Decorative sheet, decorative member and method for producing decorative sheet

Abstract

To provide a decorative sheet excellent in bender bending workability (post-processing), and imparted with designability due to a low gloss layer, while maintaining scratch resistance, film forming property and transparency of a transparent resin layer required in practical use, a decorative member and a method for producing the decorative sheet.SOLUTION: A decorative sheet 1 according to this embodiment is formed of a transparent resin layer 3 made of a resin composition containing multiple types of polypropylene resins, and a low gloss layer formed of a resin containing a matting agent provided on the transparent resin layer. The resin composition contains these multiple types of polypropylene resins, and the blending ratios of each of the multiple types of polypropylene resins, based on the mass of the resin composition, are as follows: high crystalline polypropylene is in the range of 30 mass% or more and 50 mass% or less, low crystalline polypropylene is in the range of 30 mass% or more and 50 mass% or less, and random polypropylene is in the range of 10 mass% or more and 20 mass% or less.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a decorative sheet used for interior building materials, surface materials of furniture, surface materials of household appliances, etc., a decorative member using the decorative sheet, and a method for manufacturing the decorative sheet. The decorative sheet is used as a decorative member (decorative board) by being bonded to a substrate such as wood-based boards, inorganic boards, or metal plates, for example.

Background Art

[0002] In recent years, as shown in Patent Documents 1 and 2, many decorative sheets using olefin-based resins have been proposed as decorative sheets to replace decorative sheets made of polyvinyl chloride. These decorative sheets suppress the generation of toxic gases and the like during incineration by not using vinyl chloride resin. However, conventional decorative sheets made of olefin-based resins use general polypropylene sheets, so they have poor scratch resistance on the surface and are inferior in scratch resistance compared to conventional decorative sheets made of polyvinyl chloride.

[0003] In contrast, in order to solve these drawbacks, a decorative sheet excellent in scratch resistance on the surface as described in Patent Document 3 has been proposed. However, as the uses of decorative boards using such decorative sheets are increasingly expanding and consumers' awareness of quality is also increasingly sophisticated, improvement in qualities other than scratch resistance for decorative sheets, particularly improvement in post-processing resistance such as bending processing, is required. Here, as decorative sheets with improved post-processing properties, the decorative sheets described in Patent Documents 4 to 6 have been proposed. These decorative sheets are decorative sheets having a transparent resin layer in which a soft component is added to a random polymerization type polypropylene resin. However, this decorative sheet has problems that the sheet becomes flexible with the improvement of post-processing properties, so the scratch resistance required in actual use and the film-forming property of the transparent resin layer deteriorate. In addition, in the transparent resin layer, it is also required to suppress clouding and maintain transparency. In addition, in a cosmetic sheet, a technique (glossy matte printing) for visually expressing unevenness to improve the design quality is known. For example, in Patent Document 7, a technique for visually expressing unevenness by making the gloss state different on the surface of the cosmetic sheet (providing a matte layer and a gloss-improving resin layer) has been proposed. In addition, in some cases, a low-gloss expression (matte design) is applied to the entire surface of the cosmetic sheet in order to produce a texture similar to that of natural materials. However, when forming a low-gloss layer (a resin layer containing a matting agent) on the sheet surface as a low-gloss expression method, the resin layer is likely to crack or craze due to bending. Therefore, when applying a low-gloss expression, further improvement in bendability such as bender bending is required.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present disclosure has been made paying attention to the above points, and while maintaining the scratch resistance, film-forming properties, and transparency of the transparent resin layer required in actual use, it is excellent in bender bendability (post-processing properties), and a cosmetic sheet, a cosmetic member, and a method for manufacturing a cosmetic sheet provided with design quality by a low-gloss layer are provided.

Means for Solving the Problems

[0006] In order to solve the above problems, a cosmetic sheet according to one aspect of the present disclosure includes a transparent resin layer formed of a resin composition containing a plurality of types of polypropylene resins, and a low-gloss layer provided on the transparent resin layer and formed of a resin containing a matting agent. The resin composition includes highly crystalline polypropylene, low-crystalline polypropylene, and random polypropylene as the plurality of types of polypropylene resins. The blending ratio of each of the plurality of types of polypropylene resins based on the mass of the resin composition is such that the highly crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, the low-crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, and the random polypropylene is in the range of 10% by mass or more and 20% by mass or less. Further, a cosmetic member according to one aspect of the present disclosure includes a base material and the cosmetic sheet provided on at least one surface side of the base material. Further, a method for manufacturing a cosmetic sheet according to one aspect of the present disclosure is the method for manufacturing the cosmetic sheet, in which the transparent resin layer is formed using the resin composition containing the plurality of types of polypropylene resins, and the low-gloss layer formed of a resin containing a matting agent is formed on the transparent resin layer. The plurality of types of polypropylene resins are the highly crystalline polypropylene, the low-crystalline polypropylene, and the random polypropylene. Regarding the blending ratio of each of the plurality of types of polypropylene resins based on the mass of the resin composition, the highly crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, the low-crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, and the random polypropylene is in the range of 10% by mass or more and 20% by mass or less.

Advantages of the Invention

[0007] According to one aspect of the present disclosure, it is possible to provide a cosmetic sheet, a cosmetic member, and a method for manufacturing a cosmetic sheet that maintain the scratch resistance, film formability, and transparency of the transparent resin layer required in actual use, are excellent in bender bending processability (post-processing property), and are provided with designability by the low-gloss layer.

Brief Description of the Drawings

[0008]

Figure 1

Modes for Carrying Out the Invention

[0009] The inventors have conducted intensive research and found that when a low-gloss layer is provided on a transparent resin layer formed of a resin composition containing a plurality of types of polypropylene resins in a cosmetic sheet, by satisfying specific conditions for the blending ratio of each of the plurality of types of polypropylene resins, it is possible to improve the surface strength (scratch resistance), film-forming property, and suppress the reduction of the transparency of the transparent resin layer of the cosmetic sheet, while improving the post-processing property (bender bending processability). As a result, the inventors have invented a cosmetic sheet that maintains the scratch resistance, film-forming property, and transparency of the transparent resin layer required in actual use, is excellent in bender bending processability (post-processing property), and has design properties due to the low-gloss layer.

[0010] Hereinafter, a cosmetic sheet and a cosmetic member according to an embodiment of the present disclosure will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, etc. are different from the actual ones. Further, the embodiments shown below are examples of configurations for embodying the technical idea of the present disclosure, and the technical idea of the present disclosure is not limited to the materials, shapes, structures, etc. of the constituent parts being the following. The technical idea of the present disclosure can be variously modified within the technical scope defined by the claims described in the claims. Also, the directions of "left and right" and "up and down" in the following description are merely definitions for convenience of explanation and do not limit the technical idea of the present disclosure. Therefore, for example, if the paper surface is rotated 90 degrees, "left and right" and "up and down" are read in exchange, and if the paper surface is rotated 180 degrees, "left" becomes "right" and "right" becomes "left", of course.

[0011] <Configuration of Cosmetic Sheet and Cosmetic Member> Fig. 1 shows a cross-sectional structure of an embodiment of a cosmetic sheet and a cosmetic member according to this embodiment. In the cosmetic sheet 1 of this embodiment, a plurality of resin layers are laminated on the surface side of the base material layer 6, and a transparent resin layer 3 is disposed as the resin layer on the surface side among the plurality of resin layers. Specifically, as shown in Fig. 1, in the cosmetic sheet 1 of this embodiment, a pattern layer 5, a transparent resin layer 3, a surface protective layer 2, and a low-luster pattern layer 9 are laminated in this order on one surface (front surface) of the base material layer 6 constituting the raw sheet. Reference numeral 4 indicates an adhesive layer. Further, a concealing layer 7 and a primer layer 8 are formed in this order on the other surface (back surface) of the base material layer 6. Note that the concealing layer 7 may be formed between the base material layer 6 and the pattern layer 5, or may be omitted. The cosmetic sheet 1 according to this embodiment may include a necessary layer among the layers shown in Fig. 1 according to the application, and may have at least the transparent resin layer 3 and the low-luster pattern layer 9 for improving the design.

[0012] (Design Expression of Sheet) In the cosmetic sheet 1 of this embodiment, a surface protective layer 2 formed by coating a resin between the transparent resin layer 3 and the low-luster pattern layer 9 is provided. The luster (gloss) of the low-luster pattern layer 9 may be lower than that of the surface protective layer 2. The cosmetic sheet 1 is obtained by subjecting the surface to a gloss sheet printing process. Gloss sheet printing is a technique that gives an observer an impression that the surface has irregularities by forming patterns with different glosses on the surface of the cosmetic sheet by printing. In this embodiment, the low-luster pattern layer 9 is formed on a part of the surface protective layer 2, and the gloss of the low-luster pattern layer 9 is made lower than that of the surface protective layer 2.

