resins can be used alone or in admixture of two or more.

  Moreover, as a coloring agent, what was illustrated as a coloring agent used for a base material sheet is mentioned preferably.

  The thickness of the decoration layer is usually about 0.5 to 20 μm, and preferably 1 to 10 μm. If the thickness of the decoration layer is within the above range, it is possible to impart excellent design properties to the decorative sheet and to impart concealability.

(Masking film)
The masking film is used on the surface protective layer of the decorative sheet to prevent scratches during the transportation or construction of the decorative board obtained by processing, including when the decorative sheet is processed into an adherend. It is a film preferably provided in the above. Therefore, the decorative sheet of the present invention can be a decorative sheet with a masking film having a masking film on the surface of the decorative sheet. In addition, the crack generation elongation of a surface protective layer is a value in the state of a decorative sheet without a masking film.

  The masking film usually has a structure having a masking film substrate and an adhesive layer.

  Preferred examples of the base material for the masking film include polyester films such as polyethylene terephthalate (PET) films; polyolefin films such as polyethylene films and polypropylene films; polycarbonate films and the like.

  There is no restriction | limiting in particular about the thickness of this base material for masking films, It is preferable that it is 10-100 micrometers, and it is more preferable that it is 30-70 micrometers. When the thickness is within the above range, good scratch resistance can be obtained, turning and peeling are unlikely to occur during processing, and cost can be reduced.

  The pressure-sensitive adhesive that forms the pressure-sensitive adhesive layer is, for example, an acrylic-based polymer mainly composed of a (meth) acrylic acid ester-based polymer, from the viewpoint of being difficult to peel off during storage, easy to peel off during use, and difficult to leave a pressure-sensitive adhesive residue. In addition to the pressure-sensitive adhesive, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and the like are preferable.

  Moreover, 5-40 micrometers is preferable and, as for the thickness of an adhesive layer, 10-30 micrometers is more preferable. When the thickness is within the above range, it is difficult to peel off during storage, it is easy to peel off during use, and the adhesive remains difficult to leave.

(Manufacturing method of decorative sheet)
The method for producing the decorative sheet of the present invention is not particularly limited. For example, (1) Step 1 for forming a base sheet, (2) forming a primer layer on the base sheet, and if necessary, a back primer layer Step 2 to be formed, (3) The ionizing radiation curable resin composition is applied onto the primer layer, and it is cross-cured to form a surface protective layer, which is followed by Step 3 in order.

  Step 1 is a step of forming a base sheet.

  The base sheet is obtained by forming a resin composition in which a colorant and other additives are added to a resin material as desired by a method such as a calendering method, an inflation method, or a T-die extrusion method. Here, biaxial stretching may be performed as necessary.

  From the viewpoint of improving the adhesion with the layer in contact with the obtained substrate sheet, the surface may optionally be subjected to an oxidation method such as corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method, An easy-adhesion layer may be provided by performing physical or chemical surface treatment such as a sand blasting method or a concavo-convex method such as a solvent processing method.

  Step 2 is a step of forming a primer layer on the base sheet and forming a back primer layer if necessary.

  The primer layer and the back primer layer are formed by applying the resin composition forming these layers by a known coating method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method. do it. Moreover, when providing both a primer layer and a back surface primer layer, you may form any layer previously.

  Step 3 is a step of forming a surface protective layer by applying an ionizing radiation curable resin composition on the primer layer and curing it by crosslinking.

  The application of the ionizing radiation curable resin composition is such that the thickness after curing is 7 to 16 μm, and the gravure printing method or bar coating method on the surface of the base material sheet or the primer layer provided as desired , A known method such as a roll coating method, a reverse roll coating method or a comma coating method, preferably a gravure printing method. The viscosity of the ionizing radiation curable resin composition is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer of the ionizing radiation curable resin composition on the surface of the base sheet or primer layer.

  Next, the uncured resin layer formed by applying the ionizing radiation curable resin composition is irradiated with ionizing radiation such as an electron beam and ultraviolet rays to cure the uncured resin layer, and the ionizing radiation curable resin composition A surface protective layer which is a cured product of is formed.

