JP7287554B2 - Decorative sheets and materials - Google Patents

Description

TECHNICAL FIELD The present invention relates to a decorative sheet and a decorative material.

As a decorative sheet that replaces a decorative sheet made of polyvinyl chloride, for example, a decorative sheet using an olefin-based resin has been proposed, as disclosed in Patent Document 1.

JP 2014-188941 A

In recent years, from the background of environmental problems, there has been a demand to replace the conventional petroleum-derived materials with plant-derived materials for decorative sheets. However, when biomass polyethylene is used as a plant-derived material that can be used for a decorative sheet, there is a problem that the surface hardness is lowered for use as a decorative sheet.

SUMMARY OF THE INVENTION In view of the problems described above, an object of the present invention is to provide a decorative sheet and decorative material capable of suppressing a decrease in surface hardness even when formed using a plant-derived material. .

In order to solve the above problems, one aspect of the present invention includes a colored base layer, an adhesive layer, and a transparent thermoplastic resin layer in this order, wherein the colored base layer and the transparent thermoplastic resin layer are: Each is a resin layer formed of a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin, and the transparent thermoplastic resin layer contains the biomass-derived olefin, and is 0.92 g / cm ³ or more and 0.99 g/cm ³ or less, and has a thickness of 55 μm or more and 150 μm or less, the colored substrate layer contains the biomass-derived olefin, It has a density within the range of 92 g/cm ³ or more and 1.12 g/cm ³ or less and a thickness within the range of 51 μm or more and 120 μm or less, is laminated on the other surface of the colored base layer, and is polyester It is a decorative sheet provided with a primer layer formed using a material of this type.
Further, in order to solve the above problems, one aspect of the present invention is a decorative material including a base material and a decorative sheet laminated on at least one surface of the base material.

According to one aspect of the present invention, there is provided a decorative sheet and decorative material capable of suppressing a decrease in surface hardness even when formed using plant-derived high-density polyethylene, which is a plant-derived material. It becomes possible to

1 is a cross-sectional view showing configurations of a decorative sheet and a decorative material according to a first embodiment of the present invention; FIG.

Hereinafter, embodiments of the present technology will be described with reference to the drawings. In the description of the drawings, the same or similar parts are denoted by the same or similar reference numerals, and overlapping descriptions are omitted. Each drawing is schematic and may differ from the actual one. The embodiments shown below exemplify devices and methods for embodying the technical ideas of the present technology, and the technical ideas of the present technology are specific to the devices and methods exemplified in the embodiments below. not something to do. The technical idea of this technology can be modified in various ways within the technical scope described in the claims. Further, the directions of "left and right" and "up and down" in the following description are merely definitions for convenience of description, and do not limit the technical idea of the present invention. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left." It goes without saying that

(First embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG. A specific configuration of the decorative sheet 1 will be described later.
The base material 9 is formed in a plate shape using, for example, wooden boards, inorganic boards, metal plates, etc., and the decorative sheet 1 is laminated on one surface (the upper surface in FIG. 1). there is That is, the decorative material 10 includes a substrate 9 and a decorative sheet 1 laminated on one surface of the substrate 9 .

(Configuration of decorative sheet)
As shown in FIG. 1, the decorative sheet 1 includes a colored substrate layer 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer 5, a surface protective layer 6, an uneven portion 7, and a primer layer 8. Prepare.

<Colored substrate layer>
The colored base material layer 2 is formed using a thermoplastic resin.
As the thermoplastic resin forming the colored base material layer 2, for example, a colored thermoplastic polyolefin resin can be used. Examples of polyolefin resins include polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymers, ethylene-α-olefin copolymers, propylene-α-olefin copolymers, and ethylene- Olefin copolymers such as vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-(meth)acrylic acid (ester) copolymers, ethylene-unsaturated carboxylic acid copolymer metal neutralized products (ionomers) Among polyolefin-based resins such as coalesced resins, it is possible to use single or a mixture of two or more of them, a copolymer, a composite, a laminate, and the like.

As the polyolefin-based resin, it is possible to appropriately select and use from the types described above according to the purpose of use of the decorative sheet 1 and the like. In particular, polypropylene-based resins, that is, homo- or copolymers containing propylene as a main component, are most suitable for general use. For example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, or the like may be used alone or appropriately blended, and a resin or the like appropriately blended with atactic polypropylene may also be used. Further, it may be a copolymer containing an olefinic monomer other than propylene. A propylene-α-olefin copolymer containing 15 mol % or more of one or more comonomers of 1,4-methylpentene-1, hexene-1 or octene-1 can be used. In addition, low density polyethylene, ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, styrene-butadiene copolymer, which are usually used for softening polypropylene resin It is possible to appropriately add modifiers such as polymers or hydrogenated substances.

In addition, the colored substrate layer 2 may optionally contain, for example, a coloring agent, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, and an antibacterial agent. , an antifungal agent, an antifriction agent, a light scattering agent, and a luster adjusting agent.
The thickness of the colored base material layer 2 is preferably in the range of 40 [μm] to 150 [μm], more preferably 50 [μm] to 130 [μm]. This is because, when the thickness of the colored base layer 2 is 40 [μm] or more, it is possible to absorb the irregularities and steps of the underlying floor material, etc., and improve the finish of the decorative sheet 1. Due to something. Further, when the thickness of the colored base material layer 2 is 150 [μm] or less, the manufacturing cost of the decorative sheet 1 can be reduced without forming the colored base material layer 2 thicker than necessary. due to that.

<Pattern layer>
The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored base material layer 2, and is a layer for adding a pattern for imparting design. The design layer 3 may be omitted if the coloring of the colored base material layer 2 can be used instead.
The pattern layer 3 is formed using printing ink, paint, or the like. The printing ink, paint, or the like that forms the pattern layer 3 is formed by dissolving or dispersing a coloring agent such as a dye or pigment in a suitable diluent solvent together with a suitable binder resin.

The printing ink, paint, or the like that forms the pattern layer 3 is applied using, for example, various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.
As the binder resin, for example, it is possible to use urethane-based resin, acrylic-based resin, vinyl chloride-based resin, polyimide-based resin, nitrocellulose, etc., or a mixture thereof, but is not limited to these. do not have.
Any pattern can be used as the pattern. For example, wood grain patterns, stone grain patterns, texture patterns, abstract patterns, geometric patterns, characters, symbols, single-color solid colors, etc., or combinations thereof can be used. It is possible. In addition, in order to improve the concealability of the decorative sheet 1, a concealing layer may be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer is formed, for example, using opaque printing ink or paint containing a large amount of opaque pigment such as titanium dioxide or iron oxide.

The thickness of the pattern layer 3 is preferably in the range of 1 [μm] to 10 [μm]. This is because when the pattern layer 3 has a thickness of 1 [μm] or more, clear printing is possible. Further, when the thickness of the pattern layer 3 is 10 [μm] or less, the printing workability in manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.
In addition, in order to impart various functions to the pattern layer 3, for example, an extender, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a desiccant, a curing agent, a curing accelerator and a curing agent are added. Functional additives such as retardants may be added.
In addition, the pattern layer 3 includes, for example, a solid colored base layer for concealing the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern for adding a design. It is good also as a structure which has a pattern pattern layer.

<Adhesive layer>
The adhesive layer 4 is laminated on one surface (upper surface in FIG. 1) of the pattern layer 3 and used for bonding the pattern layer 3 and the transparent resin layer 5 together.
As the material of the adhesive layer 4, for example, urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, polyolefin, or the like can be used.

<Transparent resin layer>
The transparent resin layer 5 is laminated on one surface (the upper surface in FIG. 1) of the adhesive layer 4, and is made of transparent plant-derived high-density polyethylene (for example, “Green polyethylene (SHC7260)” manufactured by Braskem). ).
In addition, plant-derived high-density polyethylene is, for example, polyethylene having a density exceeding 0.94.

A nucleating agent (for example, “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd.) is added to the high-density polyethylene forming the transparent resin layer 5 . That is, a nucleating agent is added to the resin composition containing high-density polyethylene forming the transparent resin layer 5 .
The nucleating agent is added to the high density polyethylene within the range of 500 [ppm] or more and 2000 [ppm] or less based on the mass of the high density polyethylene.
In the first embodiment, as an example, a case where a nucleating agent is added to high-density polyethylene within a range of 1500 [ppm] or more and 2000 [ppm] or less based on the mass of high-density polyethylene will be described. The density of the transparent resin layer 5 is, for example, within the range of 0.92 [g/cm ³ ] to 0.99 [g/cm ³ ], preferably 0.94 [g/cm 3 ] to 0.99 [g/cm ³ ]. It has a density within the range of 98 [g/cm ³ ] or less, more preferably within the range of 0.95 [g/cm ³ ] or more and 0.97 [g/cm ³ ] or less.

The transparent resin layer 5 may optionally contain, for example, a colorant, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, an antifungal agent. At least one selected from various additives such as agents, antifriction agents, light scattering agents and gloss modifiers may be added.
The transparent resin layer 5 preferably has a degree of transparency (colorless transparency, colored transparency, translucent) that allows the pattern of the pattern layer 3 to be seen through from the surface (upper surface) of the decorative sheet 1 .
The thickness of the transparent resin layer 5 is, for example, within the range of 20 [μm] or more and 200 [μm] or less.

<Surface protective layer>
The surface protective layer 6 is laminated on one surface (the upper surface in FIG. 1) of the transparent resin layer 5, and provides the decorative sheet 1 with weather resistance, scratch resistance, stain resistance, design properties, and the like. It is a layer provided to impart functions.
Moreover, the surface protective layer 6 is formed using, for example, an acrylic resin composition.
In addition, the surface protective layer 6 may optionally contain weather resistant agents, plasticizers, stabilizers, fillers, dispersants, coloring agents such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, and light stabilizers. , anti-blocking agents, catalyst scavengers, colorants, light scattering agents, gloss modifiers, and other additives. Moreover, the surface protective layer 6 may contain functional additives such as an antibacterial agent and an antifungal agent, if necessary.

<Uneven part>
The concave-convex portion 7 is formed by concave portions provided at a plurality of locations on the transparent resin layer 5 and the surface protective layer 6 .

<Primer layer>
The primer layer 8 is a layer serving as a base, and is a layer for improving adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9 .
Further, the primer layer 8 is laminated on the other surface (the lower surface in FIG. 1) of the colored base material layer 2 .
Furthermore, the primer layer 8 is formed using, for example, a polyester-based resin, an organic additive, a pigment, or the like.
In addition, the primer layer 8 may contain an antirust pigment for the purpose of improving corrosion resistance.
The thickness of the primer layer 8 is, for example, within the range of 1 [μm] or more and 10 [μm] or less.

The first embodiment described above is an example of the present invention, and the present invention is not limited to the first embodiment described above. Various modifications are possible according to the design and the like within the scope of not departing from the technical idea.

(Effect of the first embodiment)
If it is the decorative sheet 1 of 1st Embodiment, it will become possible to have an effect described below.
(1) A colored substrate layer 2 and a transparent resin layer 5 laminated on one side of the colored substrate layer 2, and the transparent resin layer 5 is made of a resin composition containing plant-derived high-density polyethylene. A nucleating agent is added to the resin composition that is formed by the method and contains high-density polyethylene. The density of the transparent resin layer 5 is, for example, within the range of 0.92 [g/cm ³ ] to 0.99 [g/cm ³ ], preferably 0.94 [g/cm ³ ] to 0.98 [ g/cm ³ ] or less, more preferably 0.95 [g/cm ³ ] or more and 0.97 [g/cm ³ ] or less.
Therefore, even in a configuration using plant-derived high-density polyethylene, which is a plant-derived material, the transparent resin layer 5 having a high hardness equivalent to a configuration formed using fossil fuel-derived polyethylene is formed. becomes possible.

As a result, it is possible to provide the decorative sheet 1 capable of suppressing a decrease in surface hardness even when formed using plant-derived high-density polyethylene, which is a plant-derived material.
In addition, even in a configuration using plant-derived high-density polyethylene, which is a plant-derived material, a transparent resin layer 5 having high transparency equivalent to a configuration formed using fossil fuel-derived polyethylene or the like is formed. becomes possible.

(2) The nucleating agent is added within the range of 500 [ppm] or more and 2000 [ppm] or less based on the mass of the high-density polyethylene.
As a result, it is possible to provide the decorative sheet 1 with less haze.

(3) The nucleating agent is added within the range of 1500 [ppm] or more and 2000 [ppm] or less based on the mass of the high-density polyethylene.
As a result, it is possible to provide the decorative sheet 1 with less haze than a configuration in which the nucleating agent is added at less than 1500 [ppm] based on the mass of the high-density polyethylene.

Further, with the decorative material 10 of the first embodiment, it is possible to obtain the effects described below.
(4) The base material 9 and the decorative sheet 1 laminated on at least one surface of the base material 9 are provided.
As a result, it is possible to provide the decorative material 10 capable of suppressing a decrease in surface hardness even when formed using plant-derived high-density polyethylene, which is a plant-derived material.

<Modified Example of First Embodiment>
(1) In the first embodiment, the decorative material 10 is configured to include the decorative sheet 1 laminated on one surface of the base material 9, but the present invention is not limited to this. That is, the configuration of the decorative material 10 may be such that in addition to one surface of the substrate 9, the decorative sheet 1 is laminated on the other surface of the substrate 9 (lower surface in FIG. 1).

The decorative materials of Examples 1 to 3 and the decorative materials of Comparative Examples 1 and 2 will be described below with reference to the first embodiment.

(Example 1)
The colored base material layer was formed with a thickness of 55 [μm] using a colored polyethylene resin.
The pattern layer was formed by using urethane-based printing ink after applying a corona discharge treatment to one surface of the colored substrate layer.
The adhesive layer was formed using a maleic anhydride-modified polyethylene resin.
The transparent resin layer uses "green polyethylene" manufactured by Braskem, which is plant-derived high-density polyethylene (HDPE), and 1500 [ppm] and A nucleating agent, “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd., was added to form the powder. Moreover, the thickness of the transparent resin layer was set to 70 [μm].

The surface protective layer was formed using an acrylic resin composition as a main component.
The primer layer was formed using a polyester urethane resin to a thickness of 1 [μm] or more and 2 [μm] or less after applying a corona discharge treatment to one surface of the colored substrate layer.
Then, Ruder lamination was carried out to form the decorative sheet of Example 1 having a thickness of 135 [μm].
After forming the decorative sheet of Example 1, the surface of the primer layer facing the base material is attached to the base material using "BA-10L (curing agent: BA-11B)" manufactured by Japan Coating Resin. , the decorative material of Example 1 was formed.

(Example 2)
Formed in the same manner as in Example 1, except that the nucleating agent "Rikemaster CN-002" manufactured by Riken Vitamin Co., Ltd. was added so as to be 500 [ppm] based on the mass of the high-density polyethylene. , the decorative sheet and decorative material of Example 2 were formed.
(Example 3)
Formed in the same manner as in Example 1, except that the nucleating agent "Rikemaster CN-002" manufactured by Riken Vitamin Co., Ltd. was added so as to be 2000 [ppm] based on the mass of the high-density polyethylene. , the decorative sheet and decorative material of Example 3 were formed.

(Comparative example 1)
A decorative sheet and decorative material of Comparative Example 1 were formed in the same manner as in Example 1, except that no nucleating agent was added to the high-density polyethylene.
(Comparative example 2)
A decorative sheet and decorative material of Comparative Example 3 were formed in the same manner as in Comparative Example 2, except that no nucleating agent was added to the high-density polyethylene.

(Performance evaluation, evaluation results)
Surface hardness, productivity, transmittance, and haze were evaluated for the decorative materials of Examples 1 to 3 and the decorative materials of Comparative Examples 1 and 2, respectively. As the evaluation method, the method described below was used.

<Surface hardness>
After carrying out a pencil hardness test using pencils of different hardnesses on the decorative material, damage (gouging) occurring on the surface (surface protective layer) was confirmed to evaluate the surface hardness. Then, after conducting the pencil hardness test using a pencil having a hardness of 2B or more, the case where damage occurred on the surface was evaluated as "⊚", and after conducting the pencil hardness test using a pencil having a hardness of 4B or more. , and the case where damage occurred on the surface was evaluated as "○". In addition, a case where damage occurred on the surface after conducting a pencil hardness test using a pencil having a hardness of 5B or less was evaluated as "x".
<Productivity>
Productivity was evaluated according to whether or not there was a problem in manufacturing the decorative sheet. If there is no problem in manufacturing the decorative sheet, it is evaluated as "A"; if there is no problem in manufacturing the decorative sheet, it is evaluated as "○"; It was evaluated as "x".

<Transparency>
The total light transmittance at a wavelength of 555 [nm] is measured with a spectrophotometer (integrating sphere) in a state where the thickness of the transparent resin layer is set within the range of 70 [μm] or more and 80 [μm] or less, Permeability was evaluated. Then, the case where the total light transmittance is 85% is evaluated as "◎", and the case where the total light transmittance is within the range of 80% or more and 85% or less is evaluated as "○", and the total light transmittance is evaluated as "○". A case of less than 80% was evaluated as "x".
<Haze>
Haze was evaluated by evaluating whether or not there was any hindrance to the design when used as a decorative sheet using the criteria established by the inventors.

As a result of evaluating various performances using the methods described above, the decorative materials of Examples 1 to 3 exhibited excellent performances in all evaluation tests. On the other hand, the decorative materials of Comparative Examples 1 and 2 were unable to exhibit excellent performance in all evaluation tests.

(Second embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG.
Note that the configuration of the decorative material 10 in the second embodiment is the same as that of the above-described first embodiment except for the configuration of the decorative sheet 1, so the description of the configuration other than the decorative sheet 1 will be omitted.

(Configuration of decorative sheet)
As shown in FIG. 1, the decorative sheet 1 includes a colored substrate layer 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer 5, a surface protective layer 6, an uneven portion 7, and a primer layer 8. Prepare.

<Colored substrate layer>
The colored base material layer 2 is formed using a thermoplastic resin.
As the thermoplastic resin forming the colored base material layer 2, for example, a colored thermoplastic polyolefin resin can be used. Examples of polyolefin resins include polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymers, ethylene-α-olefin copolymers, propylene-α-olefin copolymers, and ethylene- Olefin copolymers such as vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, ethylene-(meth)acrylic acid (ester) copolymers, ethylene-unsaturated carboxylic acid copolymer metal neutralized products (ionomers) Among polyolefin-based resins such as coalesced resins, it is possible to use single or a mixture of two or more of them, a copolymer, a composite, a laminate, and the like.
Moreover, the colored substrate layer 2 may be formed of a resin composition containing plant-derived high-density polyethylene. Furthermore, the colored substrate layer 2 may contain plant-derived low-density polyethylene or plant-derived linear low-density polyethylene in addition to plant-derived high-density polyethylene.

As the polyolefin-based resin, it is possible to appropriately select and use from the types described above according to the purpose of use of the decorative sheet 1 and the like. In particular, polypropylene-based resins, that is, homo- or copolymers containing propylene as a main component, are most suitable for general use. For example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, or the like may be used alone or appropriately blended, and a resin or the like appropriately blended with atactic polypropylene may also be used. Further, it may be a copolymer containing an olefinic monomer other than propylene. A propylene-α-olefin copolymer containing 15 mol % or more of one or more comonomers of 1,4-methylpentene-1, hexene-1 or octene-1 can be used. In addition, low density polyethylene, ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, styrene-butadiene copolymer, which are usually used for softening polypropylene resin It is possible to appropriately add modifiers such as polymers or hydrogenated substances.

In addition, the colored substrate layer 2 may optionally contain, for example, a coloring agent, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, and an antibacterial agent. , an antifungal agent, an antifriction agent, a light scattering agent, and a luster adjusting agent.
The thickness of the colored base material layer 2 is preferably in the range of 40 [μm] to 150 [μm], more preferably 50 [μm] to 130 [μm]. This is because, when the thickness of the colored base layer 2 is 40 [μm] or more, it is possible to absorb the irregularities and steps of the underlying floor material, etc., and improve the finish of the decorative sheet 1. Due to something. Further, when the thickness of the colored base material layer 2 is 150 [μm] or less, the manufacturing cost of the decorative sheet 1 can be reduced without forming the colored base material layer 2 thicker than necessary. due to that.
In addition, the colored base layer 2 has a weight within the range of 0.92 [g/cm ³ ] to 1.12 [g/cm 3 ], preferably 0.98 [g/cm ³ ] to 1.10 [g/cm ³ ]. It has a density within the range of [g/cm ³ ] or less.
The density of the colored base material layer 2 is a value measured according to the method specified in A method of JIS K7112-1980 after annealing according to JIS K6760-1995.
When the density of the colored base material layer 2 is 0.92 [g/cm ³ ] or more, the rigidity of the colored base layer 2 is reduced compared to when the density is less than 0.92 [g/cm ³ ]. can be increased. In addition, when the density of the colored base layer 2 is 1.12 [g/cm ³ ] or less, the transparency of the colored base layer 2 is lower than when the density exceeds 1.12 [g/cm ³ ]. It is possible to improve the durability and mechanical strength.

<Pattern layer>
The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored base material layer 2, and is a layer for adding a pattern for imparting design. The design layer 3 may be omitted if the coloring of the colored base material layer 2 can be used instead.
The pattern layer 3 is formed using printing ink, paint, or the like. The printing ink, paint, or the like that forms the pattern layer 3 is formed by dissolving or dispersing a coloring agent such as a dye or pigment in a suitable diluent solvent together with a suitable binder resin.

The printing ink, paint, or the like that forms the pattern layer 3 is applied using, for example, various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.
As the binder resin, for example, it is possible to use urethane-based resin, acrylic-based resin, vinyl chloride-based resin, polyimide-based resin, nitrocellulose, etc., or a mixture thereof, but is not limited to these. do not have.
Any pattern can be used as the pattern. For example, wood grain patterns, stone grain patterns, texture patterns, abstract patterns, geometric patterns, characters, symbols, single-color solid colors, etc., or combinations thereof can be used. It is possible. In addition, in order to improve the concealability of the decorative sheet 1, a concealing layer may be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer is formed, for example, using opaque printing ink or paint containing a large amount of opaque pigment such as titanium dioxide or iron oxide.

The thickness of the pattern layer 3 is preferably in the range of 1 [μm] to 10 [μm]. This is because when the pattern layer 3 has a thickness of 1 [μm] or more, clear printing is possible. Further, when the thickness of the pattern layer 3 is 10 [μm] or less, the printing workability in manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.
In addition, in order to impart various functions to the pattern layer 3, for example, an extender, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a desiccant, a curing agent, a curing accelerator and a curing agent are added. Functional additives such as retardants may be added.
In addition, the pattern layer 3 includes, for example, a solid colored base layer for concealing the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern for adding a design. It is good also as a structure which has a pattern pattern layer.

<Adhesive layer>
The adhesive layer 4 is laminated on one surface (upper surface in FIG. 1) of the pattern layer 3 and used for bonding the pattern layer 3 and the transparent resin layer 5 together.
As the material of the adhesive layer 4, for example, urethane, acrylic, olefin, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, polyolefin and the like can be used.

<Transparent resin layer>
The transparent resin layer 5 is laminated on one surface (the upper surface in FIG. 1) of the adhesive layer 4, and is made of transparent plant-derived high-density polyethylene (for example, “Green polyethylene (SHC7260)” manufactured by Braskem). ) is formed using a resin composition containing.
The transparent resin layer 5 may contain plant-derived low-density polyethylene or plant-derived linear low-density polyethylene.
The density of the transparent resin layer 5 is, for example, within the range of 0.92 [g/cm ³ ] to 0.99 [g/cm ³ ], preferably 0.94 [g/cm ³ ] to 0.98 [ g/cm ³ ] or less, more preferably 0.95 [g/cm ³ ] or more and 0.97 [g/cm ³ ] or less.
When the density of the transparent resin layer 5 is 0.92 [g/cm ³ ] or more, the rigidity of the transparent resin layer 5 is increased compared to when the density is less than 0.92 [g/cm ³ ]. becomes possible. Further, when the density ^of the transparent resin layer 5 is 0.99 [g/cm ³ ] or less, the transparency and It becomes possible to increase the mechanical strength.
For the transparent resin layer 5, for example, plant-derived polypropylene having a density within the range of 0.90 [g/cm ³ ] to 0.91 [g/cm ³ ] may be used.

A nucleating agent (for example, “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd.) is added to the high-density polyethylene forming the transparent resin layer 5 .
The nucleating agent is added to the high density polyethylene within the range of 500 [ppm] or more and 2000 [ppm] or less based on the mass of the high density polyethylene.
In the first embodiment, as an example, a case where a nucleating agent is added to high-density polyethylene within a range of 1500 [ppm] or more and 2000 [ppm] or less based on the mass of high-density polyethylene will be described.