[0013] Also, in the example shown in Fig. 1, the surface protective layer 2 is formed on the entire surface of the transparent resin layer 3, and the low-luster pattern layer 9 is formed on a part of the surface of the surface protective layer 2. Therefore, on the surface of the cosmetic sheet 1, a part of the surface protective layer 2 and the low-luster pattern layer 9 are visually recognized at the same time. In the decorative sheet 1, the surface protection layer 2 (and the transparent resin layer 3) with relatively high glossiness appears protruding, and the low-gloss pattern layer 9 with relatively low glossiness appears recessed. For this reason, the decorative sheet 1 produces a visual effect such that convex portions of the surface protection layer 2 visible from between the concave portions of the pattern of the low-gloss pattern layer 9 and the low-gloss pattern layer 9 are formed on the surface.

[0014] Note that the present embodiment is not limited to a configuration in which a pattern of a layer with relatively low glossiness is provided on a layer with relatively high glossiness. For example, a pattern of a layer with relatively high glossiness may be provided on a layer with relatively low glossiness. Also, patterns of the surface protection layer 2 and the low-gloss pattern layer 9 may be respectively formed on the transparent resin layer 3. In any of such configurations, a layer with relatively high glossiness (luster) appears protruding and a layer with relatively low glossiness appears recessed to an observer. Also, the low-gloss pattern layer 9 may be formed over the entire surface of the outermost surface of the surface protection layer 2 (the surface opposite to the transparent resin layer 3) to provide a low-gloss expression over the entire surface of the decorative sheet. Thereby, for example, a low-gloss texture (matte feeling) similar to a natural material can be imparted to improve the design property.

[0015] Also, the layer thickness of the decorative sheet 1 having the above configuration is, for example, considering printing workability, cost, etc., the surface protection layer 2 is 3 to 20 μm, the transparent resin layer 3 is 20 to 200 μm, the adhesive layer 4 is 1 to 20 μm, the pattern layer 5 is 0.1 to 20 μm, the base material layer 6 is 20 to 150 μm, the concealing layer 7 is 2 to 20 μm, the primer layer 8 is 0.1 to 20 μm, and the low-gloss pattern layer 9 is in the range of 1 μm or more and 15 μm or less, and the total thickness of the decorative sheet 1 is in the range of 49 to 450 μm. Note that in FIG. 1, a case where the decorative sheet 1 of the present embodiment is attached to the base material B to form the decorative member 10 is illustrated.

[0016] <Base material layer 6> The base material layer 6 is composed of paper, a resin sheet, foil, etc. Examples of the paper include tissue paper, titanium paper, resin-impregnated paper, organic or inorganic non-woven fabric, synthetic paper, etc. Examples of the resin of the resin sheet include synthetic resins such as polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic, or foams of these synthetic resins, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, rubber such as polyurethane. Examples of the foil include metal foils such as aluminum, iron, gold, silver, etc.

[0017] <Pattern layer 5> The pattern layer 5 is a layer that contributes to the design of the decorative sheet with an arbitrary pattern 5a and can be provided using known printing methods. When the base material layer 6 can be prepared in a wound state, printing for forming the pattern layer 5 can be performed with a roll-to-roll printing device. The printing method is not particularly limited, but considering productivity and the quality of the pattern, for example, the gravure printing method can be used. The pattern layer 5 is on the side opposite to the low-gloss pattern layer 9 side of the transparent resin layer 3 and is provided on the base material layer 6. The pattern design (an example of a pattern) 5a may adopt any pattern or design in consideration of the design characteristics according to the usage locations such as floor materials and wall materials. As the pattern design 5a, various wood grains are often preferably used if it is a wood-based pattern, and cork can also be used in addition to the wood grains. For example, if the pattern design 5a is an image of a stone floor such as marble, the marble grain may be used. In addition to the pattern designs of natural materials, artificial pattern designs such as artificial pattern designs and geometric patterns with them as motifs can also be used as the pattern design 5a. The color of the pattern design 5a may be different from that of other areas (areas other than the pattern design 5a) of the pattern design layer 5. For example, the pattern design 5a may be expressed in a darker color than other areas. Thereby, by arranging the pattern design 5a so as to overlap with the low-luster pattern layer 9 in plan view, a deeper shadow can be expressed and the design characteristics can be improved.

[0018] Note that the pattern design layer 5 may have the pattern design 5a and the areas other than the pattern design 5a as separate layers respectively. That is, the pattern design layer 5 may have a multi-layer structure. In this case, a pattern printing layer corresponding to the pattern design 5a may be formed on the solid printing layer (corresponding to the areas other than the pattern design 5a).

[0019] Regarding the printing ink, although it is not particularly limited, an ink corresponding to the printing method can be appropriately selected. It is preferably selected in consideration of, in particular, the adhesion to the resin base material layer 6, the printability, and the weather resistance as a decorative member. To the printing ink, colorants such as pigments and dyes, extender pigments, solvents, and binders that are normally contained in ordinary inks are added as appropriate. Examples of pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica. Note that the binder may be of any of the aqueous, solvent-based, and emulsion types, and the curing method is not particularly limited, such as a one-component type, a two-component type consisting of a main agent and a curing agent, or a type that cures by ultraviolet rays, electron beams, etc. Among them, the most common method is the two-component type, which uses a urethane-based main agent and a curing agent composed of isocyanate. In addition to this, designs may be applied by vapor deposition or sputtering of various metals.

[0020] <Adhesive layer 4> The adhesive layer 4 is provided for the purpose of firmly bonding the base material layer 6, the pattern layer 5, and the transparent resin layer 3. By having strong adhesion, bendability that follows curved surfaces or right-angled surfaces can be imparted to the decorative sheet 1. The adhesive layer 4 is preferably transparent. As for the bonding method of the adhesive layer 4, any material can be selected, and there are lamination methods such as thermal lamination, extrusion lamination, and dry lamination. The adhesive can be appropriately selected from acrylic, polyester, polyurethane, epoxy, etc. Usually, due to its cohesive force, it is of the two-component curing type, and it is particularly desirable to use a urethane-based material obtained by the reaction of a polyol using isocyanate. Note that the adhesive layer 4 may be omitted when sufficient adhesive strength between the transparent resin layer 3 and the pattern layer 5 is obtained.

[0021] <Transparent resin layer 3> The transparent resin layer 3 is manufactured and laminated, for example, as a transparent resin sheet. The transparent resin layer 3 is formed using a resin composition containing a plurality of types of polypropylene resins (hereinafter also referred to as "PP resins"). Specifically, the resin composition forming the transparent resin layer 3 contains a highly crystalline polypropylene resin, a low-crystalline polypropylene resin, and a random polypropylene resin as the plurality of types of polypropylene resins. When improving the post-processing property (bender bending processability) in a transparent resin layer containing a highly crystalline PP resin and a low-crystalline PP resin, it is necessary to increase the addition ratio of the low-crystalline PP resin to the highly crystalline PP resin. However, as the addition ratio of the low-crystalline PP resin increases, the softness increases, which may lead to a reduction in scratch resistance and film-forming property. In the cosmetic sheet 1 according to the present embodiment, by using a random PP resin in addition to the highly crystalline PP resin and the low-crystalline PP resin as described above, it is possible to improve the bender bending processability while suppressing a reduction in scratch resistance and film-forming property. Hereinafter, the details of each polypropylene resin will be described.

[0022] [Highly crystalline polypropylene resin] The highly crystalline polypropylene resin contained in the transparent resin layer 3 can be appropriately selected and designed from, for example, isotactic polypropylene, syndiotactic polypropylene, random polypropylene, block polypropylene, and mixtures thereof having different pentad fractions. In the present embodiment, it is preferable that the highly crystalline polypropylene resin is a highly crystalline homopolypropylene resin that is a homopolymer of propylene having a pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more. Also, considering the film-forming property and scratch resistance, the MFR of the highly crystalline polypropylene resin at 230°C can be designed within the range of 0.5 g / 10 min or more and 30 g / 10 min or less (more preferably within the range of 10 g / 10 min or more and 25 g / 10 min or less).