  When an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin used and the thickness of the layer, but it is preferable to cure the uncured resin layer usually at an accelerating voltage of about 70 to 300 kV.

  In electron beam irradiation, transmission capability increases as the acceleration voltage increases. Therefore, when using a material that deteriorates due to electron beams as the base layer, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal, it is possible to suppress the irradiation of the extra electron beam to the base material sheet, and it is possible to minimize the deterioration of the base material layer due to the excess electron beam.

  The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, usually 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 100 kGy (1 to 10 Mrad), more preferably 30 to 70 kGy (3 to 7 Mrad). It is selected in the range.

  The electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.

  When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

  The decorative sheet of the present invention thus obtained has excellent processability, and has good specularity even after processing, particularly after winding. Taking advantage of this feature, the decorative sheet of the present invention can be suitably used as a decorative sheet for decorating an adherend such as plastic having a curved surface. Specifically, the decorative sheet with an adhesive layer having an adhesive layer on the back surface of the decorative sheet of the present invention can be applied to various interior and exterior parts for automobiles, interior and exterior parts of buildings, building materials, furniture, and home appliances. It can use suitably by applying to a member.

  It does not specifically limit as an adhesive agent used for a decorative sheet with an adhesive bond layer, A heat sensitive adhesive, a pressure sensitive adhesive (adhesive), etc. are mentioned. Examples of the resin used for the adhesive include acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acrylic copolymer resins, polyester resins, and polyamide resins. At least one resin selected from resins and the like can be used. Further, a two-component curable polyurethane adhesive or polyester adhesive using isocyanate as a curing agent can also be applied.

  A decorative sheet with an adhesive layer is prepared by applying the above resin into a form that can be applied as a solution or emulsion, by means of a gravure printing method, a screen printing method or a reverse coating method using a gravure plate. It can form by apply | coating to (the back surface of a base material sheet), and drying as needed.

  Although there is no restriction | limiting in particular in the thickness of an adhesive bond layer, Usually, it is the range of 1-100 micrometers. By setting it as this range, the adhesiveness of a to-be-adhered material and a decorative sheet can be improved more.

2. Molded product The molded product of the present invention has the decorative sheet of the present invention on an adherend. Examples of such a molded product include a molded product having an adherend, an adhesive layer, and the decorative sheet of the present invention in this order.

  The adherend used in the molded product of the present invention is not particularly limited, and examples thereof include plastic molded products such as automobile parts. As a plastic molded article, what consists of various synthetic resins can be used. Synthetic resins include polyolefin resins, vinyl resins, polyester resins, acrylic resins, polyamide resins, cellulose resins, polystyrene resins, polycarbonate resins, polyarylate resins, polyimide resins, ABS resins, urethane resins, epoxy resins, and the like. .

  Further, in order to improve the adhesion between the plastic molded product and the decorative sheet, an oxidation method such as a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, an ozone-ultraviolet treatment method or the like may be applied to one side or both sides as desired. Alternatively, a physical or chemical surface treatment such as a concavo-convex method such as a sand blast method or a solvent treatment method can be performed.

  It does not specifically limit as an adhesive agent used for the adhesive layer agent for adhere | attaching an adherend and a decorative sheet, A heat sensitive adhesive, a pressure sensitive adhesive (adhesive) etc. are mentioned. Examples of the resin used for the adhesive constituting this adhesive layer include acrylic resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, styrene-acryl copolymer resins, At least one resin selected from polyester resins and polyamide resins is used. Further, a two-component curable polyurethane adhesive or polyester adhesive using isocyanate as a curing agent can also be applied.

  The adhesive layer is a reverse coating using a gravure printing method, a screen printing method, or a gravure plate on the back surface of the decorative sheet or the back surface of the adherend in which the above resin is applied in a solution or emulsion form. It can be formed by coating and drying by means such as a method. In addition, when using a decorative sheet with an adhesive layer in which an adhesive layer is previously provided on the back surface of the decorative sheet as described above, it is not necessary to form an adhesive layer immediately before bonding to the adherend, and workability or production Good sex.