The transparent resin layer 5 may optionally contain, for example, a colorant, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, an antifungal agent. At least one selected from various additives such as agents, antifriction agents, light scattering agents and gloss modifiers may be added.
The transparent resin layer 5 preferably has a degree of transparency (colorless transparency, colored transparency, translucent) that allows the pattern of the pattern layer 3 to be seen through from the surface (upper surface) of the decorative sheet 1 .
The thickness of the transparent resin layer 5 is, for example, within the range of 20 [μm] or more and 200 [μm] or less, preferably 55 [μm] or more and 150 [μm] or less, more preferably 60 [μm] or more and 80 [μm] or more. [μm] or less.

<Surface protective layer>
The surface protective layer 6 is laminated on one surface (the upper surface in FIG. 1) of the transparent resin layer 5, and provides the decorative sheet 1 with weather resistance, scratch resistance, stain resistance, design properties, and the like. It is a layer provided to impart functions.
Moreover, the surface protective layer 6 is formed using, for example, an acrylic resin composition.
In addition, the surface protective layer 6 may optionally contain weather resistant agents, plasticizers, stabilizers, fillers, dispersants, coloring agents such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, and light stabilizers. , anti-blocking agents, catalyst scavengers, colorants, light scattering agents, gloss modifiers, and other additives. In addition, the surface protective layer 6 may contain functional additives such as antiviral agents, antibacterial agents, antifungal agents, etc., if necessary.

<Uneven part>
The concave-convex portion 7 is formed by concave portions provided at a plurality of locations on the transparent resin layer 5 and the surface protective layer 6 .

<Primer layer>
The primer layer 8 is a layer serving as a base, and is a layer for improving adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9 .
Further, the primer layer 8 is laminated on the other surface (the lower surface in FIG. 1) of the colored base material layer 2 .
Furthermore, the primer layer 8 is formed using, for example, a polyester-based resin, an organic additive, a pigment, or the like.
In the second embodiment, as an example, a case where the primer layer 8 is formed using polyester urethane obtained by isocyanate cross-linking polyester polyol will be described.
In addition, the primer layer 8 may contain an antirust pigment for the purpose of improving corrosion resistance.
The thickness of the primer layer 8 is, for example, within the range of 1 [μm] or more and 10 [μm] or less.

The second embodiment described above is an example of the present invention, and the present invention is not limited to the second embodiment described above. Various modifications are possible according to the design and the like within the scope of not departing from the technical idea.

(Effect of Second Embodiment)
If it is the decorative sheet 1 of 2nd Embodiment, it will become possible to have an effect described below.
(1) A colored substrate layer 2 and a transparent resin layer 5 laminated on one side of the colored substrate layer 2, and the transparent resin layer 5 is made of a resin composition containing plant-derived high-density polyethylene. A nucleating agent is added to the high-density polyethylene.
Therefore, even in a configuration using plant-derived high-density polyethylene, which is a plant-derived material, the transparent resin layer 5 having a high hardness equivalent to a configuration formed using fossil fuel-derived polyethylene is formed. becomes possible.

As a result, it is possible to provide the decorative sheet 1 capable of suppressing a decrease in surface hardness even when formed using plant-derived high-density polyethylene, which is a plant-derived material.
In addition, even in a configuration using plant-derived high-density polyethylene, which is a plant-derived material, it is possible to form a transparent resin layer 5 having high transparency equivalent to a configuration formed using fossil fuel-derived polyethylene. becomes possible.

(2) The nucleating agent is added within the range of 500 [ppm] or more and 2000 [ppm] or less based on the mass of the high-density polyethylene.
As a result, it is possible to provide the decorative sheet 1 with less haze.

(3) The nucleating agent is added within the range of 1500 [ppm] or more and 2000 [ppm] or less based on the mass of the high-density polyethylene.
As a result, it is possible to provide the decorative sheet 1 with less haze than a configuration in which the nucleating agent is added at less than 1500 [ppm] based on the mass of the high-density polyethylene.

Further, with the decorative material 10 of the second embodiment, it is possible to obtain the effects described below.
(4) The base material 9 and the decorative sheet 1 laminated on at least one surface of the base material 9 are provided.
As a result, it is possible to provide the decorative material 10 capable of suppressing a decrease in surface hardness even when formed using plant-derived high-density polyethylene, which is a plant-derived material.

(Third embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG.
The configuration of the decorative material 10 in the third embodiment is the same as that of the above-described first embodiment except for the configuration of the decorative sheet 1, so the description of the configuration other than the decorative sheet 1 will be omitted.

(Configuration of decorative sheet)
As shown in FIG. 1, the decorative sheet 1 includes a colored substrate layer 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer 5, a surface protective layer 6, an uneven portion 7, and a primer layer 8. Prepare.
The configuration of the decorative sheet 1 in the third embodiment is the same as that of the above-described first embodiment except for the configuration of the colored base layer 2, so the description of the configuration other than the colored base layer 2 is omitted. do.

<Colored substrate layer>
The configuration of the colored base material layer 2 is the same as that of the above-described first embodiment, except that it is formed using a resin composition in which plant-derived high-density polyethylene and low-density polyethylene are mixed. .
As the plant-derived high-density polyethylene, for example, "Green polyethylene (SHC7260)" manufactured by Braskem is used.

Low density polyethylene is, for example, polyethylene with a density of 0.94 or less.
3rd Embodiment demonstrates the case where the low density polyethylene which forms the colored base material layer 2 is plant-derived low density polyethylene as an example.
As the plant-derived low-density polyethylene, for example, Braskem's "Green Polyethylene (SPB681)" is used.

In addition, the low-density polyethylene forming the colored substrate layer 2 is contained in the colored substrate layer 2 within a range of 5% by mass or more and 30% by mass or less in 100% by mass of the colored substrate layer 2. .
In the third embodiment, as an example, a case where the mixing ratio of high-density polyethylene and low-density polyethylene in the colored substrate layer 2 is within the range of 95:5 to 70:30 will be described.

In addition, the third embodiment described above is an example of the present invention, and the present invention is not limited to the third embodiment described above. Various modifications are possible according to the design and the like within the scope of not departing from the technical idea.

(Effect of the third embodiment)
If it is the decorative sheet 1 of 3rd Embodiment, it will become possible to have an effect described below.
(1) The colored substrate layer 2 is formed using a resin composition in which plant-derived high-density polyethylene and low-density polyethylene are mixed.
As a result, it is possible to provide the decorative sheet 1 capable of suppressing deterioration in bending suitability and deterioration in machinability.

(2) The low-density polyethylene forming the colored substrate layer 2 is plant-derived low-density polyethylene.
As a result, it is possible to reduce the load on the environment.

(3) The low-density polyethylene forming the colored substrate layer 2 is contained in the colored substrate layer 2 within a range of 5% by mass or more and 30% by mass or less in 100% by mass of the colored substrate layer 2. there is
As a result, it becomes possible to suppress the film-forming stability and strength of the decorative sheet 1 from deteriorating.
That is, when the content of the low-density polyethylene is low, the film forming stability of the decorative sheet 1 is poor, and when the content of the low-density polyethylene is high, the decorative sheet 1 becomes too soft. However, the low-density polyethylene forming the colored substrate layer 2 is contained in the colored substrate layer 2 within the range of 5% by mass or more and 30% by mass or less in 100% by mass of the colored substrate layer 2. This makes it possible to solve the problem.

(4) The mixing ratio of high-density polyethylene and low-density polyethylene in the colored substrate layer 2 is within the range of 95:5 to 70:30.
As a result, it becomes possible to suppress the film-forming stability and strength of the decorative sheet 1 from deteriorating.
That is, when the content of the low-density polyethylene is low, the film forming stability of the decorative sheet 1 is poor, and when the content of the low-density polyethylene is high, the decorative sheet 1 becomes too soft. However, the problem can be solved by setting the mixing ratio of the high-density polyethylene and the low-density polyethylene in the colored substrate layer 2 within the range of 95:5 to 70:30.

(Fourth embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG.
Note that the configuration of the decorative material 10 in the second embodiment is the same as that of the above-described first embodiment except for the configuration of the decorative sheet 1, so the description of the configuration other than the decorative sheet 1 will be omitted.

(Configuration of decorative sheet)
As shown in FIG. 1, the decorative sheet 1 includes a colored substrate layer 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer 5, a surface protective layer 6, an uneven portion 7, and a primer layer 8. Prepare.
The configuration of the decorative sheet 1 in the fourth embodiment is the same as that of the above-described second embodiment except for the configuration of the transparent resin layer 5, so the description of the configuration other than the transparent resin layer 5 will be omitted.

<Transparent resin layer>
The configuration of the transparent resin layer 5 is the same as that of the above-described first embodiment, except that it is formed using a resin composition in which plant-derived high-density polyethylene and plant-derived low-density polyethylene are mixed. is.
In the fourth embodiment, as an example, a case where the mixing ratio of high-density polyethylene and low-density polyethylene in the transparent resin layer 5 is within the range of 80:20 to 60:40 will be described.

In addition, the fourth embodiment described above is an example of the present invention, and the present invention is not limited to the second embodiment described above. Various modifications are possible according to the design and the like within the scope of not departing from the technical idea.

(Effect of the fourth embodiment)
If it is the decorative sheet 1 of 4th Embodiment, it will become possible to have an effect described below.
(1) The transparent resin layer 5 is formed using a resin composition in which plant-derived high-density polyethylene and plant-derived low-density polyethylene are mixed.
As a result, the flexibility and transparency of the transparent resin layer 5 can be improved.

(2) The mixing ratio of high-density polyethylene and low-density polyethylene in the transparent resin layer 5 is within the range of 80:20 to 60:40.
As a result, the flexibility and transparency of the transparent resin layer 5 can be improved.

The decorative materials of Examples 1 to 22 and the decorative materials of Comparative Examples 1 to 5 will be described below with reference to the second to fourth embodiments.

(Example 1)
The colored base material layer was formed with a thickness of 55 [μm] using a colored polyethylene resin.
The pattern layer was formed by using urethane-based printing ink after applying a corona discharge treatment to one surface of the colored substrate layer.
The adhesive layer was formed using a urethane-based adhesive.
The transparent resin layer uses "green polyethylene" manufactured by Braskem, which is plant-derived high-density polyethylene (HDPE), and 1500 [ppm] and A nucleating agent, “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd., was added to form the powder. Moreover, the thickness of the transparent resin layer was set to 70 [μm].

The surface protective layer was formed using an acrylic resin composition as a main component.
The primer layer was formed using a polyester urethane resin to a thickness of 1 [μm] or more and 2 [μm] or less after applying a corona discharge treatment to one surface of the colored substrate layer.
Further, by lamination, a decorative sheet of Example 1 having a thickness of 135 [μm] was formed.
After forming the decorative sheet of Example 1, the surface of the primer layer facing the base material is attached to the base material using "BA-10L (curing agent: BA-11B)" manufactured by Japan Coating Resin. , the decorative material of Example 1 was formed.

(Example 2)
Formed in the same manner as in Example 1, except that the nucleating agent "Rikemaster CN-002" manufactured by Riken Vitamin Co., Ltd. was added so as to be 500 [ppm] based on the mass of the high-density polyethylene. , the decorative sheet and decorative material of Example 2 were formed.
(Example 3)
Formed in the same manner as in Example 1, except that the nucleating agent "Rikemaster CN-002" manufactured by Riken Vitamin Co., Ltd. was added so as to be 2000 [ppm] based on the mass of the high-density polyethylene. , the decorative sheet and decorative material of Example 3 were formed.
(Example 4)
Except that the colored base layer was formed using a resin composition obtained by mixing plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) at a ratio of 95: 5. The decorative sheet and decorative material of Example 4 were formed in the same manner as in Example 1.
(Example 5)
Except that the colored base layer was formed using a resin composition obtained by mixing plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) at a ratio of 95: 5. The decorative sheet and decorative material of Example 5 were formed in the same manner as in Example 2.
(Example 6)
Except that the colored base layer was formed using a resin composition obtained by mixing plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) at a ratio of 95: 5. Forming in the same manner as in Example 3, the decorative sheet and decorative material of Example 6 were formed.
(Example 7)
Except that the colored base layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 70:30. The decorative sheet and decorative material of Example 7 were formed in the same manner as in Example 1.
(Example 8)
Except that the colored base layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 70:30. The decorative sheet and decorative material of Example 8 were formed in the same manner as in Example 2.
(Example 9)
Except that the colored base layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 70:30. Forming in the same manner as in Example 3, the decorative sheet and decorative material of Example 9 were formed.
(Example 10)
Example 4, except that the transparent resin layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 80:20. A decorative sheet and a decorative material of Example 10 were formed in the same manner.
(Example 11)
Example 5, except that the transparent resin layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 80:20. A decorative sheet and a decorative material of Example 11 were formed in the same manner.
(Example 12)
Example 6, except that the transparent resin layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 80:20. A decorative sheet and a decorative material of Example 12 were formed in the same manner.
(Example 13)
Except that the colored base layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 70:30. Formation was carried out in the same manner as in Example 10 to form the decorative sheet and decorative material of Example 13. (Example 14)
Except that the colored base layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 70:30. Formation was carried out in the same manner as in Example 11 to form the decorative sheet and decorative material of Example 14. (Example 15)
Except that the colored base layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 70:30. Forming in the same manner as in Example 12, the decorative sheet and decorative material of Example 15 were formed. (Example 16)
Example 10, except that the transparent resin layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 60:40. A decorative sheet and a decorative material of Example 16 were formed in the same manner.
(Example 17)
Example 11, except that the transparent resin layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 60:40. A decorative sheet and a decorative material of Example 17 were formed in the same manner.
(Example 18)
Example 12, except that the transparent resin layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 60:40. A decorative sheet and a decorative material of Example 18 were formed in the same manner.
(Example 19)
Except that the colored base layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 70:30. The decorative sheet and decorative material of Example 19 were formed in the same manner as in Example 16.
(Example 20)
Except that the colored base layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 70:30. Forming in the same manner as in Example 17, the decorative sheet and decorative material of Example 20 were formed. (Example 21)
Except that the colored base layer was formed using a resin composition in which plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) were mixed at a ratio of 70:30. The decorative sheet and decorative material of Example 21 were formed in the same manner as in Example 18. (Example 22)
A decorative sheet and decorative material of Example 22 were formed in the same manner as in Example 1, except that the adhesive layer was formed using a maleic anhydride-modified polyethylene resin.

(Comparative example 1)
A decorative sheet and decorative material of Comparative Example 1 were formed in the same manner as in Example 1, except that no nucleating agent was added to the high-density polyethylene.
(Comparative example 2)
Same as Example 1, except that the transparent resin layer was formed using polyethylene obtained by mixing plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) at a ratio of 50:50. By forming, a decorative sheet and a decorative material of Comparative Example 2 were formed.
(Comparative Example 3)
A decorative sheet and decorative material of Comparative Example 3 were formed in the same manner as in Comparative Example 2, except that no nucleating agent was added to the high-density polyethylene.
(Comparative Example 4)
A decorative sheet and a decorative material of Comparative Example 4 were formed in the same manner as in Example 1, except that the transparent resin layer was formed of plant-derived low-density polyethylene (LDPE).
(Comparative Example 5)
Except that the colored substrate layer was formed using a resin composition obtained by mixing plant-derived high-density polyethylene (HDPE) and plant-derived low-density polyethylene (LDPE) at a ratio of 60:40. A decorative sheet and a decorative material of Comparative Example 5 were formed in the same manner as in Example 1.

(Performance evaluation, evaluation results)
The decorative materials of Examples 1 to 22 and the decorative materials of Comparative Examples 1 to 5 were evaluated for surface hardness, productivity, permeability, haze, suitability for bending, and machinability. As the evaluation method, the method described below was used.

<Surface hardness>
After carrying out a pencil hardness test using pencils of different hardnesses on the decorative material, damage (gouging) occurring on the surface (surface protective layer) was confirmed to evaluate the surface hardness. Then, after conducting the pencil hardness test using a pencil having a hardness of 2B or more, the case where damage occurred on the surface was evaluated as "⊚", and after conducting the pencil hardness test using a pencil having a hardness of 4B or more. , and the case where damage occurred on the surface was evaluated as "○". In addition, a case where damage occurred on the surface after conducting a pencil hardness test using a pencil having a hardness of 5B or less was evaluated as "x".
<Productivity>
Productivity was evaluated according to whether or not there was a problem in manufacturing the decorative sheet. If there is no problem in manufacturing the decorative sheet, it is evaluated as "A"; if there is no problem in manufacturing the decorative sheet, it is evaluated as "○"; It was evaluated as "x".

<Transparency>
The total light transmittance at a wavelength of 555 [nm] is measured with a spectrophotometer (integrating sphere) in a state where the thickness of the transparent resin layer is set within the range of 70 [μm] or more and 80 [μm] or less, Permeability was evaluated. Then, the case where the total light transmittance is 85% is evaluated as "◎", and the case where the total light transmittance is within the range of 80% or more and 85% or less is evaluated as "○", and the total light transmittance is evaluated as "○". A case of less than 80% was evaluated as "x".
<Haze>
The haze % of the transparent resin layer was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufactured by Shimadzu Corporation: "UV-3600").
When measuring the haze % of the transparent resin layer, first, a resin having the same composition as the transparent resin layer provided in the decorative sheets of Examples 1 to 22 and the transparent resin layer provided in the decorative sheets of Comparative Examples 1 to 5 was used. was extruded with the thickness set within the range of 70 [μm] to 80 [μm] to form a resin film. Next, the haze at a wavelength of 555 [nm] was measured with a spectrophotometer (integrating sphere) to evaluate the haze. Then, when the haze is less than 15%, it is evaluated as "◎", when the haze is within the range of 15% or more and less than 25%, it is evaluated as "◯", and when the haze is 25% or more, it is evaluated as " x” was evaluated.
<Bending suitability>
Using a decorative sheet (that is, a decorative material) laminated to MDF (Medium Density Fiberboard), suitability for V-cutting (presence or absence of whitening on bending) was confirmed to evaluate suitability for bending. Then, those in which whitening did not occur were evaluated as "○" (acceptable), those in which slight whitening occurred were evaluated as "△" (acceptable), and those in which whitening occurred were evaluated as "x". (failed).
<Machinability>
The decorative sheet (that is, the decorative material) attached to the MDF is cut with a circular saw and then cut with a hand router to reach the MDF. evaluated. A case where no burrs were generated was evaluated as "good", and a case where burrs were generated on almost the entire surface and correction was difficult was evaluated as "poor".

As a result of evaluating various performances using the methods described above, the decorative materials of Examples 1 to 22 exhibited excellent performances in all evaluation tests. On the other hand, the decorative materials of Comparative Examples 1 to 5 were unable to exhibit excellent performance in all evaluation tests.

(Fifth embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG. A specific configuration of the decorative sheet 1 will be described later.
The configuration of the decorative material 10 in the fifth embodiment is the same as that of the above-described first embodiment except for the configuration of the decorative sheet 1, so the description of the configuration other than the decorative sheet 1 will be omitted.

(Configuration of decorative sheet)
As shown in FIG. 1, the decorative sheet 1 includes a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface It includes a protective layer 6 , uneven portions 7 and a primer layer 8 .

<Colored substrate layer>
The colored substrate layer 2 is a resin layer formed using a thermoplastic resin, and is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (derived from plants).
The composition of the colored substrate layer 2 will be described in detail below.
(Polyethylene derived from biomass)
In the fifth embodiment, the biomass-derived polyethylene is obtained by polymerizing a monomer containing biomass-derived ethylene. Ethylene derived from biomass is not particularly limited, and ethylene produced by a conventionally known method can be used. Since biomass-derived ethylene is used as a raw material monomer, the polymerized polyethylene is biomass-derived.
The raw material monomer for polyethylene does not have to contain 100% by mass of biomass-derived ethylene.

The monomer, which is a raw material for biomass-derived polyethylene, may further contain at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin, and may further contain a biomass-derived α-olefin.

Although the number of carbon atoms of the α-olefin is not particularly limited, those having 3 to 20 carbon atoms can usually be used, preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. In addition, by containing such an α-olefin, the polymerized polyethylene has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear polyethylene.

By using ethylene, which is a raw material derived from biomass, it is theoretically possible to manufacture from 100% biomass-derived components.

The biomass-derived ethylene concentration in the polyethylene (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the biomass-derived carbon content by radioactive carbon (C14) measurement. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in polyethylene, the ratio of biomass-derived carbon can be calculated. In the fifth embodiment, the biomass-derived carbon content Pbio can be determined as follows, where PC14 is the content of C14 in polyethylene.
Pbio (%) = PC14/105.5 x 100

In the fifth embodiment, theoretically, if all biomass-derived ethylene is used as the raw material of polyethylene, the biomass-derived ethylene concentration is 100%, and the biomass degree of biomass-derived polyethylene is 100. In addition, the biomass-derived ethylene concentration in the fossil fuel-derived polyethylene produced only from fossil fuel-derived raw materials is 0%, and the biomass degree of the fossil fuel-derived polyethylene is 0.

In the fifth embodiment, the biomass-derived polyethylene and the decorative sheet containing the polyethylene need not have a biomass degree of 100.

In the fifth embodiment, the method for polymerizing the biomass-derived ethylene-containing monomer is not particularly limited, and conventionally known methods can be used. The polymerization temperature and polymerization pressure should be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of a method for polymerizing a monomer containing ethylene is described below.

Polymerization methods for ethylene polymers and copolymers of ethylene and α-olefins vary depending on the type of polyethylene desired, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and direct It can be appropriately selected depending on the difference in density and branching of linear low density polyethylene (LLDPE) or the like. For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any method of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization, It is preferable to carry out in one stage or in multiple stages of two or more stages.

As the biomass-derived polyethylene, an ethylene polymer or an ethylene/α-olefin copolymer may be used alone, or two or more of them may be used in combination.

(Resin composition containing biomass-derived polyethylene)
In 5th Embodiment, a resin composition contains said polyethylene as a main component. The resin composition contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 95% by mass, more preferably 25 to 75% by mass, based on the total resin composition. If the concentration of biomass-derived ethylene in the resin composition is 5% by mass or more, it is possible to reduce the amount of fossil fuel used compared to conventional methods, and to realize a carbon-neutral decorative sheet.

The above resin composition may contain two or more types of polyethylene having different degrees of biomass, and the concentration of biomass-derived ethylene in the resin composition as a whole may be within the above range.

The above resin composition may further contain a fossil fuel-derived polyethylene obtained by polymerizing a monomer containing a fossil fuel-derived ethylene and at least one of a fossil fuel-derived ethylene and an α-olefin. That is, in the fifth embodiment, the resin composition may be a mixture of biomass-derived polyethylene and fossil fuel-derived polyethylene. The mixing method is not particularly limited, and conventionally known methods can be used for mixing. For example, dry blending or melt blending may be used.

According to a fifth embodiment, the resin composition preferably comprises 5-90% by weight, more preferably 25-75% by weight of biomass-derived polyethylene and preferably 10-95% by weight, more preferably 25-75% by weight. % by weight of polyethylene derived from fossil fuels. Even when such a mixed resin composition is used, the concentration of biomass-derived ethylene in the resin composition as a whole should be within the above range.

Various additives other than polyethylene, which is the main component, may be added to the resin composition produced in the production process of the resin composition as long as the characteristics are not impaired. Additives include, for example, plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slip agents, release agents, anti- Oxidizing agents, ion exchange agents, color pigments, and the like can be added. These additives are added in an amount of preferably 1 to 20% by mass, preferably 1 to 10% by mass, based on the total resin composition.

As described above, the colored substrate layer 2 contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 5% by mass or more of the entire colored substrate layer 2. comprises 40-75%. If the concentration of biomass-derived ethylene in the colored substrate layer 2 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

The colored substrate layer 2 has a weight within the range of 0.92 [g/cm ³ ] to 1.12 [g/cm ³ ], preferably 0.98 [g/cm ³ ] to 1.10 [g/cm 3 ]. ³ ] has a density within the following range. The density of the colored base material layer 2 is a value measured according to the method specified in A method of JIS K7112-1980 after annealing according to JIS K6760-1995. If the density of the colored base layer 2 is 0.92 [g/cm ³ ] or more, the rigidity of the colored base layer 2 can be increased. Further, if the density of the colored base layer 2 is 1.12 [g/cm ³ ] or less, the transparency and mechanical strength of the colored base layer 2 can be enhanced.