[0023] Note that the above pentad fraction (mmmm fraction) uses carbon C (nuclide) with a mass number of 13 13It is calculated from the numerical value (electromagnetic wave absorption rate) obtained by resonating the resin composition constituting the transparent resin layer 3 at a predetermined resonance frequency by means of 13C-NMR measurement (nuclear magnetic resonance measurement). And this pentad fraction (mmmm fraction) defines the atomic arrangement, electronic structure, and fine structure of the molecule in the resin composition. The pentad fraction of the polypropylene resin is 13 the ratio of five consecutive propylene units determined by 13C-NMR, and is used as a measure of crystallinity or stereoregularity. And such a pentad fraction is one of the important factors that mainly determine the scratch resistance of the surface. Basically, the higher the pentad fraction, the higher the crystallinity of the sheet, and thus the scratch resistance is improved. And by using a highly crystalline polypropylene resin as the main component of the transparent resin layer 3, the surface strength (scratch resistance) of the decorative sheet is increased.

[0024] [Low crystalline polypropylene resin] The low crystalline polypropylene resin added to the transparent resin layer 3 is preferably a polypropylene resin that satisfies at least one of the following characteristics. · The mesopentad fraction is 20% or more and 60% or less (More preferably, 40% or more and 55% or less) · The MFR at 230 °C is 30 g / 10 min or more and 100 g / 10 min or less (More preferably, 30 g / 10 min or more and 60 g / 10 min or less) · The mass average molecular weight (Mw) is 10,000 or more and 500,000 or less (More preferably, 50,000 or more and 200,000 or less) · The molecular weight distribution (Mw / Mn) is less than 4 · The melting point defined as the peak top of the peak observed on the highest temperature side of the melting endotherm curve obtained by using a differential scanning calorimeter (DSC), holding at -10 °C for 5 minutes in a nitrogen atmosphere and then heating at a rate of 10 °C / min is 0 °C or more and 120 °C or less (More preferably, 40 °C or more and 100 °C or less)

[0025] The low-crystalline polypropylene resin tends to have properties such as low crystallinity, softness, low melting point, and high solubility in solvents. By adopting such a low-crystalline polypropylene resin, when added to a high-crystalline polypropylene resin, it has properties such as high compatibility and retarded crystallization rate, and has little or significantly low impact on the crystallinity of the high-crystalline polypropylene resin.

[0026] [Random polypropylene resin] As the random polypropylene resin added to the transparent resin layer 3, it is preferably in the range of 10 g / 10 min or more and 50 g / 10 min or less in terms of MFR at 230°C (more preferably, in the range of 10 g / 10 min or more and 30 g / 10 min or less in terms of MFR at 230°C). By setting the MFR of the random polypropylene resin between the MFR of the aforementioned high-crystalline polypropylene resin and the MFR of the aforementioned low-crystalline polypropylene resin in this way, the compatibility of the three types of PP resins in the molten state can be enhanced, and the film-forming property of the transparent resin layer 3 can be made better. Also, the random PP resin used for the transparent resin layer 3 in the present embodiment preferably has a tensile modulus of elasticity defined by JIS K 7161 of 300 MPa to 1000 MPa (more preferably 500 MPa to 800 MPa).

[0027] Next, the blending ratio MR1 of the high-crystalline PP resin, the blending ratio MR2 of the low-crystalline PP resin, and the blending ratio MR3 of the random PP resin based on the mass of the resin composition forming the transparent resin layer 3 will be described.

[0028] In the present embodiment, the blending ratio MR3 of the random PP resin in the transparent resin layer 3 is less than either the blending ratio MR1 of the PP resin and the blending ratio MR2 of the low-crystalline PP resin (MR1 > MR3 and MR2 > MR3). That is, the random PP resin has the lowest blending ratio in the resin composition forming the transparent resin layer 3 among the plurality of types (three types in this example) of PP resins. Therefore, as the PP resin contained in the resin composition for forming the transparent resin layer 3, the addition amount of the random PP resin is the least, and the addition amounts of the highly crystalline PP resin and the lowly crystalline PP resin are both larger than that of the random PP resin.

[0029] More specifically, based on the mass of the resin composition for forming the transparent resin layer 3, the blending ratio MR1 of the highly crystalline PP resin is preferably in the range of 30% by mass or more and 50% by mass or less, the blending ratio MR2 of the lowly crystalline PP resin is preferably in the range of 30% by mass or more and 50% by mass or less, and the blending ratio MR3 of the random PP resin is preferably in the range of 10% by mass or more and 20% by mass or less in the transparent resin layer 3. More preferably, the blending ratio MR1 of the highly crystalline PP resin is in the range of 40% by mass or more and 50% by mass or less, the blending ratio MR2 of the lowly crystalline PP resin is in the range of 35% by mass or more and 45% by mass or less, and the blending ratio MR3 of the random PP resin is in the range of 10% by mass or more and 20% by mass or less. By setting the blending ratios of the three types of PP resins in the transparent resin layer 3 as described above, it is possible to maintain the scratch resistance, film formability, and transparency required in actual use. Furthermore, the stress applied to the decorative sheet during bending can be well dispersed, and the concentration of stress on the low-gloss pattern layer 9 can be suppressed, thereby imparting excellent bender bend processability (post-processability) to the transparent resin layer 3. Therefore, it is possible to provide the decorative sheet 1 having the transparent resin layer 3 excellent in bender bend processability (post-processability) while maintaining the scratch resistance, film formability, and transparency required in actual use.

[0030] On the one hand, when the blending ratio MR1 of the highly crystalline PP resin is less than 30% by mass, the softness of the low-crystalline PP resin and the random PP resin has a greater influence, so the scratch resistance (surface hardness of the decorative sheet 1) may decrease. Furthermore, when the blending ratio MR1 of the highly crystalline PP resin exceeds 50% by mass, the appropriate softness provided by the low-crystalline PP resin and the random PP resin to ensure good post-processing properties cannot be exerted, and the post-processing properties (bender bending processability in this example) of the decorative sheet 1 may decrease. For example, during bending, cracks or fractures may occur in the transparent resin layer 3, or cracks or fractures may occur in the low-gloss pattern layer 9 because the stress applied to the decorative sheet is not sufficiently dispersed. Also, when the blending ratio MR2 of the low-crystalline PP resin is less than 30% by mass, the appropriate flexibility for good post-processing properties cannot be imparted, and the post-processing properties (bender bending processability) of the decorative sheet 1 may decrease. Furthermore, when the blending ratio MR2 of the low-crystalline PP resin exceeds 50% by mass, the softness increases excessively, and neck-in or film breakage may occur during film formation, reducing the film-forming properties of the transparent resin layer 3. Here, the film-forming property indicates that film can be formed without problems during the melt extrusion of the transparent resin layer 3. Also, when the blending ratio MR3 of the random PP resin is less than 10% by mass, neck-in or film breakage may occur during film formation, reducing the film-forming properties of the transparent resin layer 3. Also, when the blending ratio MR3 of the random PP resin exceeds 20% by mass, the compatibility between the highly crystalline PP resin and the low-crystalline PP resin is inhibited, resulting in cloudiness in the transparent resin layer and reducing the transparency of the transparent resin layer 3.

[0031] In this way, by setting the blending ratios MR1, MR2, and MR3 of the three types of polypropylene resins as described above, it is possible to provide a decorative sheet 1 having a transparent resin layer 3 with excellent bender bending processability (post-processing properties) while reliably maintaining high scratch resistance, film-forming properties, and transparency.

[0032] In addition, in the present embodiment, the magnitude relationship between the blending ratio MR1 of the highly crystalline PP resin and the blending ratio MR2 of the low-crystalline PP resin is not particularly limited. That is, in the transparent resin layer 3, the blending ratio MR1 of the highly crystalline PP resin may be greater than the blending ratio MR2 of the low-crystalline PP resin (MR1>MR2). Also, the blending ratio MR2 of the low-crystalline PP resin may be greater than the blending ratio MR1 of the highly crystalline PP resin (MR1<MR2). Further, the blending ratio MR1 of the highly crystalline PP resin and the blending ratio MR2 of the low-crystalline PP resin may be equal (MR1=MR2). In addition, when the blending ratio MR2 of the low-crystalline PP resin is greater than the blending ratio MR1 of the highly crystalline PP resin (MR1<MR2), it is preferable that the difference between the blending ratio MR2 of the low-crystalline PP resin and the blending ratio MR1 of the highly crystalline PP resin is less than 20% by mass (MR2 - MR1<20% by mass). Thereby, even when the blending ratio of the low-crystalline PP resin is the highest in the transparent resin layer, the softness can be suitably controlled, and the scratch resistance and film-forming properties can be improved together with the bending processability of the bender.