  Although there is no restriction | limiting in particular in the thickness of an adhesive bond layer, Usually, it is the range of 1-100 micrometers. By setting it as this range, the adhesiveness of a to-be-adhered material and a decorative sheet can be improved more.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

Example 1
A colored polypropylene resin sheet ("Art Ply (trade name)", manufactured by Mitsubishi Plastics Co., Ltd., thickness: 110 μm) is prepared as a base sheet, and on one side thereof, for primer layer formation prepared by mixing the following components The resin composition was applied to form a primer layer (thickness: 2 μm), and the polyester-urethane resin composition was applied to the other surface to form a back primer layer (thickness: 2 μm).
(Primer layer forming resin composition)
Main agent (resin composed of polycarbonate urethane / acrylic copolymer): 100 parts by mass UV absorber (Tinuvin 400 (trade name), 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2 -Hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, manufactured by BASF Japan Ltd.): 5 parts by mass ultraviolet absorber (Tinuvin 479 (trade name), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl-4,6-bis (4-phenylphenyl) -1,3,5-triazine, manufactured by BASF Japan Ltd.): 5 parts by weight light stabilizer (Tinuvin 123 (trade name), bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, BASF Japan Ltd. Formula Company): 1 part by weight average particle size 4μm matting agent: 15 parts by weight curing agent (hexamethylene diisocyanate): 5 parts by weight

Next, an ionizing radiation curable resin composition prepared by mixing the following components was applied onto the primer layer at a coating amount of 10 g / m ² by gravure printing to form a coating film. Next, the coating film was crosslinked and cured by irradiation with an electron beam under the conditions of 175 keV and 5 Mrad (50 kGy) to form a surface protective layer (thickness: 10 μm) to obtain a decorative sheet.
(Ionizing radiation curable resin composition)
Mixture of urethane acrylate oligomer (number of functional groups: 2, weight average molecular weight: 3000) and urethane acrylate oligomer (number of functional groups: 2, weight average molecular weight: 4000) (mixing ratio (molar ratio) 5: 5): 100 parts by mass UV Absorbents (tinuvin 479 (trade name), 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl-4,6-bis (4-phenylphenyl) -1,3,5-triazine, BASF (Made by Japan Co., Ltd.): light stabilizer having 2 parts by mass of reactive functional group (Sanol LS-3410 (trade name), 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, BASF Japan Ltd.) (Made by company): 4 parts by mass reactive silicone compound (57ADDITIVE (trade name), polyether-modified silicone, east Dow Corning Co., Ltd.): 0.5 parts by weight

  About the obtained decorative sheet, the property or characteristic was evaluated with the following measuring method.

Examples 2-9 and Comparative Examples 1-5
In Example 1, the ten-point average roughness (R _zJIS ) of the back surface of the decorative sheet (the back surface of the base sheet), the thickness of the surface protective layer, the crack generation elongation, the presence or absence of reactive silicone, and the ten points of the primer layer A decorative sheet was obtained in the same manner as in Example 1 except that the average roughness (R _zJIS ) was as shown in Table 1.

  About the obtained decorative sheet, the property or characteristic was evaluated with the following measuring method.

(1) Ten-point average roughness ( _RzJIS )
The surface roughness meter (manufactured by Tokyo Seimitsu Co., Ltd., Handy Surf E-35A) was measured by a method based on JIS B0601: 2001 under the conditions of a cutoff value of 0.8 mm and an evaluation length of 4 mm.

(2) Crack generation elongation A strip-shaped test piece was cut out from the decorative sheet in accordance with JIS K7127, and the test piece was pulled at a pulling speed of 200 mm / min using a tensile tester in a room temperature environment. The film was pulled at an arbitrary elongation under the conditions of 100 mm and a width of 15 mm. Next, the space between the chucks of the test piece was colored with a whiteboard marker, the colored portion was wiped off with a cloth, and the elongation at the time when it became impossible to wipe off due to the occurrence of a crack was defined as the crack generation elongation.