The colored substrate layer 2 contains, as biomass-derived polyethylene, biomass-derived high-density polyethylene and biomass-derived low-density polyethylene, biomass-derived high-density polyethylene, and fossil fuel-derived low-density polyethylene. or high-density polyethylene derived from fossil fuels and low-density polyethylene derived from biomass.
The biomass degree of the entire colored substrate layer 2 may be in the range of 10% or more and 90% or less.
The biomass-derived high-density polyethylene refers to polyethylene having a density exceeding 0.94. In addition, biomass-derived low-density polyethylene refers to polyethylene having a density of 0.94 or less.
The colored base material layer 2 contains, as biomass-derived polyethylene, biomass-derived high-density polyethylene and low-density polyethylene (either biomass-derived or fossil fuel-derived) at a ratio of 95:5 or more. A blend within the range of 70:30 is preferred. If the content of the low-density polyethylene is low, the film-forming stability is poor, and if the content of the low-density polyethylene is high, the film becomes too soft.

The method for producing the colored base material layer 2 is not particularly limited, and it can be produced by a conventionally known method. In the fifth embodiment, it is preferable to form by calendar molding.

In addition, the colored substrate layer 2 may optionally contain, for example, a coloring agent, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, and an antibacterial agent. , an antifungal agent, an antifriction agent, a light scattering agent, and a luster adjusting agent.
The thickness of the colored substrate layer 2 is preferably in the range of 40 [μm] to 200 [μm], more preferably 51 [μm] to 120 [μm], and 55 [μm]. It is more preferable to be at least 100 [μm] or less. This is because, when the thickness of the colored substrate layer 2 made of biomass-derived polyethylene is 40 [μm] or more, it absorbs the irregularities and steps of the underlying floor material, etc., and the finish of the decorative sheet 1 is improved. This is due to the fact that it is possible to Further, when the thickness of the colored base layer 2 is 200 [μm] or less, the manufacturing cost of the decorative sheet 1 can be reduced without forming the colored base layer 2 thicker than necessary. due to that.

In addition, although 5th Embodiment demonstrated polyethylene derived from biomass as resin which comprises the colored base material layer 2 derived from biomass, this invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the fifth embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the colored substrate layer 2 .

<Pattern layer>
The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored base material layer 2, and is a layer for adding a pattern for imparting design. The design layer 3 may be omitted if the coloring of the colored base material layer 2 can be used instead.
The pattern layer 3 is formed using printing ink, paint, or the like. The printing ink, paint, or the like that forms the pattern layer 3 is formed by dissolving or dispersing a coloring agent such as a dye or pigment in a suitable diluent solvent together with a suitable binder resin.

The printing ink, paint, or the like that forms the pattern layer 3 is applied using, for example, various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.
As the binder resin, for example, it is possible to use urethane-based resin, acrylic-based resin, vinyl chloride-based resin, polyimide-based resin, nitrocellulose, etc., or a mixture thereof, but is not limited to these. do not have.
Any pattern can be used as the pattern. For example, wood grain patterns, stone grain patterns, texture patterns, abstract patterns, geometric patterns, characters, symbols, single-color solid colors, etc., or combinations thereof can be used. It is possible. In addition, in order to improve the concealability of the decorative sheet 1, a concealing layer may be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer is formed, for example, using opaque printing ink or paint containing a large amount of opaque pigment such as titanium dioxide or iron oxide.

The thickness of the pattern layer 3 is preferably in the range of 1 [μm] to 10 [μm]. This is because when the pattern layer 3 has a thickness of 1 [μm] or more, clear printing is possible. Further, when the thickness of the pattern layer 3 is 10 [μm] or less, the printing workability in manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.
In addition, in order to impart various functions to the pattern layer 3, for example, an extender, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a desiccant, a curing agent, a curing accelerator and a curing agent are added. Functional additives such as retardants may be added.
In addition, the pattern layer 3 includes, for example, a solid colored base layer for concealing the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern for adding a design. It is good also as a structure which has a pattern pattern layer.

<Adhesive layer>
The adhesive layer 4 is laminated on one surface (upper surface in FIG. 1) of the pattern layer 3 and used for bonding the pattern layer 3 and the transparent resin layer 5 together.
As the material of the adhesive layer 4, for example, urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, polyolefin, or the like can be used. A polyolefin resin is particularly preferred because of its adhesiveness to the transparent resin layer 5 .

<Transparent resin layer>
The transparent resin layer 5 is laminated on one surface (the upper surface in FIG. 1) of the adhesive layer 4, and is formed of the above resin composition containing biomass-derived (plant-derived) polyethylene. is. More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing biomass-derived polyethylene obtained by polymerizing the above-described biomass-derived ethylene-containing monomer. That is, in the transparent resin layer 5, the resin composition containing the biomass-derived polyethylene used in the colored substrate layer 2 may be used. Further, it may contain fossil fuel-derived polyethylene obtained by polymerizing a monomer containing fossil fuel-derived ethylene and at least one of fossil fuel-derived ethylene and α-olefin.

The transparent resin layer 5 contains 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 40 to 75% by mass of the biomass-derived ethylene described above with respect to the entire transparent resin layer 5. may comprise: If the concentration of biomass-derived ethylene in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

The density of the transparent resin layer 5 is in the range of 0.92 [g/cm ³ ] to 0.99 [g/cm ³ ], preferably 0.94 [g/cm 3 ] to 0.98 [g/cm ³ ]. cm ³ ] or less, more preferably 0.95 [g/cm ³ ] or more and 0.97 [g/cm ³ ] or less. The density of the transparent resin layer 5 is a value measured according to the method specified in A method of JIS K7112-1980 after performing annealing according to JIS K6760-1995. If the density of the transparent resin layer 5 is 0.92 [g/cm ³ ] or more, the rigidity of the transparent resin layer 5 can be increased. Moreover, if the density of the transparent resin layer 5 is 0.99 [g/cm ³ ] or less, the transparency and mechanical strength of the transparent resin layer 5 can be enhanced.

The transparent resin layer 5 has a thickness of 55 to 150 [μm], preferably 55 to 100 [μm], more preferably 60 to 80 [μm].

The transparent resin layer 5 may contain biomass-derived high-density polyethylene as the biomass-derived polyethylene.
In addition, the transparent resin layer 5 may contain, as biomass-derived polyethylene, polyethylene obtained by blending biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in a range of 100:0 to 20:80. .
Further, the transparent resin layer 5 may have a biomass degree of 10% or more and 90% or less.

The method for manufacturing the transparent resin layer 5 is not particularly limited, and it can be manufactured by a conventionally known method. In the fifth embodiment, it is preferably formed by extrusion molding, and more preferably extrusion molding is performed by a T-die method or an inflation method.

In the fifth embodiment, it is preferable that the transparent resin layer 5 and the colored substrate layer 2 satisfy the following specific relationship with respect to density, thickness, and biomass degree (biomass-derived ethylene concentration).

In the fifth embodiment, it is preferable that the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 satisfy d2>d1. This is because formability is required in order to function as the transparent resin layer 5 and productivity is required in order to function as the colored base material layer 2 .
The ratio (d2/d1) between the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 is preferably in the range of 1.1 to 1.5, and preferably 1.1 to 1.1. It is more preferably within the range of 3 or less, and further preferably within the range of 1.1 or more and 1.2 or less. When the density ratio of the transparent resin layer and the colored substrate layer is within this range, even when biomass-derived polyethylene is used, the decorative sheet can have the necessary extrusion suitability and bending suitability.

In the fifth embodiment, it is preferable that the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored base material layer 2 satisfy t1≧t2. This is because the thickness is required to function as the transparent resin layer 5 and the thickness as the transparent resin layer 5 is not necessary to function as the colored base material layer 2 .
The ratio (t1/t2) between the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored base material layer 2 is preferably in the range of 1.1 to 3, more preferably 1.1 to 2. more preferably within the range of 1.1 or more and 1.5 or less.

In the fifth embodiment, it is preferable that the biomass-derived ethylene concentration C1 in the transparent resin layer 5 and the biomass-derived ethylene concentration C2 in the colored substrate layer 2 satisfy C1>C2. This is because, in order to function as the transparent resin layer 5, the thickness is large and the amount of ethylene used is large.

The biomass-derived polyethylene forming the transparent resin layer 5 may be added with a nucleating agent (for example, “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd.).
The nucleating agent is preferably added to polyethylene within the range of 500 [ppm] to 2000 [ppm] based on the mass of polyethylene, and within the range of 1500 [ppm] to 2000 [ppm], It is more preferable if it is added to polyethylene.

The transparent resin layer 5 may optionally contain, for example, a colorant, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, an antifungal agent. At least one selected from various additives such as agents, antifriction agents, light scattering agents and gloss modifiers may be added.
The transparent resin layer 5 preferably has a degree of transparency (colorless transparency, colored transparency, translucent) that allows the pattern of the pattern layer 3 to be seen through from the surface (upper surface) of the decorative sheet 1 .

In the fifth embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the fifth embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin forming the transparent resin layer 5 .

<Surface protective layer>
The surface protective layer 6 is laminated on one surface (the upper surface in FIG. 1) of the transparent resin layer 5, and provides the decorative sheet 1 with weather resistance, scratch resistance, stain resistance, design properties, and the like. It is a layer provided to impart functions.
The surface protective layer 6 can be made of a thermosetting resin or an ionizing radiation curable resin, and is formed using, for example, an acrylic resin composition.
In addition, the surface protective layer 6 may optionally contain weathering agents, plasticizers, stabilizers, fillers, dispersants, coloring agents such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, and light stabilizers. , anti-blocking agents, catalyst scavengers, colorants, light scattering agents, gloss modifiers, and other additives.
Moreover, the surface protective layer 6 may contain functional additives such as an antibacterial agent and an antifungal agent, if necessary.

<Uneven part>
The concave-convex portion 7 is formed by concave portions provided at a plurality of locations on the transparent resin layer 5 and the surface protective layer 6 .

<Primer layer>
The primer layer 8 is a layer serving as a base, and is a layer for improving adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9 .
Further, the primer layer 8 is laminated on the other surface (the lower surface in FIG. 1) of the colored base material layer 2 .
Furthermore, the primer layer 8 is formed using, for example, a polyester-based resin, an organic additive, a pigment, or the like.
In addition, the primer layer 8 may contain an antirust pigment for the purpose of improving corrosion resistance.
The thickness of the primer layer 8 is, for example, within the range of 1 [μm] or more and 10 [μm] or less.

The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications are possible according to the design and the like as long as they do not deviate.

(Effect of the fifth embodiment)
If it is the decorative sheet 1 of 5th Embodiment, it will become possible to have an effect described below.
(1) The colored substrate layer 2 and the transparent resin layer 5 are resin layers each formed of a resin composition containing biomass-derived polyethylene obtained by polymerizing a monomer containing biomass-derived ethylene. It contains ethylene derived from biomass, has a density within the range of 0.92 [g/cm ³ ] or more and 0.99 [g/cm ³ ] or less, and has a density within the range of 55 [μm] or more and 150 [μm] or less The colored base material layer 2 has a thickness, contains biomass-derived ethylene, has a density within the range of 0.92 [g/cm ³ ] or more and 1.12 [g/cm ³ ] or less, and has a density of 51 It has a thickness within the range of [μm] to 120 [μm].
Therefore, even in a configuration using biomass-derived polyethylene, which is a plant-derived material, for example, the colored base layer 2 and the transparent resin layer 5 have high hardness equivalent to a configuration formed using polypropylene or the like. can be formed.

As a result, it is possible to provide the decorative sheet 1 capable of suppressing a decrease in surface hardness even when formed using biomass-derived polyethylene, which is a plant-derived material.
In addition, even with a structure using biomass-derived polyethylene, which is a plant-derived material, it is possible to form a transparent resin layer 5 having high transparency, which is equivalent to a structure formed using polypropylene or the like, for example. Become.

(2) At least one of the transparent resin layer 5 and the colored substrate layer 2 contains biomass-derived high-density polyethylene and biomass-derived low-density polyethylene as biomass-derived polyethylene.
As a result, it becomes possible to form the transparent resin layer 5 and the colored substrate layer 2 having further flexibility.

(3) The transparent resin layer 5 contains polyethylene obtained by blending biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in the range of 100:0 to 20:80 as biomass-derived polyethylene. there is As a result, it becomes possible to form the transparent resin layer 5 having a higher hardness.

(4) The colored substrate layer 2 contains biomass-derived high-density polyethylene and low-density polyethylene as biomass-derived polyethylene, and has a biomass degree within the range of 10% or more and 90% or less.
As a result, it is possible to form the colored base material layer 2 having good film-forming stability and sufficient softness as a decorative sheet.

(5) When the density of the transparent resin layer 5 is d1 and the density of the colored substrate layer 2 is d2, d2>d1 is satisfied.
As a result, it is possible to form the decorative sheet 1 having sufficient extrusion suitability.

(6) When the thickness of the transparent resin layer 5 is t1 and the thickness of the colored substrate layer 2 is t2, t1≧t2 is satisfied.
As a result, it is possible to form the decorative sheet 1 having sufficient bending suitability.

Further, with the decorative material 10 of the fifth embodiment, it is possible to obtain the effects described below.
(7) The base material 9 and the decorative sheet 1 laminated on at least one surface of the base material 9 are provided.
As a result, it is possible to provide the decorative material 10 capable of suppressing a decrease in surface hardness even when formed using biomass-derived polyethylene, which is a plant-derived material.

The decorative materials of Examples 1 to 11 and the decorative materials of Comparative Examples 1 to 5 will be described below with reference to the fifth embodiment.

(Example 1)
After applying corona discharge treatment to one side of the base material, a pattern layer printed with urethane-based printing ink, a urethane-based adhesive layer, and a maleic anhydride-modified polyethylene resin layer ( A transparent adhesive layer), a transparent resin layer, and a surface protective layer containing an acrylic resin composition as a main component were laminated in this order. After the other surface of the substrate was subjected to corona discharge treatment, a primer layer (thickness: 1 to 2 [μm]) made of polyester urethane resin was formed. Thus, a decorative sheet of Example 1 (total thickness: 135 [μm]) was obtained.
In Example 1, a colored substrate layer (thickness: 55 [μm]) formed of a resin composition containing biomass-derived high-density polyethylene and fossil fuel-derived low-density polyethylene was used as the substrate. A colored substrate layer was obtained by subjecting this resin composition to calendar molding. The biomass degree of the colored substrate layer thus formed is 80%, and the density of the colored substrate layer is 1.08 [g/cm ³ ].
As the transparent resin layer, a transparent resin layer (thickness: 80 [μm]) formed of a resin composition containing biomass-derived polyethylene (“Biomass Polyethylene” manufactured by Braskem) was used. This biomass-derived polyethylene was obtained by blending biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) so that the ratio (high-density polyethylene/low-density polyethylene) was 80/20. Resin. This resin was Ruder-laminated to obtain a transparent resin layer. The transparent resin layer thus formed has a biomass degree of 94% and a density of 0.95 [g/cm ³ ].

(Example 2)
Using Braskem's "biomass polyethylene", biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) are mixed at a ratio (high-density polyethylene/low-density polyethylene) of 100/0. A decorative sheet of Example 2 was obtained in the same manner as in Example 1, except that the resin was blended to obtain a transparent resin layer by Ruder lamination. The transparent resin layer thus formed had a biomass degree of 94% and a density of 0.96 [g/cm ³ ].

(Example 3)
Using Braskem's "biomass polyethylene", biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) are mixed at a ratio (high-density polyethylene/low-density polyethylene) of 60/40. A decorative sheet of Example 3 was obtained in the same manner as in Example 1, except that the resin was blended to obtain a transparent resin layer by Ruder lamination. The density of the transparent resin layer thus formed was 0.94 [g/cm ³ ].

(Example 4)
Using Braskem's "biomass polyethylene", biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) are mixed at a ratio (high-density polyethylene/low-density polyethylene) of 50/50. A decorative sheet of Example 4 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained by performing Ruder lamination of the resin. The density of the transparent resin layer thus formed was 0.93 [g/cm ³ ].

(Example 5)
Using Braskem's "biomass polyethylene", biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) are mixed at a ratio (high-density polyethylene/low-density polyethylene) of 30/70. A decorative sheet of Example 5 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained by performing Ruder lamination of the resin. The density of the transparent resin layer thus formed was 0.92 [g/cm ³ ].

(Example 6)
A decorative sheet of Example 6 was obtained in the same manner as in Example 1, except that the thickness of the transparent resin layer was 55 [μm] and the thickness of the colored base layer was 55 [μm].

(Example 7)
A decorative sheet of Example 7 was obtained in the same manner as in Example 1, except that the thickness of the transparent resin layer was changed to 150 [μm].

(Example 8)
A decorative sheet of Example 8 was obtained in the same manner as in Example 1, except that the density of the colored base layer was 0.92 [g/cm ³ ].

(Example 9)
A decorative sheet of Example 9 was obtained in the same manner as in Example 1, except that the density of the colored base layer was 1.12 [g/cm ³ ].

(Example 10)
A decorative sheet of Example 10 was obtained in the same manner as in Example 1, except that the thickness of the colored base layer was 51 [μm].

(Example 11)
A decorative sheet of Example 11 was obtained in the same manner as in Example 1, except that the thickness of the colored base layer was 120 [μm].

(Comparative example 1)
Using Braskem's "biomass polyethylene", biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) are mixed at a ratio (high-density polyethylene/low-density polyethylene) of 0/100. A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained by performing Ruder lamination of the resin. The density of the transparent resin layer thus formed was 0.91 [g/cm ³ ].

(Comparative example 2)
A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1, except that the thickness of the transparent resin layer was changed to 30 [μm].

(Comparative Example 3)
A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1, except that the thickness of the transparent resin layer was changed to 200 [μm].

(Comparative Example 4)
A decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1, except that the thickness of the colored base layer was 40 [μm].

(Comparative Example 5)
A decorative sheet of Comparative Example 5 was obtained in the same manner as in Example 1, except that the thickness of the colored base layer was 150 [μm].

(Performance evaluation, evaluation results)
For the decorative sheets of Examples 1 to 11 and the decorative sheets of Comparative Examples 1 to 5, respectively, "haze (%) of transparent resin layer", "pencil hardness", "Hoffman scratch test", "extrusion suitability", "Bend whitening" was evaluated. As the evaluation method, the method described below was used.

<Haze (%) of transparent resin layer>
The haze (%) of the transparent resin layer was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufacturer: Shimadzu Corporation, model number: UV-3600).
A resin having the same composition as the transparent resin layer of each example and comparative example was extruded to a thickness of 70 [μm] or more and 80 [μm] or less to obtain a resin film. The haze was evaluated by measuring the haze at a wavelength of 555 [nm] with a spectrophotometer (integrating sphere). Then, when the haze is less than 15%, it is evaluated as "◎", when the haze is within the range of 15% or more and less than 25%, it is evaluated as "◯", and when the haze is 25% or more, it is evaluated as " x” was evaluated.
In addition, in the present Example, "double-circle" and "good" were made into the pass.

<Pencil hardness>
The pencil hardness was measured with a pencil hardness tester (automatic) (manufacturer: Yoshimitsu Seiki, model number: C221A).
After conducting a pencil hardness test using pencils of different hardnesses on the decorative material including the decorative sheet of each example and comparative example, damage (gouging) occurring on the surface (surface protective layer) was confirmed. Surface hardness was evaluated. Then, after conducting the pencil hardness test using a pencil having a hardness of 2B or more, the case where damage occurred on the surface was evaluated as "⊚", and after conducting the pencil hardness test using a pencil having a hardness of 4B or more. , and the case where damage occurred on the surface was evaluated as "○". In addition, a case where damage occurred on the surface after conducting a pencil hardness test using a pencil having a hardness of 5B or less was evaluated as "x".
In addition, in the present Example, "double-circle" and "good" were made into the pass.

<Hoffman scratch test>
The Hoffman scratch test was conducted by setting a scratch blade (cylindrical blade of φ7) so as to contact the surface of the decorative sheet at an angle of 45 degrees, and moving the tester on the decorative sheet.
Gradually increasing the load (weight) within the range of 200 to 2000 g (every 200 g) and scratching, the load (g) at which the sample surface was scratched was evaluated. In addition, when the damage was caused by a load of 800 g, "600 g" was described in the table as the withstand load.
In addition, in the present Example, the case where the withstand load was "200 g" was rejected.

<Extrusion suitability>
A transparent resin layer was extruded and its production suitability (extrusion suitability) was confirmed.
As a result, if the product can be manufactured (molded) without any problems, it is rated as "○" (accepted). On the other hand, those with the possibility of defects were rated as "Δ" (failed).

<Bending whitening>
Using a decorative sheet (that is, a decorative material) laminated to MDF, suitability for V-cut processing (presence or absence of whitening upon bending) was confirmed.
As a result, "○" (pass) was given when no whitening occurred, "△" (pass) was given when slight whitening occurred, and "×" (failed) was given when whitening occurred. ).

As a result of evaluating various performances using the methods described above, the decorative sheets of Examples 1 to 11 exhibited excellent performances in all evaluation tests. On the other hand, the decorative sheets of Comparative Examples 1 to 5 exhibited insufficient performance in at least some of the evaluation tests.

(Sixth embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG. A specific configuration of the decorative sheet 1 will be described later.
Note that the configuration of the decorative material 10 in the sixth embodiment is the same as that of the above-described first embodiment except for the configuration of the decorative sheet 1, so the description of the configuration other than the decorative sheet 1 will be omitted.

(Configuration of decorative sheet)
As shown in FIG. 1, the decorative sheet 1 includes a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface It includes a protective layer 6 , uneven portions 7 and a primer layer 8 .

<Colored substrate layer>
The colored substrate layer 2 is a resin layer formed using a thermoplastic resin, and is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (derived from plants).
The composition of the colored substrate layer 2 will be described in detail below.
(Polyethylene derived from biomass)
In the sixth embodiment, the biomass-derived polyethylene is obtained by polymerizing a monomer containing biomass-derived ethylene. Ethylene derived from biomass is not particularly limited, and ethylene produced by a conventionally known method can be used. Since biomass-derived ethylene is used as a raw material monomer, the polymerized polyethylene is biomass-derived.
The raw material monomer for polyethylene does not have to contain 100% by mass of biomass-derived ethylene.

The monomer, which is a raw material for biomass-derived polyethylene, may further contain at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin, and may further contain a biomass-derived α-olefin.

Although the number of carbon atoms of the α-olefin is not particularly limited, those having 3 to 20 carbon atoms can usually be used, preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. In addition, by containing such an α-olefin, the polymerized polyethylene has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear polyethylene.

By using ethylene, which is a raw material derived from biomass, it is theoretically possible to manufacture from 100% biomass-derived components.

The biomass-derived ethylene concentration in the polyethylene (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the biomass-derived carbon content by radioactive carbon (C14) measurement. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in polyethylene, the ratio of biomass-derived carbon can be calculated. In the sixth embodiment, the biomass-derived carbon content Pbio can be obtained as follows, where PC14 is the content of C14 in polyethylene.
Pbio (%) = PC14/105.5 x 100

In the sixth embodiment, theoretically, if all biomass-derived ethylene is used as the raw material of polyethylene, the biomass-derived ethylene concentration is 100%, and the biomass degree of biomass-derived polyethylene is 100. In addition, the biomass-derived ethylene concentration in the fossil fuel-derived polyethylene produced only from fossil fuel-derived raw materials is 0%, and the biomass degree of the fossil fuel-derived polyethylene is 0.

In the sixth embodiment, the biomass-derived polyethylene and the decorative sheet containing the polyethylene need not have a biomass degree of 100.

In the sixth embodiment, the method for polymerizing the biomass-derived ethylene-containing monomer is not particularly limited, and conventionally known methods can be used. The polymerization temperature and polymerization pressure should be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of a method for polymerizing a monomer containing ethylene is described below.

Polymerization methods for ethylene polymers and copolymers of ethylene and α-olefins vary depending on the type of polyethylene desired, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and direct It can be appropriately selected depending on the difference in density and branching of linear low density polyethylene (LLDPE) or the like. For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any method of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization, It is preferable to carry out in one stage or in multiple stages of two or more stages.

As the biomass-derived polyethylene, an ethylene polymer or an ethylene/α-olefin copolymer may be used alone, or two or more of them may be used in combination.

(Resin composition containing biomass-derived polyethylene)
In 6th Embodiment, a resin composition contains said polyethylene as a main component. The resin composition contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 95% by mass, more preferably 25 to 75% by mass, based on the total resin composition. If the concentration of biomass-derived ethylene in the resin composition is 5% by mass or more, it is possible to reduce the amount of fossil fuel used compared to conventional methods, and to realize a carbon-neutral decorative sheet.

The above resin composition may contain two or more types of polyethylene having different degrees of biomass, and the concentration of biomass-derived ethylene in the resin composition as a whole may be within the above range.

The above resin composition may further contain a fossil fuel-derived polyethylene obtained by polymerizing a monomer containing a fossil fuel-derived ethylene and at least one of a fossil fuel-derived ethylene and an α-olefin. That is, in the sixth embodiment, the resin composition may be a mixture of biomass-derived polyethylene and fossil fuel-derived polyethylene. The mixing method is not particularly limited, and conventionally known methods can be used for mixing. For example, dry blending or melt blending may be used.