[0033] Moreover, in the cosmetic sheet 1 according to the present embodiment, the transparent resin layer 3 is not limited to the above configuration. In the transparent resin layer 3 of the present embodiment, the tensile elastic modulus of the low-crystalline PP resin contained in the resin composition may be 25 MPa or more and 500 MPa or less, more preferably 50 MPa or more and 120 MPa or less. Also, in this case, the low-crystalline PP resin may be added in an amount of 0.1 to 20 parts by mass with respect to 100 parts by mass of the highly crystalline PP resin. By making the blending ratio of the highly crystalline polypropylene resin the highest in the transparent resin layer 3, the surface strength (scratch resistance) of the cosmetic sheet can be further improved. In addition, since the low-crystalline polypropylene resin exhibits high compatibility with the highly crystalline polypropylene resin, by adding a low-crystalline polypropylene resin having a tensile elastic modulus in the above range, high transparency can be imparted to the transparent resin layer 3 while improving the post-processability. Furthermore, by setting the addition amount of the low-crystalline polypropylene resin within the above range, the scratch resistance and post-processability of the cosmetic sheet can be made better.

[0034] <Surface protection layer 2> On the outermost surface of the cosmetic sheet 1, a surface protective layer 2 is provided which serves to protect the surface and adjust the gloss. The surface protective layer 2 is provided between a transparent resin layer 3 and a low-gloss pattern layer 9. As shown in Fig. 1, the low-gloss pattern layer 9 is provided on at least a part of the surface of the surface protective layer 2 (the surface opposite to the transparent resin layer 3). Note that the low-gloss pattern layer 9 may be provided on the entire surface of the surface protective layer 2 to make the entire outermost surface of the cosmetic sheet 1 a matte design. As the material of the surface protective layer 2, it can be appropriately selected and used from polyurethane-based, acrylic-silicone-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based, urea-based, etc. The form of the material is not particularly limited, such as aqueous, emulsion, solvent-based, etc. Regarding the curing method, it can be appropriately selected and carried out, such as one-component type, two-component type, ultraviolet curing method, etc.

[0035] In particular, as the main component of the surface protective layer 2, urethane-based ones using isocyanate are suitable from the viewpoints of workability, price, cohesive force of the resin itself, etc. For isocyanate, tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), methylhexane diisocyanate (HTDI), methylcyclohexanone diisocyanate (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc. can be appropriately selected. Considering weather resistance, hexamethylene diisocyanate (HMDI) having a linear molecular structure is suitable. In addition, when aiming to improve the surface hardness, a resin cured by active energy rays such as ultraviolet rays or electron beams may be used. These resins can be used in combination with each other. For example, by making a hybrid type of thermosetting type and photocuring type, improvement of surface hardness, suppression of curing shrinkage, and improvement of adhesion can be achieved. In addition, the surface protection layer 2 only needs to have higher gloss (luster) than the low-luster pattern layer 9. The urethane resin used for the surface protection layer 2 may contain a gloss resin and a matte resin of an acrylic-modified resin and a curing agent. The composition and amount of the gloss resin and the matte resin are appropriately determined according to the gloss required for the surface protection layer 17.

[0036] <Low-luster pattern layer> The low-luster pattern layer 9 is provided on the transparent resin layer 3 and is formed of a resin containing a matting agent (for example, matte ink). More specifically, the low-luster pattern layer 9 is provided on at least a part of the surface of the surface protection layer 2 (the surface opposite to the transparent resin layer 3). The low-luster pattern layer 9 is arranged so as to at least partially overlap with the pattern 5a of the pattern layer 5 in plan view. That is, at least a part of the low-luster pattern layer 9 and the pattern of the pattern layer overlap in plan view. Thereby, the low-luster pattern layer 9 and the pattern 5a of the pattern layer 5 are synchronized and the visual unevenness is more emphasized, and the design property can be improved. As shown in FIG. 1, the low-luster pattern layer 9 may be formed so as to draw the same pattern as the pattern 5a of the pattern layer 5 on the surface protection layer 2. Further, the low-luster pattern layer 9 may be provided on the entire surface of the surface protection layer 2. In this case, the outermost surface of the decorative sheet 1 can be made into a matte design. The low-luster pattern layer 9 can be formed of a urethane resin. This urethane resin may contain an acrylic resin as matte ink and an isocyanate resin as a curing agent. The composition and amount of the matte ink are appropriately determined according to the gloss required for the low-luster pattern layer 9.

[0037] In this embodiment, similar to the surface protection layer 2, a resin curable by active energy rays such as ultraviolet rays or electron beams can be used for the low-luster pattern layer 9. It can be formed by a printing method using any one of ultraviolet curable resins, thermosetting resins, and photocurable resins, or a hybrid type of two or more of these.

[0038] Hereinafter, the low-luster pattern layer 9 will be described in more detail. As described above, the thickness of the low-gloss pattern layer 9 is preferably 1 μm or more and 15 μm or less. Furthermore, since the low-gloss pattern layer 9 is the outermost layer of the decorative sheet 1, it is required to have surface properties such as abrasion resistance, scratch resistance, solvent resistance, and contamination resistance, which are necessary for the decorative sheet 1. In particular, abrasion resistance and scratch resistance are affected by the layer thickness, and a thicker layer is more advantageous. Therefore, a more preferable layer thickness of the low-gloss pattern layer 9 is 2 μm or more and 12 μm or less. If it is less than 1 μm, the abrasion resistance and scratch resistance will be significantly reduced, limiting its use as a decorative sheet 1. Furthermore, if it is more than 15 μm, the flexibility will be reduced, resulting in poor processability as a decorative sheet 1. The low gloss pattern layer 9 includes at least a resin material and a gloss adjusting agent added to the resin material.

[0039] [Resin component] The main material of the resin component constituting the low gloss pattern layer 9 can be a urethane-based thermosetting resin having a polyol and an isocyanate, or a mixture of such a urethane-based curing resin and an ionizing radiation curing resin having an acrylic group or a methacrylic group. Here, the ionizing radiation curable resin having the above-mentioned acrylic or methacrylic group can be any known material, such as various monomers or commercially available oligomers. However, it is preferable to use polyfunctional monomers such as pentaerythritol triacrylate (PET3A), pentaerythritol tetraacrylate (PET4A), trimethylolpropane triacrylate (TMPTA), dipentaerythritol hexaacrylate (DPHA), polyfunctional oligomers such as Shikoh UV-1700B manufactured by Nippon Synthetic Chemical Industry, or mixtures of these.

[0040] In addition, as the isocyanate in the urethane-based thermosetting resin composed of the above polyol and isocyanate, adducts, burettes, and isocyanurates, which are derivatives such as tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), methylhexane diisocyanate (HTDI), bis(isocyanatomethyl)cyclohexane (HXDI), trimethylhexamethylene diisocyanate (TMDI), etc., can be used as curing agents. As the polyol, acrylic polyol, polycarbonate polyol, polyester polyol, etc. can be used.

[0041] In addition, as the radiation-curable resin having an acrylic group or a methacrylic group that constitutes the low gloss pattern layer 9, it is preferable to use a polyfunctional (meth)acrylate monomer or oligomer having a number average molecular weight of 300 or more and 5000 or less, and a functional group number or average functional group number of 4 or more and 15 or less. By setting it within this range, the crosslinking degree of the resin component in the gloss adjustment layer can be sufficiently increased, so that high scratch resistance can be exhibited. Further, it is more preferable to use a polyfunctional (meth)acrylate monomer having a number average molecular weight of 300 or more and 1500 or less, and a functional group number or average functional group number of 4 or more and 8 or less. By setting it within this range, the viscosity of the radiation-curable resin itself can be lowered, so that when preparing the ink for forming the gloss adjustment layer, the solid content concentration at the same viscosity can be increased, and the stability of the ink itself and the coating state can be improved. Examples of the polyfunctional (meth)acrylate monomer include pentaerythritol tetra(meth)acrylate (PET4A) and its modified products, ditrimethylolpropane tetra(meth)acrylate and its modified products, dipentaerythritol penta(meth)acrylate (DPPA) and its modified products, dipentaerythritol hexa(meth)acrylate (DPHA) and its modified products.

[0042] The method for measuring the number average molecular weight of the above ionizing radiation-curable resin is not particularly limited, but it is preferable to use gel permeation chromatography (GPC). The measuring device is not particularly limited, but the packing material of the GPC column is preferably polystyrene gel, and it is preferable to use tetrahydrofuran (THF) as the eluent. Also, a commercially available standard polystyrene polymer may be used as the standard substance for GPC. Regarding the above polyfunctional (meth)acrylate monomer, since it is composed of a single substance, if its structure is known, the number average molecular weight may be the value calculated from the structural formula.