(3) Specularity (20 ° gloss)
It measured by the method based on JISZ-8741 on the conditions of an angle of 20 degrees using the glossiness meter (BYG Gardner microgloss). The measurement was carried out at any five locations of the surface protective layer after the decorative sheet was created and after being wound up as a roll, and the average value was taken as the measured value. If the 20 ° gloss is 40 or more, it is considered acceptable.

(4) Workability evaluation (visual appearance evaluation)
An adhesive (acrylic pressure-sensitive adhesive, manufactured by Sanyo Chemical Industries, Polysic 470-S) was applied to the back surface of the decorative sheets obtained in Examples and Comparative Examples at a thickness of 20 g / m ² , and 1.0R The decorative sheet was affixed to a convex part having a curvature of 5 mm, and the appearance of the decorative sheet was visually observed under a fluorescent lamp (straight tube type), and evaluated according to the following criteria.
○: No change in appearance (no whitening or cracks observed)
Δ: slight whitening or cracking change in appearance, but no problem in actual use ×: significant change in appearance (whitening or cracking is observed)

(5) Evaluation of blocking property Sheets at the time when the surface protective layers of Examples and Comparative Examples were formed were cut into 50 mm x 50 mm to prepare test pieces. Two pieces of the test pieces were prepared, overlapped so that one surface protective layer side and the other back primer layer side were in contact with each other, and sandwiched by a blocking tester. The compression handle was then tightened and a pressure of 1 kg / cm ² was applied. Next, the blocking tester was left in a room temperature environment for 24 hours. The test piece in a state where two sheets were overlapped was peeled off, and the sound and feel at that time were evaluated based on the following evaluation criteria.
A: There was no sound or peeling feeling.
Δ: Although there was a sound and peeling feeling, there was no problem in actual use.
X: A feeling of sound and peeling was felt greatly, and the sheet was deformed.

  The evaluation results are shown in Table 1.

1. 1. Base sheet 2. Primer layer 3. 3. Surface protective layer 4. Back primer layer Masking film10. Decorative sheet

Claims (10)

A decorative sheet in which a primer layer and a surface protective layer are laminated in this order on a base sheet,
The decorative sheet has a back surface ten-point average roughness (R _zJIS ) measured in accordance with JIS B0601: 2001 of 15 μm or less,
The base sheet is made of a polyolefin resin;
The surface protective layer is a cured product of an ionizing radiation curable resin composition, the crack generation elongation measured by the following method is 20 to 130%, and the 20 ° gloss of the surface of the surface protective layer is 40. That's it,
Makeup sheet.
(Measurement of crack elongation)
A strip-shaped test piece conforming to JIS K7127 is prepared using a decorative sheet, and the test piece is arbitrarily selected in a room temperature environment using a tensile tester at a tensile speed of 200 mm / min and a distance between chucks of 100 mm. After pulling at the elongation, the inside of the chuck is colored with a whiteboard marker, and the colored portion is wiped off with a cloth. .   The decorative sheet according to claim 1, wherein the surface protective layer has a crack generation elongation of 20 to 80%.   The decorative sheet according to claim 1 or 2, wherein the surface protective layer has a thickness of 6 to 20 µm.   The decorative sheet according to any one of claims 1 to 3, wherein the surface protective layer further contains a silicone component.   The decorative sheet according to any one of claims 1 to 4, wherein the silicone component is 0.5 to 2 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin contained in the ionizing radiation curable resin composition. . The decorative sheet according to any one of claims 1 to 5, wherein the primer layer has a 10-point average roughness ( _RzJIS ) of 5 µm or less measured according to JIS B0601: 2001.   The decorative sheet according to any one of claims 1 to 6, further comprising a back primer layer on a surface opposite to the surface having the primer layer of the base material sheet.   The decorative sheet with a masking film which has a masking film on the surface of the decorative sheet in any one of Claims 1-7.   The decorative sheet with an adhesive layer which has an adhesive layer on the back surface of the decorative sheet according to claim 1.   A molded article having the decorative sheet according to any one of claims 1 to 7 or the decorative sheet with a masking film according to claim 8 on an adherend.