According to a sixth embodiment, the resin composition preferably comprises 5-90% by weight, more preferably 25-75% by weight of biomass-derived polyethylene and preferably 10-95% by weight, more preferably 25-75% by weight. % by weight of polyethylene derived from fossil fuels. Even when such a mixed resin composition is used, the concentration of biomass-derived ethylene in the resin composition as a whole should be within the above range.

Various additives other than polyethylene, which is the main component, may be added to the resin composition produced in the production process of the resin composition as long as the characteristics are not impaired.
Additives include, for example, plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slip agents, release agents, anti- Oxidizing agents, ion exchange agents, color pigments, and the like can be added. These additives are added in an amount of preferably 1 to 20% by mass, preferably 1 to 10% by mass, based on the total resin composition.

As described above, the colored substrate layer 2 contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 5% by mass or more of the entire colored substrate layer 2. comprises 40-75%. If the concentration of biomass-derived ethylene in the colored substrate layer 2 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

The colored substrate layer 2 has a weight within the range of 0.92 [g/cm ³ ] to 1.12 [g/cm ³ ], preferably 0.98 [g/cm ³ ] to 1.10 [g/cm 3 ]. ³ ] has a density within the following range. The density of the colored base material layer 2 is a value measured according to the method specified in A method of JIS K7112-1980 after annealing according to JIS K6760-1995. If the density of the colored base layer 2 is 0.92 [g/cm ³ ] or more, the rigidity of the colored base layer 2 can be increased. Further, if the density of the colored base layer 2 is 1.12 [g/cm ³ ] or less, the transparency and mechanical strength of the colored base layer 2 can be enhanced.

The colored substrate layer 2 contains, as biomass-derived polyethylene, biomass-derived high-density polyethylene and biomass-derived low-density polyethylene, biomass-derived high-density polyethylene, and fossil fuel-derived low-density polyethylene. or high-density polyethylene derived from fossil fuels and low-density polyethylene derived from biomass. The biomass degree of the entire colored substrate layer 2 may be in the range of 10% or more and 90% or less.
The biomass-derived high-density polyethylene refers to polyethylene having a density exceeding 0.94. In addition, biomass-derived low-density polyethylene refers to polyethylene having a density of 0.94 or less.
The colored base material layer 2 contains, as biomass-derived polyethylene, biomass-derived high-density polyethylene and low-density polyethylene (either biomass-derived or fossil fuel-derived) at a ratio of 95:5 or more. A blend within the range of 70:30 is preferred. If the content of the low-density polyethylene is low, the film-forming stability is poor, and if the content of the low-density polyethylene is high, the film becomes too soft.

The method for producing the colored base material layer 2 is not particularly limited, and it can be produced by a conventionally known method. In the sixth embodiment, it is preferable to form by calendar molding.

In addition, the colored substrate layer 2 may optionally contain, for example, a coloring agent, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, and an antibacterial agent. , an antifungal agent, an antifriction agent, a light scattering agent, and a luster adjusting agent.
The thickness of the colored substrate layer 2 is preferably in the range of 40 [μm] to 200 [μm], more preferably 51 [μm] to 120 [μm], and 55 [μm]. It is more preferable to be at least 100 [μm] or less. This is because, when the thickness of the colored substrate layer 2 made of biomass-derived polyethylene is 40 [μm] or more, it absorbs the irregularities and steps of the underlying floor material, etc., and the finish of the decorative sheet 1 is improved. This is due to the fact that it is possible to Further, when the thickness of the colored base layer 2 is 200 [μm] or less, the manufacturing cost of the decorative sheet 1 can be reduced without forming the colored base layer 2 thicker than necessary. due to that.

In addition, although 6th Embodiment demonstrated polyethylene derived from biomass as resin which comprises the colored base material layer 2 derived from biomass, this invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the sixth embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin that constitutes the colored substrate layer 2 .

<Pattern layer>
The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored base material layer 2, and is a layer for adding a pattern for imparting design. The design layer 3 may be omitted if the coloring of the colored base material layer 2 can be used instead.
The pattern layer 3 is formed using printing ink, paint, or the like. The printing ink, paint, or the like that forms the pattern layer 3 is formed by dissolving or dispersing a coloring agent such as a dye or pigment in a suitable diluent solvent together with a suitable binder resin.

The printing ink, paint, or the like that forms the pattern layer 3 is applied using, for example, various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.
As the binder resin, for example, it is possible to use urethane-based resin, acrylic-based resin, vinyl chloride-based resin, polyimide-based resin, nitrocellulose, etc., or a mixture thereof, but is not limited to these. do not have.
Any pattern can be used as the pattern. For example, wood grain patterns, stone grain patterns, texture patterns, abstract patterns, geometric patterns, characters, symbols, single-color solid colors, etc., or combinations thereof can be used. It is possible. In addition, in order to improve the concealability of the decorative sheet 1, a concealing layer may be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer is formed, for example, using opaque printing ink or paint containing a large amount of opaque pigment such as titanium dioxide or iron oxide.

The thickness of the pattern layer 3 is preferably in the range of 1 [μm] to 10 [μm]. This is because when the pattern layer 3 has a thickness of 1 [μm] or more, clear printing is possible. Further, when the thickness of the pattern layer 3 is 10 [μm] or less, the printing workability in manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.
In addition, in order to impart various functions to the pattern layer 3, for example, an extender, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a desiccant, a curing agent, a curing accelerator and a curing agent are added. Functional additives such as retardants may be added.
In addition, the pattern layer 3 includes, for example, a solid colored base layer for concealing the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern for adding a design. It is good also as a structure which has a pattern pattern layer.

<Adhesive layer>
The adhesive layer 4 is laminated on one surface (upper surface in FIG. 1) of the pattern layer 3 and used for bonding the pattern layer 3 and the transparent resin layer 5 together.
As the material of the adhesive layer 4, for example, urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, polyolefin, or the like can be used. A polyolefin resin is particularly preferred because of its adhesiveness to the transparent resin layer 5 .

<Transparent resin layer>
The transparent resin layer 5 is laminated on one surface (the upper surface in FIG. 1) of the adhesive layer 4, and is formed of the above resin composition containing biomass-derived (plant-derived) polyethylene. is. More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing biomass-derived polyethylene obtained by polymerizing the above-described biomass-derived ethylene-containing monomer. That is, in the transparent resin layer 5, the resin composition containing the biomass-derived polyethylene used in the colored substrate layer 2 may be used. Further, it may contain fossil fuel-derived polyethylene obtained by polymerizing a monomer containing fossil fuel-derived ethylene and at least one of fossil fuel-derived ethylene and α-olefin.

The transparent resin layer 5 contains 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 40 to 75% by mass of the biomass-derived ethylene described above with respect to the entire transparent resin layer 5. may comprise: If the concentration of biomass-derived ethylene in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

The density of the transparent resin layer 5 is in the range of 0.92 [g/cm ³ ] to 0.99 [g/cm ³ ], preferably 0.94 [g/cm 3 ] to 0.98 [g/cm ³ ]. cm ³ ] or less, more preferably 0.95 [g/cm ³ ] or more and 0.97 [g/cm ³ ] or less. The density of the transparent resin layer 5 is a value measured according to the method specified in A method of JIS K7112-1980 after performing annealing according to JIS K6760-1995. If the density of the transparent resin layer 5 is 0.92 [g/cm ³ ] or more, the rigidity of the transparent resin layer 5 can be increased. Moreover, if the density of the transparent resin layer 5 is 0.99 [g/cm ³ ] or less, the transparency and mechanical strength of the transparent resin layer 5 can be enhanced.

The transparent resin layer 5 has a thickness of 55 to 150 [μm], preferably 55 to 100 [μm], more preferably 60 to 80 [μm].

The transparent resin layer 5 may contain biomass-derived high-density polyethylene as the biomass-derived polyethylene.
In addition, the transparent resin layer 5 may contain, as biomass-derived polyethylene, polyethylene obtained by blending biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in a range of 100:0 to 20:80. .
Further, the transparent resin layer 5 may have a biomass degree of 10% or more and 90% or less.

The method for manufacturing the transparent resin layer 5 is not particularly limited, and it can be manufactured by a conventionally known method. In the sixth embodiment, it is preferably formed by extrusion molding, and more preferably extrusion molding is performed by a T-die method or an inflation method.

In the sixth embodiment, it is preferable that the transparent resin layer 5 and the colored substrate layer 2 satisfy the following specific relationship with respect to density, thickness, and biomass degree (biomass-derived ethylene concentration).

In the sixth embodiment, it is preferable that the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 satisfy d2>d1. This is because formability is required in order to function as the transparent resin layer 5 and productivity is required in order to function as the colored base material layer 2 .
The ratio (d2/d1) between the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 is preferably in the range of 1.1 to 1.5, and preferably 1.1 to 1.1. It is more preferably within the range of 3 or less, and further preferably within the range of 1.1 or more and 1.2 or less. When the density ratio of the transparent resin layer and the colored substrate layer is within this range, even when biomass-derived polyethylene is used, the decorative sheet can have the necessary extrusion suitability and bending suitability.

In the sixth embodiment, it is preferable that the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored base material layer 2 satisfy t1≧t2. This is because the thickness is required to function as the transparent resin layer 5 and the thickness as the transparent resin layer 5 is not necessary to function as the colored base material layer 2 .
The ratio (t1/t2) between the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored base material layer 2 is preferably in the range of 1.1 to 3, more preferably 1.1 to 2. more preferably within the range of 1.1 or more and 1.5 or less.

In the sixth embodiment, it is preferable that the biomass-derived ethylene concentration C1 in the transparent resin layer 5 and the biomass-derived ethylene concentration C2 in the colored substrate layer 2 satisfy C1>C2. This is because, in order to function as the transparent resin layer 5, the thickness is large and the amount of ethylene used is large.

The biomass-derived polyethylene forming the transparent resin layer 5 may be added with a nucleating agent (for example, “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd.).
The nucleating agent is preferably added to polyethylene within the range of 500 [ppm] to 2000 [ppm] based on the mass of polyethylene, and within the range of 1500 [ppm] to 2000 [ppm], It is more preferable if it is added to polyethylene.

The transparent resin layer 5 may optionally contain, for example, a colorant, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, an antifungal agent. At least one selected from various additives such as agents, antifriction agents, light scattering agents and gloss modifiers may be added.
The transparent resin layer 5 preferably has a degree of transparency (colorless transparency, colored transparency, translucent) that allows the pattern of the pattern layer 3 to be seen through from the surface (upper surface) of the decorative sheet 1 .

In addition, although 6th Embodiment demonstrated polyethylene derived from biomass as resin which comprises the transparent resin layer 5 derived from biomass, this invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the sixth embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the transparent resin layer 5 .

<Surface protective layer>
The surface protective layer 6 is laminated on one surface (the upper surface in FIG. 1) of the transparent resin layer 5, and provides the decorative sheet 1 with weather resistance, scratch resistance, stain resistance, design properties, and the like. It is a layer provided to impart functions.

The surface protective layer 6 is made of urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate. In the surface protective layer 6, at least one of the polyols, isocyanate compounds, and hydroxy(meth)acrylates constituting the urethane (meth)acrylate described above contains a biomass-derived component. That is, the surface protective layer 6 contains a biomass-derived component. At least one of the polyol, isocyanate compound, and hydroxy(meth)acrylate may or may not contain a biomass-derived component. In the following description, urethane (meth)acrylate containing a biomass-derived component is also referred to as biourethane (meth)acrylate.

Urethane (meth)acrylates are obtained, for example, by reacting polyols and isocyanates with hydroxy (meth)acrylates. In biourethane (meth)acrylate, a plant-derived polyol can be used as the polyol, a plant-derived isocyanate can be used as the isocyanate, or both the polyol and the isocyanate can be plant-derived.

The polyol may be a polyester polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid, a polyether polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate, or a reaction product of a polyfunctional alcohol and a carbonate. Certain polycarbonate polyols can be used. Each polyol will be described below.

<Polyester polyol>
When the polyester polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional carboxylic acid contains the biomass-derived component. Examples of polyester polyols containing biomass-derived components include the following.
・Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Reaction product of fossil fuel-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Biomass-derived polyfunctional alcohol and fossil fuel-derived reactant with polyfunctional carboxylic acid

As polyfunctional alcohols derived from biomass, aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugar cane, cassava, and sago palm can be used. Examples of biomass-derived aliphatic polyfunctional alcohols include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), and butylene obtained from plant materials by the following methods. There are glycol (BG), hexamethylene glycol, etc., and any of them can be used. These may be used alone or in combination.

Biomass-derived polypropylene glycol is produced from glycerol via 3-hydroxypropylaldehyde (HPA) by a fermentation process in which the plant material is degraded to yield glucose. Compared with polypropylene glycol produced by the EO production method, polypropylene glycol produced by a bio-method such as the fermentation method yields useful by-products such as lactic acid from the standpoint of safety, and the production cost can be kept low. It is also preferred that it is possible.
Biomass-derived butylene glycol can be produced by producing succinic acid obtained by producing and fermenting glycol from a plant raw material, and then hydrogenating the succinic acid.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

As polyfunctional alcohols derived from fossil fuels, compounds having 2 or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, polyfunctional alcohols derived from fossil fuels are not particularly limited and conventionally known substances can be used, for example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG) , diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl -1,5-Pentanediol, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, and the like can be used. These may be used alone or in combination of two or more.

Biomass-derived polyfunctional carboxylic acids include reproducible plant-derived oils such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, and the recycling of waste edible oils, etc. Aliphatic polyfunctional carboxylic acids obtained from plant sources such as oils can be used. Examples of biomass-derived aliphatic polyfunctional carboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced with heptyl alcohol as a by-product by alkaline thermal decomposition of ricinoleic acid obtained from castor oil. In the present invention, it is particularly preferable to use biomass-derived succinic acid or biomass-derived sebacic acid. These may be used alone or in combination of two or more.

Aliphatic polyfunctional carboxylic acids and aromatic polyfunctional carboxylic acids can be used as polyfunctional carboxylic acids derived from fossil fuels. Aliphatic polyfunctional carboxylic acids derived from fossil fuels are not particularly limited and conventionally known substances can be used. For example, adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride acid, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acid, ester compounds thereof, and the like. In addition, the aromatic polyfunctional carboxylic acid derived from fossil fuels is not particularly limited and conventionally known substances can be used. Examples include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, their ester compounds, and the like can be used. These may be used alone or in combination of two or more.

<Polyether polyol>
When the polyether polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains the biomass-derived component. Examples of polyether polyols containing biomass-derived components include the following.
・Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Reaction products of fossil fuel-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Biomass-derived polyfunctional alcohols and fossil fuel-derived polyfunctional Reactants with functional isocyanates

As the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol described in the polyester polyol can be used.

As a biomass-derived polyfunctional isocyanate, a plant-derived divalent carboxylic acid is acid-amidated, converted to a terminal amino group by reduction, and further reacted with phosgene to convert the amino group to an isocyanate group. What is obtained can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Biomass-derived diisocyanates include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. A plant-derived diisocyanate can also be obtained by using a plant-derived amino acid as a raw material and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by methyl-esterifying the carboxyl group of lysine and then converting the amino group into an isocyanate group. Also, 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group to an isocyanate group.

Other methods for synthesizing 1,5-pentamethylene diisocyanate include phosgenation and carbamate methods. More specifically, the phosgenation method includes a method of directly reacting 1,5-pentamethylenediamine or a salt thereof with phosgene, or a method of suspending hydrochloride of pentamethylenediamine in an inert solvent and reacting it with phosgene. 1,5-pentamethylene diisocyanate is synthesized by the method. In the carbamate-forming method, first, 1,5-pentamethylenediamine or a salt thereof is carbamated to form pentamethylenedicarbamate (PDC), which is then thermally decomposed to produce 1,5-pentamethylenediisocyanate. Synthesis. Polyisocyanates that are preferably used in the present invention include 1,5-pentamethylene diisocyanate-based polyisocyanates (trade name: STABIO (registered trademark)) manufactured by Mitsui Chemicals, Inc.

The polyfunctional isocyanate derived from fossil fuels is not particularly limited, and conventionally known substances can be used. 1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, 4,4′-methylenebis(phenylene isocyanate) (MDI), Aromatic diisocyanates such as dulylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4′-diisocyanate dibenzyl, and the like. In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) ), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI and other alicyclic diisocyanates. These may be used alone or in combination of two or more.

<Polycarbonate polyol>
When the polycarbonate polyol contains a biomass-derived component, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived carbonate can be used as the polycarbonate polyol. Alternatively, a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a biomass-derived component can be used. Carbonates include, for example, dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, diphenyl carbonate and the like. These can be used alone or in combination of two or more.

As the biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol described in the above polyester polyol can be used.

<Isocyanate compound>
Next, the isocyanate compound will be explained. As the isocyanate compound containing a biomass-derived component, the biomass-derived polyfunctional isocyanate described for the polyether polyol can be used.

<Hydroxy (meth)acrylate>
Next, hydroxy (meth) acrylate will be explained. Hydroxy (meth) acrylates include (meth) acryloyl groups such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Hydroxy (meth) acrylates; glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, etc. ( Hydroxy(meth)acrylates having two or more meth)acryloyl groups, and the like. Each of these may be used alone, or two or more of them may be used in combination.

Moreover, the surface protective layer 6 may be formed containing nitrocellulose in addition to the biourethane (meth)acrylate described above. That is, the surface protective layer 6 may be formed of the biourethane (meth)acrylate described above, or may be formed by adding nitrocellulose to the biourethane (meth)acrylate.

<Nitrocellulose>
Nitrocellulose is a cellulose-based resin of a nitro group-substituted product obtained by nitric acid esterification of a part of the hydroxyl groups of the cellulose skeleton. The cellulose backbone of nitrocellulose resin is a biomass material. As the nitrocellulose, general nitrocellulose can be used without any trouble, but in particular, one substituted with 1.3 to 2.7 nitro groups on average per glucose unit constituting the cellulose skeleton is used. It is preferable to use

Nitrocellulose is classified into L type and H type according to molecular weight. From the viewpoint of solubility in organic solvents, it is preferable to use the L type.

The surface protective layer 6 preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, still more preferably 10% or more and 50% or less. If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced. The weight of the surface protective layer 6 after drying is preferably 0.1 [g/m2] or more and 15 [g/m2] or less, more preferably 3 [g/m2] or more and 10 [g/m2] or less, still more preferably is 6 [g/m2] or more and 9 [g/m2] or less. The surface protective layer 6 preferably has a thickness of 0.1 [μm] to 10 [μm], more preferably 3 [μm] to 10 [μm], even more preferably 6 [μm] to 9 [μm]. have
Regarding the "biomass degree", for example, in the case of biourethane (meth)acrylate, as described above, it is obtained as a value obtained by measuring the content of biomass-derived carbon by radioactive carbon (C14) measurement.

Regarding the "biomass degree", for example, in the case of nitrocellulose, the number of hydroxyl groups contained per glucose unit (formula weight = 172) constituting the cellulose skeleton, which is the starting material, is three. can be nitrated (replacement of hydrogen by a nitro group (non-biomass material, formula weight = 46)). Then, assuming that the original cellulose skeleton consists of 100% by weight of biomass material, and the average number of substituted nitro groups per glucose unit is n, the ratio of biomass material to the entire nitrocellulose molecule ( % by weight) can be calculated by (172−n)×100/(172−n+46n).
The ratio of the biomass material to the entire nitrocellulose molecule is about 78.8% by weight when one nitro group is substituted on average per glucose unit constituting the cellulose skeleton, and two nitro groups are substituted. and about 55.0% by weight when substituted by three nitro groups (calculated by the above formula).

In addition, the surface protective layer 6 may optionally contain weathering agents, plasticizers, stabilizers, fillers, dispersants, coloring agents such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, and light stabilizers. , anti-blocking agents, catalyst scavengers, colorants, light scattering agents, gloss modifiers, and other additives. Moreover, the surface protective layer 6 may contain functional additives such as an antibacterial agent and an antifungal agent, if necessary.

<Uneven part>
The concave-convex portion 7 is formed by concave portions provided at a plurality of locations on the transparent resin layer 5 and the surface protective layer 6 .

<Primer layer>
The primer layer 8 is a layer serving as a base, and is a layer for improving adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9 .
Further, the primer layer 8 is laminated on the other surface (the lower surface in FIG. 1) of the colored base material layer 2 .
Furthermore, the primer layer 8 is formed using, for example, a polyester-based resin, an organic additive, a pigment, or the like.
In addition, the primer layer 8 may contain an antirust pigment for the purpose of improving corrosion resistance.
The thickness of the primer layer 8 is, for example, within the range of 1 [μm] or more and 10 [μm] or less.

The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications are possible according to the design and the like as long as they do not deviate.

(Effect of the sixth embodiment)
With the decorative sheet 1 of the sixth embodiment, the effects described below can be achieved.
(1) The colored substrate layer 2 and the transparent resin layer 5 are resin layers each formed of a resin composition containing biomass-derived polyolefin, and the surface protective layer 6 contains a biomass-derived component.
This makes it possible to provide a decorative sheet that can reduce the amount of fossil fuels used by using a plant-derived material and maintain physical properties suitable for use as a decorative sheet.

(2) The surface protective layer 6 is a resin layer formed of urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate, and the polyol contained in the resin composition , the isocyanate compound, and the hydroxy(meth)acrylate comprise a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to reliably reduce the amount of fossil fuel used, and to provide a decorative sheet that can reliably maintain physical properties suitable for use as a decorative sheet. .

(3) The polyol, which is a component of biourethane (meth)acrylate that forms the surface protective layer 6, is a polyester polyol containing a biomass-derived component, a polyether polyol containing a biomass-derived component, or a polycarbonate polyol containing a biomass-derived component. be.
As a result, it is possible to provide a decorative sheet that can more reliably reduce the amount of fossil fuels used by using plant-derived materials and more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(4) Among the polyols that are constituents of the biourethane (meth)acrylate, the polyester polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid containing a fossil fuel-derived component, or , a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional carboxylic acid containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(5) Among the polyols that are constituents of the biourethane (meth)acrylate, the polyether polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate containing a fossil fuel-derived component, or , a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional isocyanate containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(6) Among the polyols that are constituents of the biourethane (meth)acrylate, the polycarbonate polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a fossil fuel-derived component, or a fossil fuel. It is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(7) The isocyanate compound, which is a component of the biourethane (meth)acrylate forming the surface protective layer 6, is an isocyanate compound containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(8) The base material 9 and the decorative sheet 1 laminated on at least one surface of the base material 9 are provided.
As a result, it is possible to reduce the amount of fossil fuels used by using plant-derived materials, and to provide a decorative material that can maintain physical properties suitable for use as a decorative sheet.

The decorative materials of Examples 1 to 9 and the decorative materials of Reference Examples 1 to 3 will be described below with reference to the sixth embodiment.

(Example 1)
After applying corona discharge treatment to one side of the base material, a pattern layer printed with urethane-based printing ink, a urethane-based adhesive layer, and a maleic anhydride-modified polyethylene resin layer ( A transparent adhesive layer), a transparent resin layer, and a surface protective layer were laminated in this order. After the other surface of the substrate was subjected to corona discharge treatment, a primer layer (thickness: 1 to 2 [μm]) made of polyester urethane resin was formed. Thus, a decorative sheet of Example 1 (total thickness: 135 [μm]) was obtained.
In Example 1, a colored substrate layer (thickness: 55 [μm]) formed of a resin composition containing biomass-derived high-density polyethylene and fossil fuel-derived low-density polyethylene was used as the substrate. A colored substrate layer was obtained by subjecting this resin composition to calendar molding. The biomass degree of the colored substrate layer thus formed is 80%, and the density of the colored substrate layer is 1.08 [g/cm ³ ].
As the transparent resin layer, a transparent resin layer (thickness: 80 [μm]) formed of a resin composition containing biomass-derived polyethylene (“Biomass Polyethylene” manufactured by Braskem) was used. This biomass-derived polyethylene was obtained by blending biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) so that the ratio (high-density polyethylene/low-density polyethylene) was 80/20. Resin. This resin was Ruder-laminated to obtain a transparent resin layer. The transparent resin layer thus formed has a biomass degree of 94% and a density of 0.95 [g/cm ³ ].
Biourethane (meth)acrylate, which is a reaction product of a polyester polyol containing a biomass-derived component, a fossil fuel-derived isocyanate compound, and a fossil fuel-derived hydroxy (meth)acrylate, was used for the surface protective layer. As the polyester polyol containing a biomass-derived component, a polyester polyol which is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid derived from fossil fuel was used.

(Example 2)
Same as Example 1, except that a reaction product of a polyfunctional alcohol derived from fossil fuel and a polyfunctional carboxylic acid containing a biomass-derived component was used as the polyester polyol in the biourethane (meth)acrylate that forms the surface protective layer. A decorative sheet of Example 2 was obtained.