[0043] [Gloss adjuster] In the present embodiment, as the gloss adjuster added to the low-gloss pattern layer 9, fine particles of an inorganic material having a hydrophobic surface (hydrophobic inorganic material) may be used, or a known commercially available gloss adjuster or the like may be used. It is preferable that the hydrophobic inorganic material has been surface-treated or surface-modified with some organic compound. As the hydrophobic inorganic material, for example, known inorganic materials that have been surface-treated or surface-modified, that is, hydrophobized with some organic compound on the surface, can be used. Examples of the gloss adjuster that can constitute such a hydrophobic inorganic material include fine particles composed of inorganic materials such as silica, glass, alumina, calcium carbonate, and barium sulfate. The surface of the inorganic material that has been surface-treated or surface-modified is hydrophobic because the hydroxyl groups present on the surface during the production of the inorganic material have almost disappeared or are coated. Therefore, it is possible to suppress the adsorption of hydrophilic contaminants and the penetration into the voids present at the interface between the lower layer (surface protection layer 2, transparent resin layer 3) and the matting agent, and thus excellent stain resistance can be exhibited.

[0044] In addition, fine particles made of organic materials such as acrylic can be used as the gloss adjuster. However, when high transparency is required, it is desirable to use fine particles of silica, glass, acrylic, etc. with high transparency. In particular, among fine particles such as silica and glass, a gloss adjuster with a low bulk density formed by secondary aggregation of fine primary particles rather than solid spherical particles has a high gloss elimination effect with respect to the addition amount. Therefore, by using such a gloss adjuster, the addition amount of the gloss adjuster can be reduced.

[0045] The particle size of the gloss adjuster can be selected as any value, but it is preferably 2 μm or more and 15 μm or less. More preferably, it is 4 μm or more and 12 μm or less. When the particle size of the gloss adjuster is less than 2 μm, the gloss elimination effect is low, so the unevenness due to the difference in gloss cannot be sufficiently obtained. Also, when the particle size of the gloss adjuster is larger than 15 μm, the light scattering becomes large. Therefore, when the gloss adjuster is added, cloudiness may occur or the particle feeling by visual observation may become large, and the unevenness due to the difference in gloss may be conversely impaired.

[0046] <Hidden layer 7> The hidden layer 7 is formed by printing, for example, in the same manner as the pattern layer 5, for the purpose of maintaining concealment. As the pigment to be included in the ink, it is preferable to use an opaque pigment, titanium oxide, iron oxide, etc. It is also possible to add metals such as gold, silver, copper, and aluminum to improve the concealment. Generally, flaky aluminum is often added. Note that the hidden layer 7 can be omitted when the base material layer 6 is opaque and has concealment.

[0047] <Primer layer 8> The primer layer 8 is formed to improve the adhesion to the base material B. When the base material B is a wood-based base material, the primer layer 8 can include, for example, ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, etc. These resins can be used alone or in combination to form an adhesive composition, and can be formed using appropriate coating means such as roll coating or gravure printing. In this case, as the resin constituting the primer layer 8, a urethane-acrylate resin is preferred, that is, it is particularly preferred to be formed from a copolymer of an acrylic resin and a urethane resin and an isocyanate.

[0048] <Base material B> In this embodiment, the above-described decorative sheet 1 may be bonded to the base material B to form a decorative member 10. The decorative member 10 according to this embodiment includes a base material B and a decorative sheet 1 provided on at least one surface side of the base material B. As the base material B in the decorative member 10, for example, wood-based base materials such as MDF (Medium density fiberboard), particle board, and plywood can be used. Also, as the base material B, metal-based base materials such as steel plates and aluminum plates, and resin-based base materials such as PET, PVC, and ABS can be used. By bonding the decorative sheet 1 onto the base material B, a decorative member 11 having a transparent resin layer with excellent bendability (post-processing property) can be obtained while maintaining the scratch resistance, film-forming property, and transparency required in actual use.

[0049] <Effects of this embodiment> (1) The cosmetic sheet 1 according to this embodiment includes a transparent resin layer 3 formed of a resin composition containing a plurality of types of polypropylene resins, and a low-gloss pattern layer 9 provided on the transparent resin layer 3 and formed of a resin containing a matting agent. The resin composition includes highly crystalline polypropylene, low-crystalline polypropylene, and random polypropylene as the plurality of types of polypropylene resins. The blending ratio of each of the plurality of types of polypropylene resins based on the mass of the resin composition is such that the highly crystalline polypropylene is within the range of 30% by mass or more and 50% by mass or less, the low-crystalline polypropylene is within the range of 30% by mass or more and 50% by mass or less, and the random polypropylene is within the range of 10% by mass or more and 20% by mass or less. According to this configuration, it is possible to provide a cosmetic sheet that maintains the scratch resistance, film-forming property, and transparency of the transparent resin layer 3 required in actual use, is excellent in bendability (post-processing property), and has designability due to the low-gloss pattern layer 9. (2) In the cosmetic sheet 1, a surface protection layer 2 is provided between the transparent resin layer 3 and the low-gloss pattern layer 9, and the low-gloss pattern layer 9 may be provided on at least a part of the surface of the surface protection layer 2. According to this configuration, it is possible to improve the designability while enabling the protection of the surface of the cosmetic sheet and the adjustment of gloss. (3) In the cosmetic sheet 1, a pattern layer 5 is provided on the side of the transparent resin layer 3 opposite to the low-gloss pattern layer 9 side, and at least a part of the pattern 5a of the low-gloss pattern layer 9 and the pattern layer 5 may overlap in a plan view. According to this configuration, the pattern 5a of the low-gloss pattern layer 9 and the pattern layer 5 are synchronized to more strongly emphasize the visual unevenness, and the designability can be improved. (4) In the cosmetic sheet 1, the MFR (melt flow rate) of the random polypropylene in the transparent resin layer 3 at 230 °C may be within the range of 10 g / 10 min or more and 50 g / 10 min or less. According to this configuration, the compatibility of the three types of PP resins in the molten state can be enhanced, and the film-forming property of the transparent resin layer 3 can be made better. (5) In the cosmetic sheet 1, the low-crystalline polypropylene in the transparent resin layer 3 may have a mesopentad fraction of 20% or more and 60% or less. According to this configuration, when the low-crystalline polypropylene is added to the high-crystalline polypropylene, it has the performance of high compatibility and retardation of crystallization rate, and has little or significantly reduced influence on the crystallinity of the high-crystalline polypropylene. (6) In the cosmetic sheet 1, the low-crystalline polypropylene in the transparent resin layer 3 may have an MFR (melt flow rate) at 230 °C of 30 g / 10 min or more and 100 g / 10 min or less. According to this configuration, similar to the above (5), when the low-crystalline polypropylene is added to the high-crystalline polypropylene, it has the performance of high compatibility and retardation of crystallization rate, and has little or significantly reduced influence on the crystallinity of the high-crystalline polypropylene. (7) In the cosmetic sheet 1, the low-crystalline polypropylene in the transparent resin layer 3 may have a mass average molecular weight (Mw) of 10,000 or more and 500,000 or less. According to this configuration, similar to the above (5) and (6), when the low-crystalline polypropylene is added to the high-crystalline polypropylene, it has the performance of high compatibility and retardation of crystallization rate, and has little or significantly reduced influence on the crystallinity of the high-crystalline polypropylene. (8) In the cosmetic sheet 1, the molecular weight distribution (Mw / Mn) of the low-crystalline polypropylene in the transparent resin layer 3 may be less than 4. According to this configuration, similar to the above (5) to (7), when the low-crystalline polypropylene is added to the high-crystalline polypropylene, it has the performance of high compatibility and retardation of crystallization rate, and has little or significantly reduced influence on the crystallinity of the high-crystalline polypropylene. (9) In the cosmetic sheet 1, the low-crystalline polypropylene in the transparent resin layer 3 may have a melting point defined as the peak top of the peak observed on the highest temperature side of the endothermic melting curve obtained by holding at -10°C for 5 minutes in a nitrogen atmosphere and then raising the temperature at a rate of 10°C / min using a differential scanning calorimeter (DSC) within a range of 0°C or higher and 120°C or lower. According to this configuration, similar to the above (5) to (8), when the low-crystalline polypropylene is added to the high-crystalline polypropylene, it has properties such as high compatibility and slow crystallization rate, and has little or significantly reduced influence on the crystallinity of the high-crystalline polypropylene resin. (10) The cosmetic member 10 according to the present embodiment includes a base material B and a cosmetic sheet 1 provided on at least one surface side of the base material B. According to this configuration, it is possible to provide a cosmetic member that maintains the scratch resistance, film-forming property, and transparency of the transparent resin layer 3 required in actual use, is excellent in bender bending processability (post-processing property), and has the design property provided by the low-gloss pattern layer 9. (11) The manufacturing method of the cosmetic sheet 1 according to the present embodiment forms the transparent resin layer 3 using a resin composition containing a plurality of types of polypropylene resins, forms a low-gloss pattern layer 9 formed of a resin containing a matting agent on the transparent resin layer 3, the plurality of types of polypropylene resins are the high-crystalline polypropylene, the low-crystalline polypropylene, and the random polypropylene, and regarding the blending ratio of each of the plurality of types of polypropylene resins based on the mass of the resin composition, the high-crystalline polypropylene is within a range of 30% by mass or more and 50% by mass or less, the low-crystalline polypropylene is within a range of 30% by mass or more and 50% by mass or less, and the random polypropylene is within a range of 10% by mass or more and 20% by mass or less. According to this configuration, it is possible to provide a manufacturing method of a cosmetic sheet that maintains the scratch resistance, film-forming property, and transparency of the transparent resin layer 3 required in actual use, is excellent in bender bending processability (post-processing property), and has the design property provided by the low-gloss pattern layer 9.

[0050] <Example> Hereinafter, the present disclosure will be described in detail by showing examples and comparative examples, but the present disclosure is not limited to the following examples.

[0051] In addition, the highly crystalline polypropylene resin and the low crystalline polypropylene resin used in this example were as follows.

[0052] (Highly crystalline polypropylene resin) A highly crystalline homopolypropylene resin with a pentad fraction of 97.8%, a MFR (melt flow rate) of 15 g / 10 min (230 °C), and a molecular weight distribution MWD (Mw / Mn) of 2.3 was used. In addition, to the above highly crystalline polypropylene resin, 500 PPM of a hindered phenol antioxidant (Irganox 1010: manufactured by BASF), 2000 PPM of a benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by BASF), and 2000 PPM of a hindered amine light stabilizer (Chimasorb 944: manufactured by BASF) were added.

[0053] (Low crystalline polypropylene resin) The compositions of the low crystalline polypropylene resins A-C used in this example are shown in Table 1.

[0054]

Table 1

[0055] (Random polypropylene resin) “Prime Polypro Y-2045GP (MFR 24 g / 10 min (230 °C), tensile modulus 650 MPa)” and “Prime Polypro S235WC (MFR 11 g / 10 min (230 °C), tensile modulus 650 MPa)” (both manufactured by Prime Polymer Co., Ltd.) were used. Furthermore, a random polypropylene resin with a MFR (melt flow rate) of 50 g / 10 min (230 °C) was used.

[0056] (Example 1) A decorative sheet 1 having a transparent resin layer 3 formed using a resin composition containing a plurality of types of polypropylene resins (high-crystalline polypropylene resin, low-crystalline polypropylene resin, and random polypropylene resin) was used. The basic manufacturing method of the decorative sheet is as follows.

[0057] The above high-crystalline PP resin, the low-crystalline PP resin A shown in Table 1, and the above random PP resin (MFR: 24 g / 10 min (230 °C)) were mixed and melted to form a resin composition. The blending ratio (addition amount) of each PP resin in the above resin composition was 50% by mass for the high-crystalline PP resin, 30% by mass for the low-crystalline PP resin, and 20% by mass for the random PP resin, based on the above resin composition. More specifically, the above three types of PP resins were mixed at the above blending ratios MR1, MR2, and MR3, extruded using a melt extruder, and a transparent resin sheet made of polypropylene resin with a thickness of 80 μm was formed as the resin composition to be used as the transparent resin layer 3. Thus, regarding the blending ratio of each of the plurality of types of polypropylene resins based on the mass of the above resin composition, the blending ratio MR1 of the high-crystalline PP resin is in the range of 30% by mass or more and 50% by mass or less, the blending ratio MR2 of the low-crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, and the blending ratio MR3 of the random polypropylene is in the range of 10% by mass or more and 20% by mass or less.

[0058] Both sides of the obtained transparent resin sheet were subjected to corona treatment to make the wetting tension of the transparent resin sheet surface 40 dyn / cm or more. On the other hand, a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) was added to one surface of a 70-μm polyethylene sheet (substrate layer 6) with concealment, and a hindered amine-based light stabilizer (Chimasorb 944; manufactured by BASF) was added at 0.5% by mass based on the binder resin content of the ink. Pattern printing (pattern 5a) was performed by the gravure printing method using this ink to provide a pattern layer 5.

[0059] Further, a primer layer 8 was provided on the other surface of the base material layer 6. Thereafter, on one surface side of the base material layer 6, a dry laminating adhesive (Take lacquer A540; manufactured by Mitsui Chemicals, Inc.; coating amount 2 g / m 2 ) was used to dry laminate the transparent resin layer 3 by the dry lamination method. Then, after an embossed pattern 3a was applied to the surface of the transparent resin layer 3, a two-component curable urethane top coat (W184; manufactured by DIC Graphics Co., Ltd.) was applied at a coating thickness of 6 g / m 2 to form a surface protection layer 2. Further, a low gloss pattern layer 9 formed of a resin containing a matting agent (gloss adjuster) was formed on the transparent resin layer 3. Specifically, a two-component curable urethane top coat was applied at a coating thickness of 1 g / m 2 so as to cover the entire surface of the outermost surface (the surface opposite to the transparent resin layer 3) of the surface protection layer 2 to provide a low gloss pattern layer 9. More specifically, the low gloss pattern layer 9 was a two-component type urethane-based thermosetting resin, which was composed of 100 parts by mass of solid content of acrylic polyol (6KW-700: manufactured by Dainippon Fine Chemical Co., Ltd.) and 5 parts by mass of solid content of polyisocyanate (UR190B hardener: manufactured by Toyo Ink Co., Ltd.). Further, 10 parts by mass of a surface-treated silica-based gloss adjuster (Mizukasil P-802Y: manufactured by Mizusawa Chemical Industry Co., Ltd.) was added to the low gloss pattern layer 9. Thereby, the decorative sheet of the present disclosure shown in FIG. 1 with a total thickness of 170 μm was obtained.

[0060] (Example 2) The above-mentioned random PP resin (MFR 11 g / 10 min (230 °C)) was added to the transparent resin layer 3. Otherwise, a decorative sheet according to Example 2 was obtained in the same manner as in Example 1.

[0061] (Example 3) The low crystalline PP resin added to the transparent resin layer 3 was the low crystalline PP resin B shown in Table 1. Otherwise, a decorative sheet according to Example 3 was obtained in the same manner as in Example 1. (Example 4) The low crystalline PP resin added to the transparent resin layer 3 was the low crystalline PP resin C shown in Table 1. Otherwise, a decorative sheet according to Example 4 was obtained in the same manner as in Example 1.

[0062] (Example 5) Regarding the blending ratio (addition amount) of each PP resin in the resin composition for forming the transparent resin layer 3, based on the resin composition, the blending ratio MR1 of the highly crystalline PP resin was 40% by mass, the blending ratio MR2 of the low crystalline PP resin was 50% by mass, and the blending ratio MR3 of the random PP resin was 10% by mass. Otherwise, a decorative sheet according to Example 5 was obtained in the same manner as in Example 1. (Example 6) The low crystalline PP resin added to the transparent resin layer 3 was the low crystalline PP resin B shown in Table 1. Otherwise, a decorative sheet according to Example 6 was obtained in the same manner as in Example 5. (Example 7) The low crystalline PP resin added to the transparent resin layer 3 was the low crystalline PP resin C shown in Table 1. Otherwise, a decorative sheet according to Example 7 was obtained in the same manner as in Example 5.

[0063] (Example 8) Regarding the blending ratio (addition amount) of each PP resin in the resin composition for forming the transparent resin layer 3, based on the resin composition, the blending ratio MR1 of the highly crystalline PP resin was 30% by mass, the blending ratio MR2 of the low crystalline PP resin was 50% by mass, and the blending ratio MR3 of the random PP resin was 20% by mass. Otherwise, a decorative sheet according to Example 8 was obtained in the same manner as in Example 1. (Example 9) The low crystalline PP resin added to the transparent resin layer 3 was the low crystalline PP resin B shown in Table 1. Otherwise, a decorative sheet according to Example 9 was obtained in the same manner as in Example 8. (Example 10) The low crystalline PP resin added to the transparent resin layer 3 was the low crystalline PP resin C shown in Table 1. Otherwise, a decorative sheet according to Example 10 was obtained in the same manner as in Example 8.