(Example 3)
As the bio-urethane (meth)acrylate that forms the surface protective layer, bio-urethane (meth) is a reaction product of a fossil fuel-derived polyester polyol, an isocyanate compound containing a biomass-derived component, and a fossil fuel-derived hydroxy (meth)acrylate. A decorative sheet of Example 3 was obtained in the same manner as in Example 1, except that acrylate was used.

(Example 4)
A decorative sheet of Example 4 was obtained in the same manner as in Example 1, except that polyether polyol was used as the polyol in the biourethane (meth)acrylate forming the surface protective layer. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from a fossil fuel was used as the polyether polyol.

(Example 5)
As the polyether polyol in the biourethane (meth)acrylate forming the surface protective layer, the same procedure as in Example 4 was performed except that a reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional isocyanate containing a biomass-derived component was used. Thus, a decorative sheet of Example 5 was obtained.

(Example 6)
A decorative sheet of Example 6 was obtained in the same manner as in Example 3, except that a polyether polyol derived from a fossil fuel was used as the polyol in the biourethane (meth)acrylate forming the surface protective layer.

(Example 7)
A decorative sheet of Example 7 was obtained in the same manner as in Example 1, except that a polycarbonate polyol was used as the polyol in the biourethane (meth)acrylate forming the surface protective layer. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived carbonate was used as the polycarbonate polyol.

(Example 8)
A decorative sheet of Example 8 was obtained in the same manner as in Example 3, except that a fossil fuel-derived polycarbonate polyol was used as the polyol in the bio-urethane (meth)acrylate forming the surface protective layer.

(Example 9)
The biomass-derived polyethylene used for the transparent resin layer is a biomass-derived high-density polyethylene (SHC7260) and a biomass-derived low-density polyethylene (SPB681) with a ratio (high-density polyethylene/low-density polyethylene) of 100/0. A decorative sheet of Example 9 was obtained in the same manner as in Example 1, except that a resin blended in such a manner that

(Reference example 1)
A decorative sheet of Reference Example 1 was obtained in the same manner as in Example 1, except that the surface protective layer was formed from an acrylic resin-based UV-curable resin.

(Reference example 2)
A decorative sheet of Reference Example 2 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained by Ruder laminating only a fossil fuel-derived homopolypropylene resin manufactured by Prime Polymer Co., Ltd.

(Reference example 3)
A decorative sheet of Reference Example 3 was obtained in the same manner as in Example 1, except that the colored base layer was obtained using only the fossil fuel-derived colored polyethylene resin.

(Performance evaluation, evaluation results)
For the decorative sheets of Examples 1 to 9 and the decorative sheets of Reference Examples 1 to 3, "haze (%) of transparent resin layer", "pencil hardness", "Hoffman scratch test", "extrusion suitability", "Bend whitening" was evaluated. As the evaluation method, the method described below was used.

<Haze (%) of transparent resin layer>
The haze (%) of the transparent resin layer was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufacturer: Shimadzu Corporation, model number: UV-3600).
A resin having the same composition as the transparent resin layer of each example and reference example was extruded to a thickness of 70 [μm] or more and 80 [μm] or less to obtain a resin film. Haze was evaluated by measuring haze at a wavelength of 555 nm with a spectrophotometer (integrating sphere). Then, when the haze is less than 15%, it is evaluated as "◎", when the haze is within the range of 15% or more and less than 25%, it is evaluated as "◯", and when the haze is 25% or more, it is evaluated as " x” was evaluated.
In addition, in the present Example, "double-circle" and "good" were made into the pass.

<Pencil hardness>
The pencil hardness was measured with a pencil hardness tester (automatic) (manufacturer: Yoshimitsu Seiki, model number: C221A).
After performing a pencil hardness test using pencils of different hardness on the decorative material including the decorative sheet of each example and reference example, damage (gouging) occurring on the surface (surface protective layer) was confirmed. Surface hardness was evaluated. Then, after conducting the pencil hardness test using a pencil having a hardness of 2B or more, the case where damage occurred on the surface was evaluated as "⊚", and after conducting the pencil hardness test using a pencil having a hardness of 4B or more. , and the case where damage occurred on the surface was evaluated as "○". In addition, a case where damage occurred on the surface after conducting a pencil hardness test using a pencil having a hardness of 5B or less was evaluated as "x".
In addition, in the present Example, "double-circle" and "good" were made into the pass.

<Hoffman scratch test>
The Hoffman scratch test was conducted by setting a scratch blade (cylindrical blade of φ7) so as to contact the surface of the decorative sheet at an angle of 45 degrees, and moving the tester on the decorative sheet.
Gradually increasing the load (weight) within the range of 200 to 2000 g (every 200 g) and scratching, the load (g) at which the sample surface was scratched was evaluated. In addition, when the damage was caused by a load of 800 g, "600 g" was described in the table as the withstand load.
In addition, in this example, the case where the withstand load was "200 g" was rejected.

<Extrusion suitability>
A transparent resin layer was extruded and its production suitability (extrusion suitability) was confirmed.
As a result, if the product can be manufactured (molded) without any problems, it is rated as "○" (accepted). On the other hand, those with the possibility of defects were rated as "Δ" (failed).

<Bending whitening>
Using a decorative sheet (that is, a decorative material) laminated to MDF, suitability for V-cut processing (presence or absence of whitening upon bending) was confirmed.
As a result, "○" (pass) was given when no whitening occurred, "△" (pass) was given when slight whitening occurred, and "×" (failed) was given when whitening occurred. ).

As a result of evaluating various performances using the methods described above, the decorative sheets of Examples 1 to 9 exhibited excellent performances equal to or higher than those of Reference Examples 1-3 in all evaluation tests. In other words, it was found that the decorative sheets of Examples 1 to 9 can reduce the amount of fossil fuels used by using plant-derived materials, and can maintain physical properties suitable for use as decorative sheets. rice field.

(Seventh embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG. A specific configuration of the decorative sheet 1 will be described later.
The configuration of the decorative material 10 in the seventh embodiment is the same as that of the above-described first embodiment except for the configuration of the decorative sheet 1, so the description of the configuration other than the decorative sheet 1 will be omitted.

(Configuration of decorative sheet)
As shown in FIG. 1, the decorative sheet 1 includes a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface It includes a protective layer 6 , uneven portions 7 and a primer layer 8 .

<Colored substrate layer>
The colored substrate layer 2 is a resin layer formed using a thermoplastic resin, and is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (derived from plants).
The composition of the colored substrate layer 2 will be described in detail below.
(Polyethylene derived from biomass)
In the seventh embodiment, the biomass-derived polyethylene is obtained by polymerizing a monomer containing biomass-derived ethylene. Ethylene derived from biomass is not particularly limited, and ethylene produced by a conventionally known method can be used. Since biomass-derived ethylene is used as a raw material monomer, the polymerized polyethylene is biomass-derived.
The raw material monomer for polyethylene does not have to contain 100% by mass of biomass-derived ethylene.

The monomer, which is a raw material for biomass-derived polyethylene, may further contain at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin, and may further contain a biomass-derived α-olefin.

Although the number of carbon atoms of the α-olefin is not particularly limited, those having 3 to 20 carbon atoms can usually be used, preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. In addition, by containing such an α-olefin, the polymerized polyethylene has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear polyethylene.

By using ethylene, which is a raw material derived from biomass, it is theoretically possible to manufacture from 100% biomass-derived components.

The biomass-derived ethylene concentration in the polyethylene (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the biomass-derived carbon content by radioactive carbon (C14) measurement. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in polyethylene, the ratio of biomass-derived carbon can be calculated. In the seventh embodiment, the biomass-derived carbon content Pbio can be obtained as follows, where PC14 is the content of C14 in polyethylene.
Pbio (%) = PC14/105.5 x 100

In the seventh embodiment, theoretically, if all biomass-derived ethylene is used as the raw material of polyethylene, the biomass-derived ethylene concentration is 100%, and the biomass degree of the biomass-derived polyethylene is 100. In addition, the biomass-derived ethylene concentration in the fossil fuel-derived polyethylene produced only from fossil fuel-derived raw materials is 0%, and the biomass degree of the fossil fuel-derived polyethylene is 0.

In the seventh embodiment, the biomass-derived polyethylene and the decorative sheet containing the polyethylene need not have a biomass degree of 100.

In the seventh embodiment, the method for polymerizing the biomass-derived ethylene-containing monomer is not particularly limited, and a conventionally known method can be used. The polymerization temperature and polymerization pressure should be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of a method for polymerizing a monomer containing ethylene is described below.

Polymerization methods for ethylene polymers and copolymers of ethylene and α-olefins vary depending on the type of polyethylene desired, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and direct It can be appropriately selected depending on the difference in density and branching of linear low density polyethylene (LLDPE) or the like. For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any method of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization, It is preferable to carry out in one stage or in multiple stages of two or more stages.

As the biomass-derived polyethylene, an ethylene polymer or an ethylene/α-olefin copolymer may be used alone, or two or more of them may be used in combination.

(Resin composition containing biomass-derived polyethylene)
In 7th Embodiment, a resin composition contains said polyethylene as a main component. The resin composition contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 95% by mass, more preferably 25 to 75% by mass, based on the total resin composition. If the concentration of biomass-derived ethylene in the resin composition is 5% by mass or more, it is possible to reduce the amount of fossil fuel used compared to conventional methods, and to realize a carbon-neutral decorative sheet.

The above resin composition may contain two or more types of polyethylene having different degrees of biomass, and the concentration of biomass-derived ethylene in the resin composition as a whole may be within the above range.

The above resin composition may further contain a fossil fuel-derived polyethylene obtained by polymerizing a monomer containing a fossil fuel-derived ethylene and at least one of a fossil fuel-derived ethylene and an α-olefin. That is, in the seventh embodiment, the resin composition may be a mixture of biomass-derived polyethylene and fossil fuel-derived polyethylene. The mixing method is not particularly limited, and conventionally known methods can be used for mixing. For example, dry blending or melt blending may be used.

According to a seventh embodiment, the resin composition preferably comprises 5 to 90% by weight, more preferably 25 to 75% by weight biomass-derived polyethylene and preferably 10 to 95% by weight, more preferably 25 to 75% by weight. % by weight of polyethylene derived from fossil fuels. Even when such a mixed resin composition is used, the concentration of biomass-derived ethylene in the resin composition as a whole should be within the above range.

Various additives other than polyethylene, which is the main component, may be added to the resin composition produced in the production process of the resin composition as long as the characteristics are not impaired. Additives include, for example, plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slip agents, release agents, anti- Oxidizing agents, ion exchange agents, color pigments, and the like can be added. These additives are added in an amount of preferably 1 to 20% by mass, preferably 1 to 10% by mass, based on the total resin composition.

As described above, the colored substrate layer 2 contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 5% by mass or more of the entire colored substrate layer 2. comprises 40-75%. If the concentration of biomass-derived ethylene in the colored substrate layer 2 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

The colored substrate layer 2 has a weight within the range of 0.92 [g/cm ³ ] to 1.12 [g/cm ³ ], preferably 0.98 [g/cm ³ ] to 1.10 [g/cm 3 ]. ³ ] has a density within the following range. The density of the colored base material layer 2 is a value measured according to the method specified in A method of JIS K7112-1980 after annealing according to JIS K6760-1995. If the density of the colored base layer 2 is 0.92 [g/cm ³ ] or more, the rigidity of the colored base layer 2 can be increased. Further, if the density of the colored base layer 2 is 1.12 [g/cm ³ ] or less, the transparency and mechanical strength of the colored base layer 2 can be enhanced.

The colored substrate layer 2 contains, as biomass-derived polyethylene, biomass-derived high-density polyethylene and biomass-derived low-density polyethylene, biomass-derived high-density polyethylene, and fossil fuel-derived low-density polyethylene. or high-density polyethylene derived from fossil fuels and low-density polyethylene derived from biomass. The biomass degree of the entire colored substrate layer 2 may be in the range of 10% or more and 90% or less.
The biomass-derived high-density polyethylene refers to polyethylene having a density exceeding 0.94. In addition, biomass-derived low-density polyethylene refers to polyethylene having a density of 0.94 or less.
The colored base material layer 2 contains, as biomass-derived polyethylene, biomass-derived high-density polyethylene and low-density polyethylene (either biomass-derived or fossil fuel-derived) at a ratio of 95:5 or more. A blend within the range of 70:30 is preferred. If the content of the low-density polyethylene is low, the film-forming stability is poor, and if the content of the low-density polyethylene is high, the film becomes too soft.

The method for producing the colored base material layer 2 is not particularly limited, and it can be produced by a conventionally known method. In the seventh embodiment, it is preferable to form by calendar molding.

In addition, the colored substrate layer 2 may optionally contain, for example, a coloring agent, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, and an antibacterial agent. , an antifungal agent, an antifriction agent, a light scattering agent, and a luster adjusting agent.
The thickness of the colored substrate layer 2 is preferably in the range of 40 [μm] to 200 [μm], more preferably 51 [μm] to 120 [μm], and 55 [μm]. It is more preferable to be at least 100 [μm] or less. This is because, when the thickness of the colored substrate layer 2 made of biomass-derived polyethylene is 40 [μm] or more, it absorbs the irregularities and steps of the underlying floor material, etc., and the finish of the decorative sheet 1 is improved. This is due to the fact that it is possible to Further, when the thickness of the colored base layer 2 is 200 [μm] or less, the manufacturing cost of the decorative sheet 1 can be reduced without forming the colored base layer 2 thicker than necessary. due to that.

In addition, although 7th Embodiment demonstrated polyethylene derived from biomass as resin which comprises the colored base material layer 2 derived from biomass, this invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the seventh embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the colored substrate layer 2 .

<Pattern layer>
The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored base material layer 2, and is a layer for adding a pattern for imparting design.
The pattern layer 3 is formed using printing ink, paint, or the like. The printing ink, paint, or the like that forms the pattern layer 3 is formed by dissolving or dispersing a coloring agent such as a dye or pigment in a suitable diluent solvent together with a suitable binder resin.

The printing ink, paint, or the like that forms the pattern layer 3 is applied using, for example, various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.

The pattern layer 3 is formed containing the above-described colorant and binder resin. The binder resin used for the pattern layer 3 in the seventh embodiment will be described below.

[Binder resin]
The binder resin contained in the pattern layer 3 contains urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate. In the pattern layer 3, at least one of the polyols, isocyanate compounds, and hydroxy(meth)acrylates constituting the urethane (meth)acrylate described above contains a biomass-derived component. At least one of the polyol, isocyanate compound, and hydroxy(meth)acrylate may or may not contain a biomass-derived component. In the following description, urethane (meth)acrylate containing a biomass-derived component is also referred to as biourethane (meth)acrylate.
That is, the pattern layer 3 is a resin layer containing the above-described colorant and biourethane (meth)acrylate. That is, the pattern layer 3 contains a coloring agent and a biomass-derived component.

Urethane (meth)acrylates are obtained, for example, by reacting polyols and isocyanates with hydroxy (meth)acrylates. In biourethane (meth)acrylate, a plant-derived polyol can be used as the polyol, a plant-derived isocyanate can be used as the isocyanate, or both the polyol and the isocyanate can be plant-derived.

The polyol may be a polyester polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid, a polyether polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate, or a reaction product of a polyfunctional alcohol and a carbonate. Certain polycarbonate polyols can be used. Each polyol will be described below.

<Polyester polyol>
When the polyester polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional carboxylic acid contains the biomass-derived component. Examples of polyester polyols containing biomass-derived components include the following.
・Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Reaction product of fossil fuel-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Biomass-derived polyfunctional alcohol and fossil fuel-derived reactant with polyfunctional carboxylic acid

As polyfunctional alcohols derived from biomass, aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugar cane, cassava, and sago palm can be used. Examples of biomass-derived aliphatic polyfunctional alcohols include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), and butylene obtained from plant materials by the following methods. There are glycol (BG), hexamethylene glycol, etc., and any of them can be used. These may be used alone or in combination.

Biomass-derived polypropylene glycol is produced from glycerol via 3-hydroxypropylaldehyde (HPA) by a fermentation process in which the plant material is degraded to yield glucose. Compared with polypropylene glycol produced by the EO production method, polypropylene glycol produced by a bio-method such as the fermentation method yields useful by-products such as lactic acid from the standpoint of safety, and the production cost can be kept low. It is also preferred that it is possible.
Biomass-derived butylene glycol can be produced by producing succinic acid obtained by producing and fermenting glycol from a plant raw material, and then hydrogenating the succinic acid.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

As polyfunctional alcohols derived from fossil fuels, compounds having 2 or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, polyfunctional alcohols derived from fossil fuels are not particularly limited and conventionally known substances can be used, for example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG) , diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl -1,5-Pentanediol, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, and the like can be used. These may be used alone or in combination of two or more.

Biomass-derived polyfunctional carboxylic acids include reproducible plant-derived oils such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, and the recycling of waste edible oils, etc. Aliphatic polyfunctional carboxylic acids obtained from plant sources such as oils can be used. Examples of biomass-derived aliphatic polyfunctional carboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced with heptyl alcohol as a by-product by alkaline thermal decomposition of ricinoleic acid obtained from castor oil. In the present invention, it is particularly preferable to use biomass-derived succinic acid or biomass-derived sebacic acid. These may be used alone or in combination of two or more.

Aliphatic polyfunctional carboxylic acids and aromatic polyfunctional carboxylic acids can be used as polyfunctional carboxylic acids derived from fossil fuels. Aliphatic polyfunctional carboxylic acids derived from fossil fuels are not particularly limited and conventionally known substances can be used. For example, adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride acid, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acid, ester compounds thereof, and the like. In addition, the aromatic polyfunctional carboxylic acid derived from fossil fuels is not particularly limited and conventionally known substances can be used. Examples include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, their ester compounds, and the like can be used. These may be used alone or in combination of two or more.

<Polyether polyol>
When the polyether polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains the biomass-derived component. Examples of polyether polyols containing biomass-derived components include the following.
・Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Reaction products of fossil fuel-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Biomass-derived polyfunctional alcohols and fossil fuel-derived polyfunctional Reactants with functional isocyanates

As the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol described in the polyester polyol can be used.

As a biomass-derived polyfunctional isocyanate, a plant-derived divalent carboxylic acid is acid-amidated, converted to a terminal amino group by reduction, and further reacted with phosgene to convert the amino group to an isocyanate group. What is obtained can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Biomass-derived diisocyanates include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. A plant-derived diisocyanate can also be obtained by using a plant-derived amino acid as a raw material and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by methyl-esterifying the carboxyl group of lysine and then converting the amino group to an isocyanate group. Also, 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group to an isocyanate group.

Other methods for synthesizing 1,5-pentamethylene diisocyanate include phosgenation and carbamate methods. More specifically, the phosgenation method includes a method of directly reacting 1,5-pentamethylenediamine or a salt thereof with phosgene, or a method of suspending hydrochloride of pentamethylenediamine in an inert solvent and reacting it with phosgene. 1,5-pentamethylene diisocyanate is synthesized by the method. In the carbamate-forming method, first, 1,5-pentamethylenediamine or a salt thereof is carbamated to form pentamethylenedicarbamate (PDC), which is then thermally decomposed to produce 1,5-pentamethylenediisocyanate. Synthesis. Polyisocyanates that are preferably used in the present invention include 1,5-pentamethylene diisocyanate-based polyisocyanates (trade name: STABIO (registered trademark)) manufactured by Mitsui Chemicals, Inc.

The polyfunctional isocyanate derived from fossil fuels is not particularly limited, and conventionally known substances can be used. 1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, 4,4′-methylenebis(phenylene isocyanate) (MDI), Aromatic diisocyanates such as dulylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4′-diisocyanate dibenzyl, and the like. In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) ), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI and other alicyclic diisocyanates. These may be used alone or in combination of two or more.

<Polycarbonate polyol>
When the polycarbonate polyol contains a biomass-derived component, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived carbonate can be used as the polycarbonate polyol. Alternatively, a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a biomass-derived component can be used. Carbonates include, for example, dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, diphenyl carbonate and the like. These can be used alone or in combination of two or more.

As the biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol described in the above polyester polyol can be used.

<Isocyanate compound>
Next, the isocyanate compound will be explained. As the isocyanate compound containing a biomass-derived component, the biomass-derived polyfunctional isocyanate described for the polyether polyol can be used.

<Hydroxy (meth)acrylate>
Next, hydroxy (meth) acrylate will be explained. Hydroxy (meth) acrylates include (meth) acryloyl groups such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Hydroxy (meth) acrylates; glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, etc. ( Hydroxy(meth)acrylates having two or more meth)acryloyl groups, and the like. Each of these may be used alone, or two or more of them may be used in combination.

Further, the binder resin of the pattern layer 3 may contain nitrocellulose in addition to the biourethane (meth)acrylate described above. That is, the pattern layer 3 may contain the biourethane (meth)acrylate described above, or may contain nitrocellulose in addition to the biourethane (meth)acrylate.

<Nitrocellulose>
Nitrocellulose is a cellulose-based resin of a nitro group-substituted product obtained by nitric acid esterification of a part of the hydroxyl groups of the cellulose skeleton. The cellulose backbone of nitrocellulose resin is a biomass material. As the nitrocellulose, general nitrocellulose can be used without any trouble, but in particular, one substituted with 1.3 to 2.7 nitro groups on average per glucose unit constituting the cellulose skeleton is used. It is preferable to use

Nitrocellulose is classified into L type and H type according to molecular weight. From the viewpoint of solubility in organic solvents, it is preferable to use the L type.

The pattern layer 3 preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, still more preferably 10% or more and 50% or less. If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced. The weight of the pattern layer 3 after drying is preferably 0.1 [g/m2] or more and 15 [g/m2] or less, more preferably 3 [g/m2] or more and 10 [g/m2] or less, still more preferably It is 6 [g/m2] or more and 9 [g/m2] or less. The pattern layer 3 preferably has a thickness of 0.1 [μm] or more and 10 [μm] or less, more preferably 0.5 [μm] or more and 5 [μm] or less, and still more preferably 0.7 [μm] or more and 3 [μm]. It has a thickness of A plurality of pattern layers 3 having such weight and thickness may be provided.
Regarding the "biomass degree", for example, in the case of biourethane (meth)acrylate, as described above, it is obtained as a value obtained by measuring the content of biomass-derived carbon by radioactive carbon (C14) measurement.

Regarding the "biomass degree", for example, in the case of nitrocellulose, the number of hydroxyl groups contained per glucose unit (formula weight = 172) constituting the cellulose skeleton, which is the starting material, is three. can be nitrated (replacement of hydrogen by a nitro group (non-biomass material, formula weight = 46)). Then, assuming that the original cellulose skeleton consists of 100% by weight of biomass material, and the average number of substituted nitro groups per glucose unit is n, the ratio of biomass material to the entire nitrocellulose molecule ( % by weight) can be calculated by (172−n)×100/(172−n+46n).
The ratio of the biomass material to the entire nitrocellulose molecule is about 78.8% by weight when one nitro group is substituted on average per glucose unit constituting the cellulose skeleton, and two nitro groups are substituted. and about 55.0% by weight when substituted by three nitro groups (calculated by the above formula).

Further, when the thickness of the pattern layer 3 is 10 [μm] or less, the printing workability in manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.
In addition, in order to impart various functions to the pattern layer 3, for example, an extender, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a desiccant, a curing agent, a curing accelerator and a curing agent are added. Functional additives such as retardants may be added.

Any pattern can be used as the pattern of the pattern layer 3. For example, a wood grain pattern, a stone grain pattern, a texture pattern, an abstract pattern, a geometric pattern, a character, a symbol, a single solid color, or a combination thereof. etc. can be used. In addition, in order to improve the concealability of the decorative sheet 1, a concealing layer may be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer is formed, for example, using opaque printing ink or paint containing a large amount of opaque pigment such as titanium dioxide or iron oxide.
In addition, the pattern layer 3 includes, for example, a solid colored base layer for concealing the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern for adding a design. It is good also as a structure which has a pattern pattern layer.

<Adhesive layer>
The adhesive layer 4 is laminated on one surface (upper surface in FIG. 1) of the pattern layer 3 and used for bonding the pattern layer 3 and the transparent resin layer 5 together.
As the material of the adhesive layer 4, for example, urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, polyolefin, or the like can be used. A polyolefin resin is particularly preferred because of its adhesiveness to the transparent resin layer 5 .