[0064] (Example 11) In the resin composition for forming the transparent resin layer 3, the blending ratio (addition amount) of each PP resin was set as follows based on the resin composition: the blending ratio MR1 of the highly crystalline PP resin was 40% by mass, the blending ratio MR2 of the low crystalline PP resin was 40% by mass, and the blending ratio MR3 of the random PP resin was 20% by mass. Otherwise, a decorative sheet according to Example 11 was obtained in the same manner as in Example 1. (Example 12) The low crystalline PP resin added to the transparent resin layer 3 was the low crystalline PP resin B shown in Table 1. Otherwise, a decorative sheet according to Example 12 was obtained in the same manner as in Example 11. (Example 13) The low crystalline PP resin added to the transparent resin layer 3 was the low crystalline PP resin C shown in Table 1. Otherwise, a decorative sheet according to Example 13 was obtained in the same manner as in Example 11. (Example 14) At a part of the outermost surface of the surface protective layer 2, at a position overlapping with the pattern 5a of the pattern layer 5 in plan view, a low gloss pattern layer 9 was formed so as to be synchronized with the pattern 5a. Otherwise, a decorative sheet according to Example 14 was obtained in the same manner as in Example 1.

[0065] (Comparative Example 1) In the resin composition for forming the transparent resin layer, the blending ratio (addition amount) of each PP resin was set as follows based on the resin composition: the blending ratio MR1 of the highly crystalline PP resin was 20% by mass, the blending ratio MR2 of the low crystalline PP resin was 50% by mass, and the blending ratio MR3 of the random PP resin was 30% by mass. Otherwise, a decorative sheet according to Comparative Example 1 was obtained in the same manner as in Example 1. (Comparative Example 2) The low crystalline PP resin added to the transparent resin layer was the low crystalline PP resin B shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 2 was obtained in the same manner as in Comparative Example 1. (Comparative Example 3) The low crystalline PP resin added to the transparent resin layer was the low crystalline PP resin C shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 3 was obtained in the same manner as in Comparative Example 1.

[0066] (Comparative Example 4) In the resin composition for forming the transparent resin layer, the blending ratio (addition amount) of each PP resin was set as follows based on the resin composition: the blending ratio MR1 of the highly crystalline PP resin was 60% by mass, the blending ratio MR2 of the low crystalline PP resin was 30% by mass, and the blending ratio MR3 of the random PP resin was 10% by mass. Otherwise, a decorative sheet according to Comparative Example 4 was obtained in the same manner as in Example 1. (Comparative Example 5) The low crystalline PP resin added to the transparent resin layer was the low crystalline PP resin B shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 5 was obtained in the same manner as in Comparative Example 4. (Comparative Example 6) The low crystalline PP resin added to the transparent resin layer was the low crystalline PP resin C shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 6 was obtained in the same manner as in Comparative Example 4.

[0067] (Comparative Example 7) In the resin composition for forming the transparent resin layer, the blending ratio (addition amount) of each PP resin was set as follows based on the resin composition: the blending ratio MR1 of the highly crystalline PP resin was 30% by mass, the blending ratio MR2 of the low crystalline PP resin was 60% by mass, and the blending ratio MR3 of the random PP resin was 10% by mass. Otherwise, a decorative sheet according to Comparative Example 7 was obtained in the same manner as in Example 1. (Comparative Example 8) The low crystalline PP resin added to the transparent resin layer was the low crystalline PP resin B shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 8 was obtained in the same manner as in Comparative Example 7. (Comparative Example 9) The low crystalline PP resin added to the transparent resin layer was the low crystalline PP resin C shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 9 was obtained in the same manner as in Comparative Example 7.

[0068] (Comparative Example 10) In the resin composition for forming the transparent resin layer, the blending ratio (addition amount) of each PP resin was set as follows based on the resin composition: the blending ratio MR1 of the highly crystalline PP resin was 45% by mass, the blending ratio MR2 of the low crystalline PP resin was 50% by mass, and the blending ratio MR3 of the random PP resin was 5% by mass. Otherwise, a decorative sheet according to Comparative Example 10 was obtained in the same manner as in Example 1. (Comparative Example 11) The low-crystalline PP resin added to the transparent resin layer was the low-crystalline PP resin B shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 11 was obtained in the same manner as in Comparative Example 10. (Comparative Example 12) The low-crystalline PP resin added to the transparent resin layer was the low-crystalline PP resin C shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 12 was obtained in the same manner as in Comparative Example 10.

[0069] (Comparative Example 13) In the resin composition forming the transparent resin layer, the blending ratio (addition amount) of each PP resin was such that the blending ratio MR1 of the highly crystalline PP resin was 60% by mass, the blending ratio MR2 of the low-crystalline PP resin was 20% by mass, and the blending ratio MR3 of the random PP resin was 20% by mass, based on the resin composition. Otherwise, a decorative sheet according to Comparative Example 13 was obtained in the same manner as in Example 1. (Comparative Example 14) The low-crystalline PP resin added to the transparent resin layer was the low-crystalline PP resin B shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 14 was obtained in the same manner as in Comparative Example 13. (Comparative Example 15) The low-crystalline PP resin added to the transparent resin layer was the low-crystalline PP resin C shown in Table 1. Otherwise, a decorative sheet according to Comparative Example 15 was obtained in the same manner as in Comparative Example 13. (Comparative Example 16) The low-gloss pattern layer 9 was not provided on the surface protective layer 2. Otherwise, a decorative sheet according to Comparative Example 13 was obtained in the same manner as in Example 1.

[0070] <Performance Evaluation> The decorative sheets of each Example and the decorative sheets of each Comparative Example were evaluated for film-forming property, transparency, scratch resistance, and post-processing property. The results are shown in Table 2 together with the configuration of the transparent resin layer.

[0071]

Table 2

[0072] [Film-forming property] The state of the transparent resin sheet during melt extrusion was visually observed. The evaluation was carried out in the following two steps. ◎: Good (No neck-in or film breakage was confirmed) ×: Inferior (Neck-in or film breakage was observed) [Transparency] The manufactured transparent resin layer 3 was visually observed and evaluated based on the visibility of the pattern on the lower layer. The evaluation was carried out in the following three steps. ◎: Good (Transparent) 〇: The designability is not a problem, but it is slightly cloudy (at a level where there is no practical problem) ×: Inferior (Cloudy) [Scratch resistance] Evaluation was performed by a pencil hardness test. First, on one surface of a 0.5-mm-thick steel plate that constitutes the base material B, each of the decorative sheets 1 of the examples and comparative examples prepared by the above method was attached using an adhesive for steel plates to form a decorative member. The test method conformed to JIS-K5600. As the evaluation method, when the highest hardness at which no dents were formed on the surface of the transparent resin layer 3 was 2B or higher, it was rated as "◎"; when it was 3B, it was rated as "○"; and when it was 4B or lower, it was rated as "×".

[0073] [Post-processability] Evaluation was performed by a bender bending process suitability test. The detailed method of the bender bending process suitability test is described below. First, on one surface of a 0.5-mm-thick steel plate that constitutes the base material B, each of the decorative sheets 1 of the examples and comparative examples prepared by the above method was attached using an adhesive for steel plates to form a decorative member. The decorative member was bent at a curvature radius of 0.5 mm and an angle of 90 degrees on the side of the base material B using a bending tester "Bending Machine EG-4010 (manufactured by Amada Co., Ltd.)". Then, the presence or absence of appearance changes such as whitening and cracking at the bent portion of the surface of the decorative sheet 1 was observed using an optical microscope "Digital Microscope VHX-970F (manufactured by Keyence Corporation)", and the bender post-processability was evaluated. The evaluation was carried out in the following three steps. ◎: No appearance changes such as whitening and cracking were observed 〇: Slight whitening and cracking are observed, but it is at a level that causes no practical problems. ×: Whitening and cracking that are unacceptable for a decorative sheet were observed.

[0074] [Appearance Observation (Designability)] Appearance observation was carried out by visual inspection of the observer, and it was judged whether the design of the decorative sheet had a matte feeling (reduction of glossiness) on the surface due to the low-gloss pattern layer 9. The evaluation was carried out in the following three levels. ◎: In the appearance observation, the observer felt that there were visual irregularities (a gloss-matte feeling) on the surface of the decorative sheet due to the gloss difference between the surface protection layer 2 and the low-gloss pattern layer 9. 〇: In the appearance observation, the observer felt that there was a matte feeling on the surface of the decorative sheet due to the low-gloss pattern layer 9. ×: In the appearance observation, the entire surface of the decorative sheet had gloss, and the observer did not feel a matte feeling (reduction of gloss) on the surface of the decorative sheet.