<Transparent resin layer>
The transparent resin layer 5 is laminated on one surface (the upper surface in FIG. 1) of the adhesive layer 4, and is formed of the above resin composition containing biomass-derived (plant-derived) polyethylene. is. More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing biomass-derived polyethylene obtained by polymerizing the above-described biomass-derived ethylene-containing monomer. That is, in the transparent resin layer 5, the resin composition containing the biomass-derived polyethylene used in the colored substrate layer 2 may be used. Further, it may contain fossil fuel-derived polyethylene obtained by polymerizing a monomer containing fossil fuel-derived ethylene and at least one of fossil fuel-derived ethylene and α-olefin.

The transparent resin layer 5 contains 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 40 to 75% by mass of the biomass-derived ethylene described above with respect to the entire transparent resin layer 5. may comprise: If the concentration of biomass-derived ethylene in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

The density of the transparent resin layer 5 is in the range of 0.92 [g/cm ³ ] to 0.99 [g/cm ³ ], preferably 0.94 [g/cm 3 ] to 0.98 [g/cm ³ ]. cm ³ ] or less, more preferably 0.95 [g/cm ³ ] or more and 0.97 [g/cm ³ ] or less. The density of the transparent resin layer 5 is a value measured according to the method specified in A method of JIS K7112-1980 after performing annealing according to JIS K6760-1995. If the density of the transparent resin layer 5 is 0.92 [g/cm ³ ] or more, the rigidity of the transparent resin layer 5 can be increased. Moreover, if the density of the transparent resin layer 5 is 0.99 [g/cm ³ ] or less, the transparency and mechanical strength of the transparent resin layer 5 can be enhanced.

The transparent resin layer 5 has a thickness of 55 to 150 [μm], preferably 55 to 100 [μm], more preferably 60 to 80 [μm].

The transparent resin layer 5 may contain biomass-derived high-density polyethylene as the biomass-derived polyethylene.
In addition, the transparent resin layer 5 may contain, as biomass-derived polyethylene, polyethylene obtained by blending biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in a range of 100:0 to 20:80. .
Further, the transparent resin layer 5 may have a biomass degree of 10% or more and 90% or less.

The method for manufacturing the transparent resin layer 5 is not particularly limited, and it can be manufactured by a conventionally known method. In the seventh embodiment, it is preferably formed by extrusion molding, and more preferably extrusion molding is performed by a T-die method or an inflation method.

In the seventh embodiment, it is preferable that the transparent resin layer 5 and the colored substrate layer 2 satisfy the following specific relationship with respect to density, thickness, and biomass degree (biomass-derived ethylene concentration).

In the seventh embodiment, it is preferable that the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 satisfy d2>d1. This is because formability is required in order to function as the transparent resin layer 5 and productivity is required in order to function as the colored base material layer 2 .
The ratio (d2/d1) between the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 is preferably in the range of 1.1 to 1.5, and preferably 1.1 to 1.1. It is more preferably within the range of 3 or less, and further preferably within the range of 1.1 or more and 1.2 or less. When the density ratio of the transparent resin layer and the colored substrate layer is within this range, even when biomass-derived polyethylene is used, the decorative sheet can have the necessary extrusion suitability and bending suitability.

In the seventh embodiment, it is preferable that the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored base material layer 2 satisfy t1≧t2. This is because the thickness is required to function as the transparent resin layer 5 and the thickness as the transparent resin layer 5 is not necessary to function as the colored base material layer 2 .
The ratio (t1/t2) between the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored base material layer 2 is preferably in the range of 1.1 to 3, more preferably 1.1 to 2. more preferably within the range of 1.1 or more and 1.5 or less.

In the seventh embodiment, it is preferable that the biomass-derived ethylene concentration C1 in the transparent resin layer 5 and the biomass-derived ethylene concentration C2 in the colored substrate layer 2 satisfy C1>C2. This is because, in order to function as the transparent resin layer 5, the thickness is large and the amount of ethylene used is large.

The biomass-derived polyethylene forming the transparent resin layer 5 may be added with a nucleating agent (for example, “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd.).
The nucleating agent is preferably added to polyethylene within the range of 500 [ppm] to 2000 [ppm] based on the mass of polyethylene, and within the range of 1500 [ppm] to 2000 [ppm], It is more preferable if it is added to polyethylene.

The transparent resin layer 5 may optionally contain, for example, a colorant, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, an antifungal agent. At least one selected from various additives such as agents, antifriction agents, light scattering agents and gloss modifiers may be added.
The transparent resin layer 5 preferably has a degree of transparency (colorless transparency, colored transparency, translucent) that allows the pattern of the pattern layer 3 to be seen through from the surface (upper surface) of the decorative sheet 1 .

In the seventh embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the seventh embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the transparent resin layer 5 .

<Surface protective layer>
The surface protective layer 6 is laminated on one surface (the upper surface in FIG. 1) of the transparent resin layer 5, and provides the decorative sheet 1 with weather resistance, scratch resistance, stain resistance, design properties, and the like. It is a layer provided to impart functions.
The surface protective layer 6 can be made of a thermosetting resin or an ionizing radiation curable resin, and is formed using, for example, an acrylic resin composition.
In addition, the surface protective layer 6 may optionally contain weathering agents, plasticizers, stabilizers, fillers, dispersants, coloring agents such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, and light stabilizers. , anti-blocking agents, catalyst scavengers, colorants, light scattering agents, gloss modifiers, and other additives. Moreover, the surface protective layer 6 may contain functional additives such as an antibacterial agent and an antifungal agent, if necessary.

<Uneven part>
The concave-convex portion 7 is formed by concave portions provided at a plurality of locations on the transparent resin layer 5 and the surface protective layer 6 .

<Primer layer>
The primer layer 8 is a layer serving as a base, and is a layer for improving adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9 .
Further, the primer layer 8 is laminated on the other surface (the lower surface in FIG. 1) of the colored base material layer 2 .
Furthermore, the primer layer 8 is formed using, for example, a polyester-based resin, an organic additive, a pigment, or the like.
In addition, the primer layer 8 may contain an antirust pigment for the purpose of improving corrosion resistance.
The thickness of the primer layer 8 is, for example, within the range of 1 [μm] or more and 10 [μm] or less.

The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications are possible according to the design and the like as long as they do not deviate.

(Effect of the seventh embodiment)
If it is the decorative sheet 1 of 7th Embodiment, it will become possible to have an effect described below.
(1) The colored substrate layer 2 and the transparent resin layer 5 are each a resin layer formed of a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin. The colored substrate layer 2 contains 5% by mass or more of biomass-derived olefin and has a density within the range of 0.92 [g/cm ³ ] to 0.99 [g/cm ³ ]. It contains 5% by mass or more of olefin, has a density within the range of 0.92 [g/cm ³ ] or more and 1.12 [g/cm ³ ] or less, and the pattern layer 3 contains a coloring agent and a biomass-derived component. include.
This makes it possible to provide a decorative sheet that can reduce the amount of fossil fuels used by using a plant-derived material and maintain physical properties suitable for use as a decorative sheet.

(2) The pattern layer 3 is a resin layer containing urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate, and the polyol and isocyanate contained in the resin composition. At least one component of the compound and hydroxy(meth)acrylate includes a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to reliably reduce the amount of fossil fuel used, and to provide a decorative sheet that can reliably maintain physical properties suitable for use as a decorative sheet. .

(3) The polyol that is a component of biourethane (meth)acrylate contained in the pattern layer 3 is a polyester polyol containing a biomass-derived component, a polyether polyol containing a biomass-derived component, or a polycarbonate polyol containing a biomass-derived component. .
As a result, it is possible to provide a decorative sheet that can more reliably reduce the amount of fossil fuels used by using plant-derived materials and more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(4) Among the polyols that are constituents of the biourethane (meth)acrylate, the polyester polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid containing a fossil fuel-derived component, or , a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional carboxylic acid containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(5) Among the polyols that are constituents of the biourethane (meth)acrylate, the polyether polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate containing a fossil fuel-derived component, or , a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional isocyanate containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(6) Among the polyols that are constituents of the biourethane (meth)acrylate, the polycarbonate polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a fossil fuel-derived component, or a fossil fuel. It is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(7) The isocyanate compound, which is a component of the biourethane (meth)acrylate contained in the pattern layer 3, is an isocyanate compound containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(8) The base material 9 and the decorative sheet 1 laminated on at least one surface of the base material 9 are provided.
As a result, it is possible to reduce the amount of fossil fuels used by using plant-derived materials, and to provide a decorative material that can maintain physical properties suitable for use as a decorative sheet.

The decorative materials of Examples 1 to 9 and the decorative materials of Reference Examples 1 to 3 will be described below with reference to the seventh embodiment.

(Example 1)
After applying corona discharge treatment to one side of the substrate, one side of the substrate is coated with a pattern layer, a urethane-based adhesive layer, a maleic anhydride-modified polyethylene resin layer (transparent adhesive layer), and a transparent resin. A layer and a surface protective layer containing an acrylic resin composition as a main component were laminated in this order. After the other surface of the substrate was subjected to corona discharge treatment, a primer layer (thickness: 1 to 2 [μm]) made of polyester urethane resin was formed. Thus, a decorative sheet of Example 1 (total thickness: 135 [μm]) was obtained.
In Example 1, a colored substrate layer (thickness: 55 [μm]) formed of a resin composition containing biomass-derived high-density polyethylene and fossil fuel-derived low-density polyethylene was used as the substrate. A colored substrate layer was obtained by subjecting this resin composition to calendar molding. The biomass degree of the colored substrate layer thus formed is 80%, and the density of the colored substrate layer is 1.08 [g/cm ³ ].
As the transparent resin layer, a transparent resin layer (thickness: 80 [μm]) formed of a resin composition containing biomass-derived polyethylene (“Biomass Polyethylene” manufactured by Braskem) was used. This biomass-derived polyethylene was obtained by blending biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) so that the ratio (high-density polyethylene/low-density polyethylene) was 80/20. Resin. This resin was Ruder-laminated to obtain a transparent resin layer. The transparent resin layer thus formed has a biomass degree of 94% and a density of 0.95 [g/cm ³ ].
Biourethane (meth)acrylate, which is a reaction product of a polyester polyol containing a biomass-derived component, a fossil fuel-derived isocyanate compound, and a fossil fuel-derived hydroxy (meth)acrylate, was used as the binder resin of the pattern layer. As the polyester polyol containing a biomass-derived component, a polyester polyol which is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid derived from fossil fuel was used.

(Example 2)
As the polyester polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer, the reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional carboxylic acid containing a biomass-derived component was used. A decorative sheet of Example 2 was obtained in the same manner.

(Example 3)
Bio-urethane (meth)acrylate, which is a binder resin for the pattern layer, is bio-urethane (meth)acrylate, which is a reaction product of a fossil fuel-derived polyester polyol, an isocyanate compound containing a biomass-derived component, and a fossil fuel-derived hydroxy (meth)acrylate. ) A decorative sheet of Example 3 was obtained in the same manner as in Example 1, except that acrylate was used.

(Example 4)
A decorative sheet of Example 4 was obtained in the same manner as in Example 1, except that polyether polyol was used as the polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from a fossil fuel was used as the polyether polyol.

(Example 5)
Same as Example 4 except that a reaction product of a polyfunctional alcohol derived from fossil fuel and a polyfunctional isocyanate containing a biomass-derived component was used as the polyether polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer. Then, a decorative sheet of Example 5 was obtained.

(Example 6)
A decorative sheet of Example 6 was obtained in the same manner as in Example 3, except that a polyether polyol derived from a fossil fuel was used as the polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer.

(Example 7)
A decorative sheet of Example 7 was obtained in the same manner as in Example 1, except that a polycarbonate polyol was used as the polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived carbonate was used as the polycarbonate polyol.

(Example 8)
A decorative sheet of Example 8 was obtained in the same manner as in Example 3, except that a fossil fuel-derived polycarbonate polyol was used as the polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer.

(Example 9)
Biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) are blended so that the ratio (high-density polyethylene/low-density polyethylene) is 100/0, and the resin is Ruder-laminated. A decorative sheet of Example 9 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained in this way.

(Reference example 1)
A decorative sheet of Reference Example 1 was obtained in the same manner as in Example 1, except that the design layer was formed from a urethane-based printing ink.

(Reference example 2)
A decorative sheet of Reference Example 2 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained by Ruder laminating only a fossil fuel-derived homopolypropylene resin manufactured by Prime Polymer Co., Ltd.

(Reference example 3)
A decorative sheet of Reference Example 3 was obtained in the same manner as in Example 1, except that the colored base layer was obtained using only the fossil fuel-derived colored polyethylene resin.

(Performance evaluation, evaluation results)
For the decorative sheets of Examples 1 to 9 and the decorative sheets of Reference Examples 1 to 3, "haze (%) of transparent resin layer", "pencil hardness", "Hoffman scratch test", "extrusion suitability", "Bend whitening" was evaluated. As the evaluation method, the method described below was used.

<Haze (%) of transparent resin layer>
The haze (%) of the transparent resin layer was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufacturer: Shimadzu Corporation, model number: UV-3600).
A resin having the same composition as the transparent resin layer of each example and reference example was extruded to a thickness of 70 [μm] or more and 80 [μm] or less to obtain a resin film. Haze was evaluated by measuring haze at a wavelength of 555 nm with a spectrophotometer (integrating sphere). Then, when the haze is less than 15%, it is evaluated as "◎", when the haze is within the range of 15% or more and less than 25%, it is evaluated as "◯", and when the haze is 25% or more, it is evaluated as " ×” was evaluated.
In addition, in the present Example, "double-circle" and "good" were made into the pass.

<Pencil hardness>
The pencil hardness was measured with a pencil hardness tester (automatic) (manufacturer: Yoshimitsu Seiki, model number: C221A).
After performing a pencil hardness test using pencils of different hardness on the decorative material including the decorative sheet of each example and reference example, damage (gouging) occurring on the surface (surface protective layer) was confirmed. Surface hardness was evaluated. Then, after conducting the pencil hardness test using a pencil having a hardness of 2B or more, the case where damage occurred on the surface was evaluated as "⊚", and after conducting the pencil hardness test using a pencil having a hardness of 4B or more. , and the case where damage occurred on the surface was evaluated as "○". In addition, a case where damage occurred on the surface after conducting a pencil hardness test using a pencil having a hardness of 5B or less was evaluated as "x".
In addition, in the present Example, "double-circle" and "good" were made into the pass.

<Hoffman scratch test>
The Hoffman scratch test was conducted by setting a scratch blade (cylindrical blade of φ7) so as to contact the surface of the decorative sheet at an angle of 45 degrees, and moving the tester on the decorative sheet.
Gradually increasing the load (weight) within the range of 200 to 2000 g (every 200 g) and scratching, the load (g) at which the sample surface was scratched was evaluated. In addition, when the damage was caused by a load of 800 g, "600 g" was described in the table as the withstand load.
In addition, in this example, the case where the withstand load was "200 g" was rejected.

<Extrusion suitability>
A transparent resin layer was extruded and its production suitability (extrusion suitability) was confirmed.
As a result, if the product can be manufactured (molded) without any problems, it is rated as "○" (accepted). On the other hand, those with the possibility of defects were rated as "Δ" (failed).

<Bending whitening>
Using a decorative sheet (that is, a decorative material) laminated to MDF, suitability for V-cut processing (presence or absence of whitening upon bending) was confirmed.
As a result, "○" (pass) was given when no whitening occurred, "△" (pass) was given when slight whitening occurred, and "×" (failed) was given when whitening occurred. ).

As a result of evaluating various performances using the methods described above, the decorative sheets of Examples 1 to 9 exhibited excellent performances equal to or higher than those of Reference Examples 1-3 in all evaluation tests. In other words, it was found that the decorative sheets of Examples 1 to 9 can reduce the amount of fossil fuels used by using plant-derived materials, and can maintain physical properties suitable for use as decorative sheets. rice field.

(Eighth embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG. A specific configuration of the decorative sheet 1 will be described later.
Note that the configuration of the decorative material 10 in the eighth embodiment is the same as that of the above-described first embodiment except for the configuration of the decorative sheet 1, so the description of the configuration other than the decorative sheet 1 will be omitted.

(Configuration of decorative sheet)
As shown in FIG. 1, the decorative sheet 1 includes a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface It includes a protective layer 6 , uneven portions 7 and a primer layer 8 .

<Colored substrate layer>
The colored substrate layer 2 is a resin layer formed using a thermoplastic resin, and is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (derived from plants).
The composition of the colored substrate layer 2 will be described in detail below.
(Polyethylene derived from biomass)
In the eighth embodiment, the biomass-derived polyethylene is obtained by polymerizing a monomer containing biomass-derived ethylene. Ethylene derived from biomass is not particularly limited, and ethylene produced by a conventionally known method can be used. Since biomass-derived ethylene is used as a raw material monomer, the polymerized polyethylene is biomass-derived.
The raw material monomer for polyethylene does not have to contain 100% by mass of biomass-derived ethylene.

The monomer, which is a raw material for biomass-derived polyethylene, may further contain at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin, and may further contain a biomass-derived α-olefin.

Although the number of carbon atoms of the α-olefin is not particularly limited, those having 3 to 20 carbon atoms can usually be used, preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. In addition, by containing such an α-olefin, the polymerized polyethylene has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear polyethylene.

By using ethylene, which is a raw material derived from biomass, it is theoretically possible to manufacture from 100% biomass-derived components.

The biomass-derived ethylene concentration in the polyethylene (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the biomass-derived carbon content by radioactive carbon (C14) measurement. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in polyethylene, the ratio of biomass-derived carbon can be calculated. In the eighth embodiment, the biomass-derived carbon content Pbio can be obtained as follows, where PC14 is the content of C14 in polyethylene.
Pbio (%) = PC14/105.5 x 100

In the eighth embodiment, theoretically, if all biomass-derived ethylene is used as the raw material of polyethylene, the biomass-derived ethylene concentration is 100%, and the biomass degree of the biomass-derived polyethylene is 100. In addition, the biomass-derived ethylene concentration in the fossil fuel-derived polyethylene produced only from fossil fuel-derived raw materials is 0%, and the biomass degree of the fossil fuel-derived polyethylene is 0.

In the eighth embodiment, the biomass-derived polyethylene and the decorative sheet containing the polyethylene need not have a biomass degree of 100.

In the eighth embodiment, the method for polymerizing the biomass-derived ethylene-containing monomer is not particularly limited, and conventionally known methods can be used. The polymerization temperature and polymerization pressure should be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of a method for polymerizing a monomer containing ethylene is described below.

Polymerization methods for ethylene polymers and copolymers of ethylene and α-olefins vary depending on the type of polyethylene desired, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and direct It can be appropriately selected depending on the difference in density and branching of linear low density polyethylene (LLDPE) or the like. For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any method of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization, It is preferable to carry out in one stage or in multiple stages of two or more stages.

As the biomass-derived polyethylene, an ethylene polymer or an ethylene/α-olefin copolymer may be used alone, or two or more of them may be used in combination.

(Resin composition containing biomass-derived polyethylene)
In the eighth embodiment, the resin composition contains polyethylene as a main component. The resin composition contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 95% by mass, more preferably 25 to 75% by mass, based on the total resin composition. If the concentration of biomass-derived ethylene in the resin composition is 5% by mass or more, it is possible to reduce the amount of fossil fuel used compared to conventional methods, and to realize a carbon-neutral decorative sheet.

The above resin composition may contain two or more types of polyethylene having different degrees of biomass, and the concentration of biomass-derived ethylene in the resin composition as a whole may be within the above range.

The above resin composition may further contain a fossil fuel-derived polyethylene obtained by polymerizing a monomer containing a fossil fuel-derived ethylene and at least one of a fossil fuel-derived ethylene and an α-olefin. That is, in the eighth embodiment, the resin composition may be a mixture of biomass-derived polyethylene and fossil fuel-derived polyethylene. The mixing method is not particularly limited, and conventionally known methods can be used for mixing. For example, dry blending or melt blending may be used.

According to an eighth embodiment, the resin composition preferably comprises 5 to 90% by weight, more preferably 25 to 75% by weight biomass-derived polyethylene and preferably 10 to 95% by weight, more preferably 25 to 75% by weight. % by weight of polyethylene derived from fossil fuels. Even when such a mixed resin composition is used, the concentration of biomass-derived ethylene in the resin composition as a whole should be within the above range.

Various additives other than polyethylene, which is the main component, may be added to the resin composition produced in the production process of the resin composition as long as the characteristics are not impaired. Additives include, for example, plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slip agents, release agents, anti- Oxidizing agents, ion exchange agents, color pigments, and the like can be added. These additives are added in an amount of preferably 1 to 20% by mass, preferably 1 to 10% by mass, based on the total resin composition.

As described above, the colored substrate layer 2 contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 5% by mass or more of the entire colored substrate layer 2. comprises 40-75%. If the concentration of biomass-derived ethylene in the colored substrate layer 2 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

The colored substrate layer 2 has a weight within the range of 0.92 [g/cm ³ ] to 1.12 [g/cm ³ ], preferably 0.98 [g/cm ³ ] to 1.10 [g/cm 3 ]. ³ ] has a density within the following range. The density of the colored base material layer 2 is a value measured according to the method specified in A method of JIS K7112-1980 after annealing according to JIS K6760-1995. If the density of the colored base layer 2 is 0.92 [g/cm ³ ] or more, the rigidity of the colored base layer 2 can be increased. Further, if the density of the colored base layer 2 is 1.12 [g/cm ³ ] or less, the transparency and mechanical strength of the colored base layer 2 can be enhanced.

The colored substrate layer 2 contains, as biomass-derived polyethylene, biomass-derived high-density polyethylene and biomass-derived low-density polyethylene, biomass-derived high-density polyethylene, and fossil fuel-derived low-density polyethylene. or high-density polyethylene derived from fossil fuels and low-density polyethylene derived from biomass. The biomass degree of the entire colored substrate layer 2 may be in the range of 10% or more and 90% or less.
The biomass-derived high-density polyethylene refers to polyethylene having a density exceeding 0.94. In addition, biomass-derived low-density polyethylene refers to polyethylene having a density of 0.94 or less.
The colored base material layer 2 contains, as biomass-derived polyethylene, biomass-derived high-density polyethylene and low-density polyethylene (either biomass-derived or fossil fuel-derived) at a ratio of 95:5 or more. A blend within the range of 70:30 is preferred. If the content of the low-density polyethylene is low, the film-forming stability is poor, and if the content of the low-density polyethylene is high, the film becomes too soft.

The method for producing the colored base material layer 2 is not particularly limited, and it can be produced by a conventionally known method. In the eighth embodiment, it is preferable to form by calendar molding.

In addition, the colored substrate layer 2 may optionally contain, for example, a coloring agent, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, and an antibacterial agent. , an antifungal agent, an antifriction agent, a light scattering agent, and a luster adjusting agent.
The thickness of the colored substrate layer 2 is preferably in the range of 40 [μm] to 200 [μm], more preferably 51 [μm] to 120 [μm], and 55 [μm]. It is more preferable to be at least 100 [μm] or less. This is because, when the thickness of the colored substrate layer 2 made of biomass-derived polyethylene is 40 [μm] or more, it absorbs the irregularities and steps of the underlying floor material, etc., and the finish of the decorative sheet 1 is improved. This is due to the fact that it is possible to Further, when the thickness of the colored base layer 2 is 200 [μm] or less, the manufacturing cost of the decorative sheet 1 can be reduced without forming the colored base layer 2 thicker than necessary. due to that.

In the eighth embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the colored substrate layer 2, but the present invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the eighth embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin that constitutes the colored base material layer 2 .

<Pattern layer>
The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored base material layer 2, and is a layer for adding a pattern for imparting design.
The pattern layer 3 is formed using printing ink, paint, or the like. The printing ink, paint, or the like that forms the pattern layer 3 is formed by dissolving or dispersing a coloring agent such as a dye or pigment in a suitable diluent solvent together with a suitable binder resin.

The printing ink, paint, or the like that forms the pattern layer 3 is applied using, for example, various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.

The pattern layer 3 is formed containing the above-described colorant and binder resin. The binder resin used for the pattern layer 3 in the eighth embodiment will be described below.

[Binder resin]
The binder resin contained in the pattern layer 3 contains urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate. In the pattern layer 3, at least one of the polyols, isocyanate compounds, and hydroxy(meth)acrylates constituting the urethane (meth)acrylate described above contains a biomass-derived component. At least one of the polyol, isocyanate compound, and hydroxy(meth)acrylate may or may not contain a biomass-derived component. In the following description, urethane (meth)acrylate containing a biomass-derived component is also referred to as biourethane (meth)acrylate.
That is, the pattern layer 3 is a resin layer containing the above-described colorant and biourethane (meth)acrylate. That is, the pattern layer 3 contains a coloring agent and a biomass-derived component.

Urethane (meth)acrylates are obtained, for example, by reacting polyols and isocyanates with hydroxy (meth)acrylates. In biourethane (meth)acrylate, a plant-derived polyol can be used as the polyol, a plant-derived isocyanate can be used as the isocyanate, or both the polyol and the isocyanate can be plant-derived.

The polyol may be a polyester polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional carboxylic acid, a polyether polyol that is a reaction product of a polyfunctional alcohol and a polyfunctional isocyanate, or a reaction product of a polyfunctional alcohol and a carbonate. Certain polycarbonate polyols can be used. Each polyol will be described below.

<Polyester polyol>
When the polyester polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional carboxylic acid contains the biomass-derived component. Examples of polyester polyols containing biomass-derived components include the following.
・Reaction product of biomass-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Reaction product of fossil fuel-derived polyfunctional alcohol and biomass-derived polyfunctional carboxylic acid ・Biomass-derived polyfunctional alcohol and fossil fuel-derived reactant with polyfunctional carboxylic acid

As polyfunctional alcohols derived from biomass, aliphatic polyfunctional alcohols obtained from plant materials such as corn, sugar cane, cassava, and sago palm can be used. Examples of biomass-derived aliphatic polyfunctional alcohols include polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG), diethylene glycol (DEG), and butylene obtained from plant materials by the following methods. There are glycol (BG), hexamethylene glycol, etc., and any of them can be used. These may be used alone or in combination.

Biomass-derived polypropylene glycol is produced from glycerol via 3-hydroxypropylaldehyde (HPA) by a fermentation process in which the plant material is degraded to yield glucose. Compared with polypropylene glycol produced by the EO production method, polypropylene glycol produced by a bio-method such as the fermentation method yields useful by-products such as lactic acid from the standpoint of safety, and the production cost can be kept low. It is also preferred that it is possible.
Biomass-derived butylene glycol can be produced by producing succinic acid obtained by producing and fermenting glycol from a plant raw material, and then hydrogenating the succinic acid.
Biomass-derived ethylene glycol can be produced, for example, from bioethanol obtained by a conventional method via ethylene.

As polyfunctional alcohols derived from fossil fuels, compounds having 2 or more, preferably 2 to 8 hydroxyl groups in one molecule can be used. Specifically, polyfunctional alcohols derived from fossil fuels are not particularly limited and conventionally known substances can be used, for example, polypropylene glycol (PPG), neopentyl glycol (NPG), ethylene glycol (EG) , diethylene glycol (DEG), butylene glycol (BG), hexamethylene glycol, triethylene glycol, dipropylene glycol, 1,4-cyclohexanedimethanol, trimethylolpropane, glycerin, 1,9-nonanediol, 3-methyl -1,5-Pentanediol, polyether polyols, polycarbonate polyols, polyolefin polyols, acrylic polyols, and the like can be used. These may be used alone or in combination of two or more.

Biomass-derived polyfunctional carboxylic acids include reproducible plant-derived oils such as soybean oil, linseed oil, tung oil, coconut oil, palm oil, and castor oil, and the recycling of waste edible oils, etc. Aliphatic polyfunctional carboxylic acids obtained from plant sources such as oils can be used. Examples of biomass-derived aliphatic polyfunctional carboxylic acids include sebacic acid, succinic acid, phthalic acid, adipic acid, glutaric acid, and dimer acid. For example, sebacic acid is produced with heptyl alcohol as a by-product by alkaline thermal decomposition of ricinoleic acid obtained from castor oil. In the present invention, it is particularly preferable to use biomass-derived succinic acid or biomass-derived sebacic acid. These may be used alone or in combination of two or more.

Aliphatic polyfunctional carboxylic acids and aromatic polyfunctional carboxylic acids can be used as polyfunctional carboxylic acids derived from fossil fuels. Aliphatic polyfunctional carboxylic acids derived from fossil fuels are not particularly limited and conventionally known substances can be used. For example, adipic acid, dodecanedioic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride acid, itaconic anhydride, sebacic acid, succinic acid, glutaric acid, dimer acid, ester compounds thereof, and the like. In addition, the aromatic polyfunctional carboxylic acid derived from fossil fuels is not particularly limited and conventionally known substances can be used. Examples include isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid, their ester compounds, and the like can be used. These may be used alone or in combination of two or more.

<Polyether polyol>
When the polyether polyol contains a biomass-derived component, at least one of the polyfunctional alcohol and the polyfunctional isocyanate contains the biomass-derived component. Examples of polyether polyols containing biomass-derived components include the following.
・Reaction products of biomass-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Reaction products of fossil fuel-derived polyfunctional alcohols and biomass-derived polyfunctional isocyanates ・Biomass-derived polyfunctional alcohols and fossil fuel-derived polyfunctional Reactants with functional isocyanates

As the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol and the fossil fuel-derived polyfunctional alcohol described in the polyester polyol can be used.

As a biomass-derived polyfunctional isocyanate, a plant-derived divalent carboxylic acid is acid-amidated, converted to a terminal amino group by reduction, and further reacted with phosgene to convert the amino group to an isocyanate group. What is obtained can be used. The biomass-derived polyfunctional isocyanate is, for example, a biomass-derived diisocyanate. Biomass-derived diisocyanates include dimer acid diisocyanate (DDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. A plant-derived diisocyanate can also be obtained by using a plant-derived amino acid as a raw material and converting the amino group into an isocyanate group. For example, lysine diisocyanate (LDI) is obtained by methyl-esterifying the carboxyl group of lysine and then converting the amino group into an isocyanate group. Also, 1,5-pentamethylene diisocyanate can be obtained by decarboxylating the carboxyl group of lysine and then converting the amino group to an isocyanate group.

Other methods for synthesizing 1,5-pentamethylene diisocyanate include phosgenation and carbamate methods. More specifically, the phosgenation method includes a method of directly reacting 1,5-pentamethylenediamine or a salt thereof with phosgene, or a method of suspending hydrochloride of pentamethylenediamine in an inert solvent and reacting it with phosgene. 1,5-pentamethylene diisocyanate is synthesized by the method. In the carbamate-forming method, first, 1,5-pentamethylenediamine or a salt thereof is carbamated to form pentamethylenedicarbamate (PDC), which is then thermally decomposed to produce 1,5-pentamethylenediisocyanate. Synthesis. Polyisocyanates that are preferably used in the present invention include 1,5-pentamethylene diisocyanate-based polyisocyanates (trade name: STABIO (registered trademark)) manufactured by Mitsui Chemicals, Inc.

The polyfunctional isocyanate derived from fossil fuels is not particularly limited, and conventionally known substances can be used. 1,3-phenylene diisocyanate, 4-chloro-1,3-phenylene diisocyanate, 4-butoxy-1,3-phenylene diisocyanate, 2,4-diisocyanatodiphenyl ether, 4,4′-methylenebis(phenylene isocyanate) (MDI), Aromatic diisocyanates such as dulylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate (XDI), 1,5-naphthalene diisocyanate, benzidine diisocyanate, o-nitrobenzidine diisocyanate, 4,4′-diisocyanate dibenzyl, and the like. In addition, aliphatic diisocyanates such as methylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, and 1,10-decamethylene diisocyanate; 1,4-cyclohexylene diisocyanate, 4,4-methylenebis(cyclohexyl isocyanate) ), 1,5-tetrahydronaphthalene diisocyanate, isophorone diisocyanate, hydrogenated MDI, hydrogenated XDI and other alicyclic diisocyanates. These may be used alone or in combination of two or more.

<Polycarbonate polyol>
When the polycarbonate polyol contains a biomass-derived component, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived carbonate can be used as the polycarbonate polyol. Alternatively, a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a biomass-derived component can be used. Carbonates include, for example, dimethyl carbonate, dipropyl carbonate, diethyl carbonate, diethylene carbonate, dibutyl carbonate, ethylene carbonate, diphenyl carbonate and the like. These can be used alone or in combination of two or more.

As the biomass-derived polyfunctional alcohol, the biomass-derived polyfunctional alcohol described in the above polyester polyol can be used.

<Isocyanate compound>
Next, the isocyanate compound will be explained. As the isocyanate compound containing a biomass-derived component, the biomass-derived polyfunctional isocyanate described for the polyether polyol can be used.

<Hydroxy (meth)acrylate>
Next, hydroxy (meth) acrylate will be explained. Hydroxy (meth) acrylates include (meth) acryloyl groups such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. Hydroxy (meth) acrylates; glycerin di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, sorbitol penta (meth) acrylate, etc. ( Hydroxy(meth)acrylates having two or more meth)acryloyl groups, and the like. Each of these may be used alone, or two or more of them may be used in combination.

Further, the binder resin of the pattern layer 3 may contain nitrocellulose in addition to the biourethane (meth)acrylate described above. That is, the pattern layer 3 may contain the biourethane (meth)acrylate described above, or may contain nitrocellulose in addition to the biourethane (meth)acrylate.

<Nitrocellulose>
Nitrocellulose is a cellulose-based resin of a nitro group-substituted product obtained by nitric acid esterification of a part of the hydroxyl groups of the cellulose skeleton. The cellulose backbone of nitrocellulose resin is a biomass material. As the nitrocellulose, general nitrocellulose can be used without any trouble, but in particular, one substituted with 1.3 to 2.7 nitro groups on average per glucose unit constituting the cellulose skeleton is used. It is preferable to use

Nitrocellulose is classified into L type and H type according to molecular weight. From the viewpoint of solubility in organic solvents, it is preferable to use the L type.

The pattern layer 3 preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, still more preferably 10% or more and 50% or less. If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced. The weight of the pattern layer 3 after drying is preferably 0.1 [g/m2] or more and 15 [g/m2] or less, more preferably 3 [g/m2] or more and 10 [g/m2] or less, still more preferably It is 6 [g/m2] or more and 9 [g/m2] or less. The pattern layer 3 preferably has a thickness of 0.1 [μm] or more and 10 [μm] or less, more preferably 0.5 [μm] or more and 5 [μm] or less, and still more preferably 0.7 [μm] or more and 3 [μm]. It has a thickness of A plurality of pattern layers 3 having such weight and thickness may be provided.
Regarding the "biomass degree", for example, in the case of biourethane (meth)acrylate, as described above, it is obtained as a value obtained by measuring the content of biomass-derived carbon by radioactive carbon (C14) measurement.

Regarding the "biomass degree", for example, in the case of nitrocellulose, the number of hydroxyl groups contained per glucose unit (formula weight = 172) constituting the cellulose skeleton, which is the starting material, is three. can be nitrated (replacement of hydrogen by a nitro group (non-biomass material, formula weight = 46)). Then, assuming that the original cellulose skeleton consists of 100% by weight of biomass material, and the average number of substituted nitro groups per glucose unit is n, the ratio of biomass material to the entire nitrocellulose molecule ( % by weight) can be calculated by (172−n)×100/(172−n+46n).
The ratio of the biomass material to the entire nitrocellulose molecule is about 78.8% by weight when one nitro group is substituted on average per glucose unit constituting the cellulose skeleton, and two nitro groups are substituted. and about 55.0% by weight when substituted by three nitro groups (calculated by the above formula).

Further, when the thickness of the pattern layer 3 is 10 [μm] or less, the printing workability in manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.
In addition, in order to impart various functions to the pattern layer 3, for example, an extender, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a desiccant, a curing agent, a curing accelerator and a curing agent are added. Functional additives such as retardants may be added.

Any pattern can be used as the pattern of the pattern layer 3. For example, a wood grain pattern, a stone grain pattern, a texture pattern, an abstract pattern, a geometric pattern, a character, a symbol, a single solid color, or a combination thereof. etc. can be used. In addition, in order to improve the concealability of the decorative sheet 1, a concealing layer may be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer is formed, for example, using opaque printing ink or paint containing a large amount of opaque pigment such as titanium dioxide or iron oxide.
In addition, the pattern layer 3 includes, for example, a solid colored base layer for concealing the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern for adding a design. It is good also as a structure which has a pattern pattern layer.

<Adhesive layer>
The adhesive layer 4 is laminated on one surface (upper surface in FIG. 1) of the pattern layer 3 and used for bonding the pattern layer 3 and the transparent resin layer 5 together.
As the material of the adhesive layer 4, for example, urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, polyolefin, or the like can be used. A polyolefin resin is particularly preferred because of its adhesiveness to the transparent resin layer 5 .

<Transparent resin layer>
The transparent resin layer 5 is laminated on one surface (the upper surface in FIG. 1) of the adhesive layer 4, and is formed of the above resin composition containing biomass-derived (plant-derived) polyethylene. is. More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing biomass-derived polyethylene obtained by polymerizing the above-described biomass-derived ethylene-containing monomer. That is, in the transparent resin layer 5, the resin composition containing the biomass-derived polyethylene used in the colored substrate layer 2 may be used. Further, it may contain fossil fuel-derived polyethylene obtained by polymerizing a monomer containing fossil fuel-derived ethylene and at least one of fossil fuel-derived ethylene and α-olefin.

The transparent resin layer 5 contains 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 40 to 75% by mass of the biomass-derived ethylene described above with respect to the entire transparent resin layer 5. may comprise: If the concentration of biomass-derived ethylene in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

The density of the transparent resin layer 5 is in the range of 0.92 [g/cm ³ ] to 0.99 [g/cm ³ ], preferably 0.94 [g/cm 3 ] to 0.98 [g/cm ³ ]. cm ³ ] or less, more preferably 0.95 [g/cm ³ ] or more and 0.97 [g/cm ³ ] or less. The density of the transparent resin layer 5 is a value measured according to the method specified in A method of JIS K7112-1980 after performing annealing according to JIS K6760-1995. If the density of the transparent resin layer 5 is 0.92 [g/cm ³ ] or more, the rigidity of the transparent resin layer 5 can be increased. Moreover, if the density of the transparent resin layer 5 is 0.99 [g/cm ³ ] or less, the transparency and mechanical strength of the transparent resin layer 5 can be enhanced.

The transparent resin layer 5 has a thickness of 55 to 150 [μm], preferably 55 to 100 [μm], more preferably 60 to 80 [μm].

The transparent resin layer 5 may contain biomass-derived high-density polyethylene as the biomass-derived polyethylene.
In addition, the transparent resin layer 5 may contain, as biomass-derived polyethylene, polyethylene obtained by blending biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in a range of 100:0 to 20:80. .
Further, the transparent resin layer 5 may have a biomass degree of 10% or more and 90% or less.

The method for manufacturing the transparent resin layer 5 is not particularly limited, and it can be manufactured by a conventionally known method. In the eighth embodiment, it is preferably formed by extrusion molding, and more preferably extrusion molding is performed by a T-die method or an inflation method.

In the eighth embodiment, it is preferable that the transparent resin layer 5 and the colored substrate layer 2 satisfy the following specific relationship with respect to density, thickness, and biomass degree (biomass-derived ethylene concentration).

In the eighth embodiment, it is preferable that the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 satisfy d2>d1. This is because formability is required in order to function as the transparent resin layer 5 and productivity is required in order to function as the colored base material layer 2 .
The ratio (d2/d1) between the density d1 of the transparent resin layer 5 and the density d2 of the colored substrate layer 2 is preferably in the range of 1.1 to 1.5, and preferably 1.1 to 1.1. It is more preferably within the range of 3 or less, and further preferably within the range of 1.1 or more and 1.2 or less. When the density ratio of the transparent resin layer and the colored substrate layer is within this range, even when biomass-derived polyethylene is used, the decorative sheet can have the necessary extrusion suitability and bending suitability.

In the eighth embodiment, it is preferable that the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored base material layer 2 satisfy t1≧t2. This is because the thickness is required to function as the transparent resin layer 5 and the thickness as the transparent resin layer 5 is not necessary to function as the colored base material layer 2 .
The ratio (t1/t2) between the thickness t1 of the transparent resin layer 5 and the thickness t2 of the colored base material layer 2 is preferably in the range of 1.1 to 3, more preferably 1.1 to 2. more preferably within the range of 1.1 or more and 1.5 or less.

In the eighth embodiment, it is preferable that the biomass-derived ethylene concentration C1 in the transparent resin layer 5 and the biomass-derived ethylene concentration C2 in the colored substrate layer 2 satisfy C1>C2. This is because, in order to function as the transparent resin layer 5, the thickness is large and the amount of ethylene used is large.

The biomass-derived polyethylene forming the transparent resin layer 5 may be added with a nucleating agent (for example, “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd.).
The nucleating agent is preferably added to polyethylene within the range of 500 [ppm] to 2000 [ppm] based on the mass of polyethylene, and within the range of 1500 [ppm] to 2000 [ppm], It is more preferable if it is added to polyethylene.

The transparent resin layer 5 may optionally contain, for example, a colorant, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, an antifungal agent. At least one selected from various additives such as agents, antifriction agents, light scattering agents and gloss modifiers may be added.
The transparent resin layer 5 preferably has a degree of transparency (colorless transparency, colored transparency, translucent) that allows the pattern of the pattern layer 3 to be seen through from the surface (upper surface) of the decorative sheet 1 .

In the eighth embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the transparent resin layer 5, but the present invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the eighth embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the transparent resin layer 5 .

<Surface protective layer>
The surface protective layer 6 is laminated on one surface (the upper surface in FIG. 1) of the transparent resin layer 5, and provides the decorative sheet 1 with weather resistance, scratch resistance, stain resistance, design properties, and the like. It is a layer provided to impart functions.

The surface protective layer 6 can be formed using the same material as the binder resin of the pattern layer 3 . Therefore, the structure of the surface protective layer 6 is the same as that of the pattern layer 3 except that it does not contain a coloring agent.
The surface protective layer 6 is made of urethane (meth)acrylate, that is, biourethane (meth)acrylate, which is a resin composition containing at least polyol, an isocyanate compound, and hydroxy (meth)acrylate. In the surface protective layer 6, at least one of the polyols, isocyanate compounds, and hydroxy(meth)acrylates constituting the urethane (meth)acrylate described above contains a biomass-derived component. That is, the surface protective layer 6 contains a biomass-derived component.

Further, the surface protective layer 6 may be formed containing nitrocellulose in addition to the biourethane (meth)acrylate described above, similarly to the binder resin of the pattern layer 3 . That is, the surface protective layer 6 may be formed of the biourethane (meth)acrylate described above, or may be formed by adding nitrocellulose to the biourethane (meth)acrylate.

The surface protective layer 6 preferably has a biomass degree of 5% or more, more preferably 5% or more and 50% or less, still more preferably 10% or more and 50% or less. If the degree of biomass is within the above range, the amount of fossil fuel used can be reduced, and the environmental load can be reduced. The weight of the surface protective layer 6 after drying is preferably 0.1 [g/m2] or more and 15 [g/m2] or less, more preferably 3 [g/m2] or more and 10 [g/m2] or less, still more preferably is 6 [g/m2] or more and 9 [g/m2] or less. The surface protective layer 6 preferably has a thickness of 0.1 [μm] to 10 [μm], more preferably 3 [μm] to 10 [μm], even more preferably 6 [μm] to 9 [μm]. have

In addition, the surface protective layer 6 may optionally contain weathering agents, plasticizers, stabilizers, fillers, dispersants, coloring agents such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, and light stabilizers. , anti-blocking agents, catalyst scavengers, colorants, light scattering agents, gloss modifiers, and other additives. Moreover, the surface protective layer 6 may contain functional additives such as an antibacterial agent and an antifungal agent, if necessary.

<Uneven part>
The concave-convex portion 7 is formed by concave portions provided at a plurality of locations on the transparent resin layer 5 and the surface protective layer 6 .

<Primer layer>
The primer layer 8 is a layer serving as a base, and is a layer for improving adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9 .
Further, the primer layer 8 is laminated on the other surface (the lower surface in FIG. 1) of the colored base material layer 2 .
Furthermore, the primer layer 8 is formed using, for example, a polyester-based resin, an organic additive, a pigment, or the like.
In addition, the primer layer 8 may contain an antirust pigment for the purpose of improving corrosion resistance.
The thickness of the primer layer 8 is, for example, within the range of 1 [μm] or more and 10 [μm] or less.

The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications are possible according to the design and the like as long as they do not deviate.

(Effect of the eighth embodiment)
If it is the decorative sheet 1 of 8th Embodiment, it will become possible to have an effect described below.
(1) The colored substrate layer 2 and the transparent resin layer 5 are each a resin layer formed of a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin. The colored substrate layer 2 contains 5% by mass or more of biomass-derived olefin and has a density within the range of 0.92 [g/cm ³ ] to 0.99 [g/cm ³ ]. It contains 5% by mass or more of olefin, has a density within the range of 0.92 [g/cm ³ ] or more and 1.12 [g/cm ³ ] or less, and the pattern layer 3 contains a colorant and a biomass-derived component. and the surface protective layer 6 contains a biomass-derived component.
This makes it possible to provide a decorative sheet that can reduce the amount of fossil fuels used by using a plant-derived material and maintain physical properties suitable for use as a decorative sheet.

(2) The pattern layer 3 is a resin layer containing urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate, and the surface protective layer 6 is composed of the urethane (meth)acrylate. ) A resin layer formed of an acrylate, and at least one of the polyol, the isocyanate compound, and the hydroxy (meth)acrylate contained in the urethane (meth)acrylate contains a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to reliably reduce the amount of fossil fuel used, and to provide a decorative sheet that can reliably maintain physical properties suitable for use as a decorative sheet. .

(3) The polyol, which is a component of biourethane (meth)acrylate contained in the pattern layer 3 and the surface protective layer 6, is a polyester polyol containing a biomass-derived component, a polyether polyol containing a biomass-derived component, or a biomass-derived component. Polycarbonate polyol containing.
As a result, it is possible to provide a decorative sheet that can more reliably reduce the amount of fossil fuels used by using plant-derived materials and more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(4) Among the polyols that are constituents of the biourethane (meth)acrylate, the polyester polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid containing a fossil fuel-derived component, or , a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional carboxylic acid containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(5) Among the polyols that are constituents of the biourethane (meth)acrylate, the polyether polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate containing a fossil fuel-derived component, or , a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a polyfunctional isocyanate containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(6) Among the polyols that are constituents of the biourethane (meth)acrylate, the polycarbonate polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a fossil fuel-derived component, or a fossil fuel. It is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(7) The isocyanate compound, which is a component of biourethane (meth)acrylate contained in the pattern layer 3 and the surface protective layer 6, is an isocyanate compound containing a biomass-derived component.
As a result, the use of plant-derived materials makes it possible to further reliably reduce the amount of fossil fuels used, and to provide a decorative sheet that can more reliably maintain physical properties suitable for use as a decorative sheet. becomes.

(8) The base material 9 and the decorative sheet 1 laminated on at least one surface of the base material 9 are provided.
As a result, it is possible to reduce the amount of fossil fuels used by using plant-derived materials, and to provide a decorative material that can maintain physical properties suitable for use as a decorative sheet.

The decorative materials of Examples 1 to 16 and the decorative materials of Reference Examples 1 to 3 will be described below with reference to the eighth embodiment.

(Example 1)
After applying corona discharge treatment to one side of the substrate, one side of the substrate is coated with a pattern layer, a urethane-based adhesive layer, a maleic anhydride-modified polyethylene resin layer (transparent adhesive layer), and a transparent resin. A layer and a surface protective layer containing an acrylic resin composition as a main component were laminated in this order. After the other surface of the substrate was subjected to corona discharge treatment, a primer layer (thickness: 1 to 2 [μm]) made of polyester urethane resin was formed. Thus, a decorative sheet of Example 1 (total thickness: 135 [μm]) was obtained.
In Example 1, a colored substrate layer (thickness: 55 [μm]) formed of a resin composition containing biomass-derived high-density polyethylene and fossil fuel-derived low-density polyethylene was used as the substrate. A colored substrate layer was obtained by subjecting this resin composition to calendar molding. The biomass degree of the colored substrate layer thus formed is 80%, and the density of the colored substrate layer is 1.08 [g/cm ³ ].
As the transparent resin layer, a transparent resin layer (thickness: 80 [μm]) formed of a resin composition containing biomass-derived polyethylene (“Biomass Polyethylene” manufactured by Braskem) was used. This biomass-derived polyethylene was obtained by blending biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) so that the ratio (high-density polyethylene/low-density polyethylene) was 80/20. Resin. This resin was Ruder-laminated to obtain a transparent resin layer. The transparent resin layer thus formed has a biomass degree of 94% and a density of 0.95 [g/cm ³ ].
Biourethane (meth)acrylate, which is a reaction product of a polyester polyol containing a biomass-derived component, a fossil fuel-derived isocyanate compound, and a fossil fuel-derived hydroxy (meth)acrylate, was used as the binder resin of the pattern layer. As the polyester polyol containing a biomass-derived component, a polyester polyol which is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid derived from fossil fuel was used.
The surface protective layer was formed using the same biourethane (meth)acrylate as the binder resin of the pattern layer.

(Example 2)
Same as Example 1, except that a reaction product of a polyfunctional alcohol derived from fossil fuel and a polyfunctional carboxylic acid containing a biomass-derived component was used as the polyester polyol in the biourethane (meth)acrylate that forms the surface protective layer. A decorative sheet of Example 2 was obtained.