[0075] As shown in Examples 1-14 of Table 2, regarding the blending ratios of the three types of polypropylene resins based on the mass of the above resin composition, the highly crystalline PP resin is within the range of 30% to 50% by mass, the low-crystalline PP resin is within the range of 30% to 50% by mass, and the random PP resin is within the range of 10% to 20% by mass. By doing so, while maintaining the scratch resistance, film-forming property, and transparency of the transparent resin layer required in actual use, a decorative sheet with excellent bender bending processability (post-processing property) and designability imparted by the low-gloss layer can be obtained. Also, in the decorative sheet of Example 14, by synchronizing the pattern 5a of the pattern layer 5 and the low-gloss pattern layer 9, a gloss-matte feeling due to the gloss difference between the surface protection layer 2 and the low-gloss pattern layer 9 was imparted to the sheet surface, and the designability was significantly improved.

[0076] On the other hand, in the decorative sheets of Comparative Examples 1-3, it can be seen that the scratch resistance deteriorated because the blending ratio of the highly crystalline PP resin was less than 30% by mass, and further, clouding occurred in the transparent resin layer because the blending ratio of the random PP resin exceeded 20% by mass. In addition, in the cosmetic sheets of Comparative Examples 4-6, since the blending ratio of the highly crystalline PP resin exceeded 50% by mass, whitening and cracking occurred during the bender bending process. In addition, in the cosmetic sheets of Comparative Examples 7-9, since the blending ratio of the low crystalline PP resin exceeded 50% by mass, neck-in occurred during melt extrusion, resulting in poor film formation. In addition, in the cosmetic sheets of Comparative Examples 10-12, since the blending ratio of the random PP resin was less than 10% by mass, neck-in occurred during melt extrusion, resulting in poor film formation. In addition, in the cosmetic sheets of Comparative Examples 13-15, since the blending ratio of the highly crystalline PP resin exceeded 50% by mass and the blending ratio of the low crystalline PP resin was less than 30% by mass, whitening and cracking occurred during the bender bending process. In addition, in the cosmetic sheet of Comparative Example 16, since the low gloss pattern layer 9 was not formed, a matte feeling was not imparted to the sheet surface, resulting in insufficient design.

[0077] Note that the cosmetic sheet and the cosmetic member of the present disclosure are not limited to the above-described embodiments and examples, and various modifications are possible without impairing the features of the invention.

[0078] In addition, for example, the present disclosure can adopt the following configurations. (1) A transparent resin layer formed of a resin composition containing a plurality of types of polypropylene resins, A low gloss layer provided on the transparent resin layer and formed of a resin containing a matting agent, The resin composition includes highly crystalline polypropylene, low crystalline polypropylene, and random polypropylene as the plurality of types of polypropylene resins, The blending ratio of each of the plurality of types of polypropylene resins based on the mass of the resin composition is such that the highly crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, the low crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, and the random polypropylene is in the range of 10% by mass or more and 20% by mass or less. A cosmetic sheet characterized by the above. (2) A surface protection layer is provided between the transparent resin layer and the low-gloss layer, and the low-gloss layer is provided on at least a part of the surface of the surface protection layer. The cosmetic sheet according to (1) above, characterized in that. (3) A pattern layer is provided on the side of the transparent resin layer opposite to the low-gloss layer side, and at least a part of the pattern of the low-gloss layer and the pattern of the pattern layer overlap in plan view. The cosmetic sheet according to (1) or (2) above, characterized in that. (4) The MFR (melt flow rate) of the random polypropylene at 230 °C is in the range of 10 g / 10 min or more and 50 g / 10 min or less The cosmetic sheet according to any one of (1) to (3) above, characterized in that. (5) The low-crystalline polypropylene has a mesopentad fraction of 20% or more and 60% or less, and the cosmetic sheet according to any one of (1) to (4) above, characterized in that. (6) The low-crystalline polypropylene has an MFR (melt flow rate) at 230 °C of 30 g / 10 min or more and 100 g / 10 min or less, and the cosmetic sheet according to any one of (1) to (5) above, characterized in that. (7) The low-crystalline polypropylene has a mass average molecular weight (Mw) of 10,000 or more and 500,000 or less, and the cosmetic sheet according to any one of (1) to (6) above, characterized in that. (8) The molecular weight distribution (Mw / Mn) of the low-crystalline polypropylene is less than 4, and the cosmetic sheet according to any one of (1) to (7) above, characterized in that. (9) The low-crystalline polypropylene is defined as the peak top of the peak observed on the highest temperature side of the melting endotherm curve obtained by holding at -10°C for 5 minutes in a nitrogen atmosphere and then raising the temperature at a rate of 10°C / min using a differential scanning calorimeter (DSC), and the melting point is 0°C or higher and 120°C or lower. The cosmetic sheet according to any one of the above (1) to (8). (10) A base material, The cosmetic sheet according to any one of the above (1) to (9) provided on at least one surface side of the base material, and a cosmetic member characterized by comprising the same. (11) A method for manufacturing the cosmetic sheet according to any one of the above (1) to (9), The transparent resin layer is formed using the resin composition containing the plurality of types of polypropylene resins, and the low-gloss layer formed of a resin containing a matting agent is formed on the transparent resin layer, The plurality of types of polypropylene resins are the high-crystalline polypropylene, the low-crystalline polypropylene, and the random polypropylene, Regarding the blending ratio of each of the plurality of types of polypropylene resins based on the mass of the resin composition, the high-crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, the low-crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, and the random polypropylene is in the range of 10% by mass or more and 20% by mass or less A method for manufacturing a cosmetic sheet, characterized by the above.

Explanation of symbols

[0079] 1 Cosmetic sheet 2 Surface protective layer 3 Transparent resin layer 3a Embossed pattern 4 Adhesive layer 5 Pattern layer 5a Pattern 6 Base material layer 7 Concealing layer 8 Primer layer 9 Low-gloss pattern layer 10 Cosmetic member B Base material

Claims

1. A transparent resin layer formed of a resin composition containing a plurality of types of polypropylene resins, and a low-gloss layer provided on the transparent resin layer and formed of a resin containing a matting agent, wherein the resin composition includes highly crystalline polypropylene, low-crystalline polypropylene, and random polypropylene as the plurality of types of polypropylene resins, and the blending ratio of each of the plurality of types of polypropylene resins based on the mass of the resin composition is such that the highly crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, the low-crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, and the random polypropylene is in the range of 10% by mass or more and 20% by mass or less. A cosmetic sheet characterized by the above.

2. A surface protection layer is provided between the transparent resin layer and the low-gloss layer, and the low-gloss layer is provided on at least a part of the surface of the surface protection layer. The cosmetic sheet according to claim 1, characterized by the above.

3. A pattern layer is provided on the side of the transparent resin layer opposite to the low-gloss layer side, and at least a part of the pattern of the low-gloss layer and the pattern of the pattern layer overlap in plan view. The cosmetic sheet according to claim 2, characterized by the above.

4. The melt flow rate (MFR) of the random polypropylene at 230 °C is in the range of 10 g / 10 min or more and 50 g / 10 min or less. The cosmetic sheet according to claim 1, characterized by the above.

5. The low-crystalline polypropylene has a mesopentad fraction of 20% or more and 60% or less. The cosmetic sheet according to claim 4, characterized by the above.

6. The low-crystalline polypropylene has an MFR (melt flow rate) at 230 °C of 30 g / 10 min or more and 100 g / 10 min or less, and the cosmetic sheet according to claim 5 is characterized by this.

7. The low-crystalline polypropylene has a mass average molecular weight (Mw) of 10,000 or more and 500,000 or less, and the cosmetic sheet according to claim 6 is characterized by this.

8. The molecular weight distribution (Mw / Mn) of the low-crystalline polypropylene is less than 4, and the cosmetic sheet according to claim 7 is characterized by this.

9. The low-crystalline polypropylene is defined as the peak top of the peak observed on the highest temperature side of the melting endotherm curve obtained by holding at -10 °C for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 °C / min using a differential scanning calorimeter (DSC), and the melting point is 0 °C or more and 120 °C or less, and the cosmetic sheet according to claim 8 is characterized by this.

10. A base material, The cosmetic sheet according to any one of claims 1 to 9 provided on at least one surface side of the base material, and A cosmetic member characterized by this.

11. A method for manufacturing the cosmetic sheet according to any one of claims 1 to 9, The transparent resin layer is formed using the resin composition containing the plurality of types of polypropylene resins, and the low-gloss layer formed of a resin containing a matting agent is formed on the transparent resin layer, The plurality of types of polypropylene resins are the high-crystalline polypropylene, the low-crystalline polypropylene, and the random polypropylene, Regarding the blending ratio of each of the plurality of types of polypropylene resins based on the mass of the resin composition, the highly crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, the low crystalline polypropylene is in the range of 30% by mass or more and 50% by mass or less, and the random polypropylene is in the range of 10% by mass or more and 20% by mass or less. A method for manufacturing a cosmetic sheet, characterized by the above.

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