(Example 3)
As the bio-urethane (meth)acrylate that forms the surface protective layer, bio-urethane (meth) is a reaction product of a fossil fuel-derived polyester polyol, an isocyanate compound containing a biomass-derived component, and a fossil fuel-derived hydroxy (meth)acrylate. A decorative sheet of Example 3 was obtained in the same manner as in Example 1, except that acrylate was used.

(Example 4)
A decorative sheet of Example 4 was obtained in the same manner as in Example 1, except that polyether polyol was used as the polyol in the biourethane (meth)acrylate forming the surface protective layer. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from a fossil fuel was used as the polyether polyol.

(Example 5)
As the polyether polyol in the biourethane (meth)acrylate forming the surface protective layer, the same procedure as in Example 4 was performed except that a reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional isocyanate containing a biomass-derived component was used. Thus, a decorative sheet of Example 5 was obtained.

(Example 6)
A decorative sheet of Example 6 was obtained in the same manner as in Example 3, except that a polyether polyol derived from a fossil fuel was used as the polyol in the biourethane (meth)acrylate forming the surface protective layer.

(Example 7)
A decorative sheet of Example 7 was obtained in the same manner as in Example 1, except that a polycarbonate polyol was used as the polyol in the biourethane (meth)acrylate forming the surface protective layer. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived carbonate was used as the polycarbonate polyol.

(Example 8)
A decorative sheet of Example 8 was obtained in the same manner as in Example 3, except that a fossil fuel-derived polycarbonate polyol was used as the polyol in the bio-urethane (meth)acrylate forming the surface protective layer.

(Example 9)
As the polyester polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer, the reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional carboxylic acid containing a biomass-derived component was used. A decorative sheet of Example 9 was obtained in the same manner.

(Example 10)
Bio-urethane (meth)acrylate, which is a binder resin for the pattern layer, is bio-urethane (meth)acrylate, which is a reaction product of a fossil fuel-derived polyester polyol, an isocyanate compound containing a biomass-derived component, and a fossil fuel-derived hydroxy (meth)acrylate. ) A decorative sheet of Example 10 was obtained in the same manner as in Example 1 except that acrylate was used.

(Example 11)
A decorative sheet of Example 11 was obtained in the same manner as in Example 1, except that polyether polyol was used as the polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate derived from a fossil fuel was used as the polyether polyol.

(Example 12)
Same as in Example 11 except that a reaction product of a polyfunctional alcohol derived from a fossil fuel and a polyfunctional isocyanate containing a biomass-derived component was used as the polyether polyol in the biourethane (meth)acrylate that is the binder resin of the pattern layer. Then, a decorative sheet of Example 12 was obtained.

(Example 13)
A decorative sheet of Example 13 was obtained in the same manner as in Example 10, except that a polyether polyol derived from a fossil fuel was used as the polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer.

(Example 14)
A decorative sheet of Example 14 was obtained in the same manner as in Example 1, except that a polycarbonate polyol was used as the polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer. Specifically, a reaction product of a polyfunctional alcohol containing a biomass-derived component and a fossil fuel-derived carbonate was used as the polycarbonate polyol.

(Example 15)
A decorative sheet of Example 15 was obtained in the same manner as in Example 10, except that a fossil fuel-derived polycarbonate polyol was used as the polyol in biourethane (meth)acrylate, which is the binder resin of the pattern layer.

(Example 16)
Biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) are blended so that the ratio (high-density polyethylene/low-density polyethylene) is 100/0, and the resin is Ruder-laminated. A decorative sheet of Example 16 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained in this manner.

(Reference example 1)
A decorative sheet of Reference Example 1 was obtained in the same manner as in Example 1, except that the pattern layer was formed from a urethane-based printing ink, and the surface protective layer was formed from an acrylic resin-based UV-curable resin.

(Reference example 2)
A decorative sheet of Reference Example 2 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained by Ruder laminating only a fossil fuel-derived homopolypropylene resin manufactured by Prime Polymer Co., Ltd.

(Reference example 3)
A decorative sheet of Reference Example 3 was obtained in the same manner as in Example 1, except that the colored base layer was obtained using only the fossil fuel-derived colored polyethylene resin.

(Performance evaluation, evaluation results)
For the decorative sheets of Examples 1 to 16 and the decorative sheets of Reference Examples 1 to 3, respectively, "haze (%) of transparent resin layer", "pencil hardness", "Hoffman scratch test", "extrusion suitability", "Bend whitening" was evaluated. As the evaluation method, the method described below was used.

<Haze (%) of transparent resin layer>
The haze (%) of the transparent resin layer was measured using an ultraviolet-visible-near-infrared spectrophotometer (manufacturer: Shimadzu Corporation, model number: UV-3600).
A resin having the same composition as the transparent resin layer of each example and reference example was extruded to a thickness of 70 [μm] or more and 80 [μm] or less to obtain a resin film. Haze was evaluated by measuring haze at a wavelength of 555 nm with a spectrophotometer (integrating sphere). Then, when the haze is less than 15%, it is evaluated as "◎", when the haze is within the range of 15% or more and less than 25%, it is evaluated as "◯", and when the haze is 25% or more, it is evaluated as " x” was evaluated.
In addition, in the present Example, "double-circle" and "good" were made into the pass.

<Pencil hardness>
The pencil hardness was measured with a pencil hardness tester (automatic) (manufacturer: Yoshimitsu Seiki, model number: C221A).
After performing a pencil hardness test using pencils of different hardness on the decorative material including the decorative sheet of each example and reference example, damage (gouging) occurring on the surface (surface protective layer) was confirmed. Surface hardness was evaluated. Then, after conducting the pencil hardness test using a pencil having a hardness of 2B or more, the case where damage occurred on the surface was evaluated as "⊚", and after conducting the pencil hardness test using a pencil having a hardness of 4B or more. , and the case where damage occurred on the surface was evaluated as "○". In addition, a case where damage occurred on the surface after conducting a pencil hardness test using a pencil having a hardness of 5B or less was evaluated as "x".
In addition, in the present Example, "double-circle" and "good" were made into the pass.

<Hoffman scratch test>
The Hoffman scratch test was conducted by setting a scratch blade (cylindrical blade of φ7) so as to contact the surface of the decorative sheet at an angle of 45 degrees, and moving the tester on the decorative sheet.
Gradually increasing the load (weight) within the range of 200 to 2000 g (every 200 g) and scratching, the load (g) at which the sample surface was scratched was evaluated. In addition, when the damage was caused by a load of 800 g, "600 g" was described in the table as the withstand load.
In addition, in this example, the case where the withstand load was "200 g" was rejected.

<Extrusion suitability>
A transparent resin layer was extruded and its production suitability (extrusion suitability) was confirmed.
As a result, if the product can be manufactured (molded) without any problems, it is rated as "○" (accepted). On the other hand, those with the possibility of defects were rated as "Δ" (failed).

<Bending whitening>
Using a decorative sheet (that is, a decorative material) laminated to MDF, suitability for V-cut processing (presence or absence of whitening upon bending) was confirmed.
As a result, "○" (pass) was given when no whitening occurred, "△" (pass) was given when slight whitening occurred, and "×" (failed) was given when whitening occurred. ).

As a result of evaluating various performances using the methods described above, the decorative sheets of Examples 1 to 16 exhibited excellent performance equivalent to or better than that of Reference Examples 1-3 in all evaluation tests. In other words, the decorative sheets of Examples 1 to 16 were found to be able to reduce the amount of fossil fuels used by using plant-derived materials and to maintain physical properties suitable for use as decorative sheets. rice field.

(Ninth embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG. A specific configuration of the decorative sheet 1 will be described later.
Note that the configuration of the decorative material 10 in the ninth embodiment is the same as that of the above-described first embodiment except for the configuration of the decorative sheet 1, so the description of the configuration other than the decorative sheet 1 will be omitted.

(Configuration of decorative sheet)
As shown in FIG. 1, the decorative sheet 1 includes a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, an adhesive layer 4, a transparent resin layer (transparent thermoplastic resin layer) 5, a surface It includes a protective layer 6 , uneven portions 7 and a primer layer 8 .

<Colored substrate layer>
The colored base material layer 2 is a resin layer formed using a thermoplastic resin, a colored resin layer formed of a resin composition containing biomass-derived (plant-derived) polyethylene, and further the colored resin layer. contains inorganic matter.
The composition of the colored substrate layer 2 will be described in detail below.
(Polyethylene derived from biomass)
In the ninth embodiment, the biomass-derived polyethylene is obtained by polymerizing a monomer containing biomass-derived ethylene. Ethylene derived from biomass is not particularly limited, and ethylene produced by a conventionally known method can be used. Since biomass-derived ethylene is used as a raw material monomer, the polymerized polyethylene is biomass-derived.
The raw material monomer for polyethylene does not have to contain 100% by mass of biomass-derived ethylene.

The monomer, which is a raw material for biomass-derived polyethylene, may further contain at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin, and may further contain a biomass-derived α-olefin.

Although the number of carbon atoms of the α-olefin is not particularly limited, those having 3 to 20 carbon atoms can usually be used, preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. In addition, by containing such an α-olefin, the polymerized polyethylene has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear polyethylene.

By using ethylene, which is a raw material derived from biomass, it is theoretically possible to manufacture from 100% biomass-derived components.

The biomass-derived ethylene concentration in the polyethylene (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the biomass-derived carbon content by radioactive carbon (C14) measurement. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in polyethylene, the ratio of biomass-derived carbon can be calculated. In the ninth embodiment, the biomass-derived carbon content Pbio can be obtained as follows, where PC14 is the content of C14 in polyethylene.
Pbio (%) = PC14/105.5 x 100

In the ninth embodiment, theoretically, if all biomass-derived ethylene is used as the raw material for polyethylene, the concentration of biomass-derived ethylene is 100%, and the biomass degree of biomass-derived polyethylene is 100. In addition, the biomass-derived ethylene concentration in the fossil fuel-derived polyethylene produced only from fossil fuel-derived raw materials is 0%, and the biomass degree of the fossil fuel-derived polyethylene is 0.

In the ninth embodiment, the biomass-derived polyethylene and the decorative sheet containing the polyethylene need not have a biomass degree of 100.

In the ninth embodiment, the method for polymerizing the biomass-derived ethylene-containing monomer is not particularly limited, and a conventionally known method can be used. The polymerization temperature and polymerization pressure should be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of a method for polymerizing a monomer containing ethylene is described below.

Polymerization methods for ethylene polymers and copolymers of ethylene and α-olefins vary depending on the type of polyethylene desired, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and direct It can be appropriately selected depending on the difference in density and branching of linear low density polyethylene (LLDPE) or the like. For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any method of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization, It is preferable to carry out in one stage or in multiple stages of two or more stages.

As the biomass-derived polyethylene, an ethylene polymer or an ethylene/α-olefin copolymer may be used alone, or two or more of them may be used in combination.

(Resin composition containing biomass-derived polyethylene)
In the ninth embodiment, the resin composition contains polyethylene as a main component. The resin composition contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 95% by mass, more preferably 25 to 75% by mass, based on the total resin composition. If the concentration of biomass-derived ethylene in the resin composition is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the case where conventional fossil fuels are used, and a carbon-neutral decorative sheet can be realized. .

The above resin composition may contain two or more types of polyethylene having different degrees of biomass, and the concentration of biomass-derived ethylene in the resin composition as a whole may be within the above range.

The above resin composition may further contain a fossil fuel-derived polyethylene obtained by polymerizing a monomer containing a fossil fuel-derived ethylene and at least one of a fossil fuel-derived ethylene and an α-olefin. That is, in the ninth embodiment, the resin composition may be a mixture of biomass-derived polyethylene and fossil fuel-derived polyethylene. The mixing method is not particularly limited, and conventionally known methods can be used for mixing. For example, dry blending or melt blending may be used.

According to the ninth embodiment, the resin composition contains 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass of biomass-derived polyethylene. The resin composition may contain a mixture of biomass-derived polyethylene and, for example, fossil fuel-derived polyethylene. The concentration of ethylene should be 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass.

Various additives other than polyethylene, which is the main component, may be added to the resin composition produced in the production process of the resin composition as long as the characteristics are not impaired. Additives include, for example, plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slip agents, release agents, anti- Oxidizing agents, ion exchange agents, color pigments, and the like can be added. These additives are added in an amount of preferably 1 to 20% by mass, preferably 1 to 10% by mass, based on the total resin composition.
(inorganic matter)
The colored base material layer 2 contains an inorganic substance, and the specific gravity of the colored base material layer 2 is 0.97 or more and 1.5 or less.
As inorganic substances, for example, any one or more of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides can be applied.

As described above, the colored substrate layer 2 contains 5% by mass or more of biomass-derived ethylene with respect to the entire colored substrate layer 2 . If the concentration of biomass-derived ethylene in the colored substrate layer 2 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

Further, an inorganic substance is added to the colored base material layer 2 so that the specific gravity is 0.97 or more and 1.5 or less. By adding an inorganic substance to the colored base material layer 2 so that the specific gravity is 0.97 or more and 1.5 or less, the concealability of the colored base material layer 2 can be enhanced.

The colored substrate layer 2 includes, as biomass-derived polyethylene, biomass-derived high-density polyethylene and biomass-derived low-density polyethylene, biomass-derived high-density polyethylene and fossil fuel-derived polyethylene, and fossil fuel-derived polyethylene. It may be any of those containing fuel-derived high-density polyethylene and biomass-derived low-density polyethylene, and the biomass degree of the entire colored base material layer 2 is within the range of 10% or more and 90% or less. good too.
The biomass-derived high-density polyethylene refers to polyethylene having a density exceeding 0.94. In addition, biomass-derived low-density polyethylene refers to polyethylene having a density of 0.94 or less.
The colored substrate layer 2 is composed of biomass-derived high-density polyethylene and low-density polyethylene (either biomass-derived or fossil fuel-derived) at a ratio of 95:5. Brent in the range of ~70:30 is good. If the content of the low-density polyethylene is low, the film-forming stability is poor, and if the content of the low-density polyethylene is high, the film becomes too soft.

The method for producing the colored base material layer 2 is not particularly limited, and it can be produced by a conventionally known method. In the ninth embodiment, it is preferable to form by calendar molding.

In addition, the colored substrate layer 2 may optionally contain, for example, a coloring agent, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, and an antibacterial agent. , an antifungal agent, an antifriction agent, a light scattering agent, and a luster adjusting agent.
The thickness of the colored base material layer 2 is preferably in the range of 40 [μm] to 200 [μm], more preferably 51 [μm] to 200 [μm], and 55 [μm]. It is more preferable to be at least 100 [μm] or less. This is because, when the thickness of the colored base layer 2 is 40 [μm] or more, it is possible to absorb the irregularities and steps of the underlying floor material, etc., and improve the finish of the decorative sheet 1. Due to something. Further, when the thickness of the colored base layer 2 is 200 [μm] or less, the manufacturing cost of the decorative sheet 1 can be reduced without forming the colored base layer 2 thicker than necessary. due to that.

In the ninth embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the colored substrate layer 2, but the present invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the ninth embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin that constitutes the colored substrate layer 2 .

<Pattern layer>
The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored base material layer 2, and is a layer for adding a pattern for imparting design. The design layer 3 may be omitted if the coloring of the colored base material layer 2 can be used instead.
The pattern layer 3 is formed using printing ink, paint, or the like. The printing ink, paint, or the like that forms the pattern layer 3 is formed by dissolving or dispersing a coloring agent such as a dye or pigment in a suitable diluent solvent together with a suitable binder resin.

The printing ink, paint, or the like that forms the pattern layer 3 is applied using, for example, various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.
As the binder resin, for example, it is possible to use urethane-based resin, acrylic-based resin, vinyl chloride-based resin, polyimide-based resin, nitrocellulose, etc., or a mixture thereof, but is not limited to these. do not have.
Any pattern can be used as the pattern. For example, wood grain patterns, stone grain patterns, texture patterns, abstract patterns, geometric patterns, characters, symbols, single-color solid colors, etc., or combinations thereof can be used. It is possible. In addition, in order to improve the concealability of the decorative sheet 1, a concealing layer may be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer is formed, for example, using opaque printing ink or paint containing a large amount of opaque pigment such as titanium dioxide or iron oxide.

The thickness of the pattern layer 3 is preferably in the range of 1 [μm] to 10 [μm]. This is because when the pattern layer 3 has a thickness of 1 [μm] or more, clear printing is possible. Further, when the thickness of the pattern layer 3 is 10 [μm] or less, the printing workability in manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.
In addition, in order to impart various functions to the pattern layer 3, for example, an extender, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a desiccant, a curing agent, a curing accelerator and a curing agent are added. Functional additives such as retardants may be added.
In addition, the pattern layer 3 includes, for example, a solid colored base layer for concealing the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern for adding a design. It is good also as a structure which has a pattern pattern layer.

<Adhesive layer>
The adhesive layer 4 is laminated on one surface (upper surface in FIG. 1) of the pattern layer 3 and used for bonding the pattern layer 3 and the transparent resin layer 5 together.
As the material of the adhesive layer 4, for example, urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, polyolefin, or the like can be used. A polyolefin resin is particularly preferred because of its adhesiveness to the transparent resin layer 5 .

<Transparent resin layer>
The transparent resin layer 5 is laminated on one surface (the upper surface in FIG. 1) of the adhesive layer 4, and is made of a resin composition containing the above-described biomass-derived (plant-derived) polyethylene or fossil fuel-derived polyethylene. It is a transparent resin layer formed of a resin composition containing More specifically, the transparent resin layer 5 is a resin layer formed of a resin composition containing biomass-derived polyethylene obtained by polymerizing the above-described biomass-derived ethylene-containing monomer. That is, in the transparent resin layer 5 , the resin composition containing biomass-derived polyethylene used in the colored substrate layer 2 may be made of a resin composition to which no inorganic substance is added. In other words, both the colored substrate layer 2 and the transparent resin layer 5 are formed of a resin composition containing biomass-derived (plant-derived) polyethylene. No inorganic substance is added to the resin layer 5 . No inorganic substance is added to the transparent resin layer 5 on the pattern layer 3, and the inorganic substance is added only to the colored substrate layer 2 which is the lower layer of the pattern layer 3, so that the transparency of the transparent resin layer 5 is maintained. By increasing the concealability of the colored base material layer 2 while suppressing the pattern layer 3 from being concealed, the color and pattern of the base to which the decorative sheet 1 is adhered can be concealed.

The transparent resin layer 5 contains 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 40 to 75% by mass of the biomass-derived ethylene described above with respect to the entire transparent resin layer 5. may comprise: If the concentration of biomass-derived ethylene in the transparent resin layer 5 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

The transparent resin layer 5 may contain biomass-derived high-density polyethylene as the biomass-derived polyethylene.
In addition, the transparent resin layer 5 may contain, as biomass-derived polyethylene, polyethylene obtained by blending biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in a range of 100:0 to 20:80. .
Further, the transparent resin layer 5 may have a biomass degree of 10% or more and 90% or less.

The method for manufacturing the transparent resin layer 5 is not particularly limited, and it can be manufactured by a conventionally known method. In the ninth embodiment, it is preferably formed by extrusion molding, and more preferably extrusion molding is performed by a T-die method or an inflation method.

The biomass-derived polyethylene forming the transparent resin layer 5 may be added with a nucleating agent (for example, “Rikemaster CN-002” manufactured by Riken Vitamin Co., Ltd.).
The nucleating agent is preferably added to polyethylene within the range of 500 [ppm] to 2000 [ppm] based on the mass of polyethylene, and within the range of 1500 [ppm] to 2000 [ppm], It is more preferable if it is added to polyethylene.

The transparent resin layer 5 may optionally contain, for example, a colorant, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, an antifungal agent. At least one selected from various additives such as agents, antifriction agents, light scattering agents and gloss modifiers may be added.
The transparent resin layer 5 preferably has a degree of transparency (colorless transparency, colored transparency, translucent) that allows the pattern of the pattern layer 3 to be seen through from the surface (upper surface) of the decorative sheet 1 .

<Surface protective layer>
The surface protective layer 6 is laminated on one surface (the upper surface in FIG. 1) of the transparent resin layer 5, and provides the decorative sheet 1 with weather resistance, scratch resistance, stain resistance, design properties, and the like. It is a layer provided to impart functions.
Moreover, the surface protective layer 6 is formed using, for example, an acrylic resin composition.
In addition, the surface protective layer 6 may optionally contain weathering agents, plasticizers, stabilizers, fillers, dispersants, coloring agents such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, and light stabilizers. , anti-blocking agents, catalyst scavengers, colorants, light scattering agents, gloss modifiers, and other additives. Moreover, the surface protective layer 6 may contain functional additives such as an antibacterial agent and an antifungal agent, if necessary.

<Uneven part>
The concave-convex portion 7 is formed by concave portions provided at a plurality of locations on the transparent resin layer 5 and the surface protective layer 6 .

<Primer layer>
The primer layer 8 is a layer serving as a base, and is a layer for improving adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9 .
Further, the primer layer 8 is laminated on the other surface (the lower surface in FIG. 1) of the colored base material layer 2 .
Furthermore, the primer layer 8 is formed using, for example, a polyester-based resin, an organic additive, a pigment, or the like.
In addition, the primer layer 8 may contain an antirust pigment for the purpose of improving corrosion resistance.
The thickness of the primer layer 8 is, for example, within the range of 1 [μm] or more and 10 [μm] or less.
<Concentration of biomass-derived ethylene in decorative sheet>
As described above, the colored substrate layer 2 and the transparent resin layer 5 each contain 5% by mass or more of biomass-derived ethylene, and the entire decorative sheet 1 preferably contains 5% by mass or more of the biomass-derived material.
<Specific gravity of entire decorative sheet>
The specific gravity of the entire decorative sheet 1 is preferably 0.97 or more and 1.5 or less by adding an inorganic substance to the colored thermoplastic resin layer. By doing so, for example, it is possible to form the decorative sheet 1 having a concealing property equivalent to that of a structure formed using polyethylene derived from fossil fuel.

The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications are possible according to the design and the like as long as they do not deviate.

(Effect of the ninth embodiment)
With the decorative sheet 1 of the ninth embodiment, the effects described below can be achieved.
(1) The colored substrate layer 2 is a resin layer formed of a resin composition containing biomass-derived ethylene, containing 5% by mass or more of biomass-derived ethylene, and an inorganic substance added to the colored substrate layer 2. The specific gravity of the colored base material layer 2 is 0.97 or more and 1.5 or less.
Therefore, even in a configuration using biomass-derived polyethylene, which is a plant-derived material, for example, the colored base layer 2 having the same degree of concealability as a configuration formed using polyethylene derived from fossil fuels. can be formed.

As a result, it is possible to provide the decorative sheet 1 capable of suppressing deterioration of concealability even when formed using biomass-derived polyethylene, which is a plant-derived material.

(2) At least one of the transparent resin layer 5 and the colored substrate layer 2 may contain biomass-derived high-density polyethylene and biomass-derived low-density polyethylene as biomass-derived polyethylene.
As a result, it becomes possible to form the transparent resin layer 5 and the colored substrate layer 2 having further flexibility.

(3) The transparent resin layer 5 contains polyethylene obtained by blending biomass-derived high-density polyethylene and biomass-derived low-density polyethylene in the range of 100:0 to 20:80 as biomass-derived polyethylene. You can
As a result, it becomes possible to form the transparent resin layer 5 having high hardness.

(4) The colored substrate layer 2 contains biomass-derived high-density polyethylene and biomass-derived low-density polyethylene as biomass-derived polyethylene, and has a biomass degree within the range of 10% or more and 90% or less. may
As a result, it is possible to form the colored base material layer 2 having good film-forming stability and sufficient softness as a decorative sheet.

Further, with the decorative material 10 of the ninth embodiment, it is possible to obtain the effects described below.
(5) The base material 9 and the decorative sheet 1 laminated on at least one surface of the base material 9 are provided.
As a result, it is possible to provide the decorative material 10 capable of suppressing a decrease in concealability even when formed using biomass-derived polyethylene, which is a plant-derived material.

The decorative sheets of Examples 1 to 6 and the decorative sheets of Comparative Examples 1 to 3 will be described below with reference to the ninth embodiment.

(Example 1)
After applying corona discharge treatment to one side of the base material, a pattern layer printed with urethane-based printing ink, a urethane-based adhesive layer, and a maleic anhydride-modified polyethylene resin layer ( adhesive layer), a transparent resin layer, and a surface protective layer containing an acrylic resin composition as a main component were laminated in this order. Further, after the other surface of the substrate was subjected to corona discharge treatment, a primer layer (thickness: 1 to 2 [μm]) made of a polyester urethane resin was formed on the other surface of the substrate. Thus, a decorative sheet of Example 1 (total thickness: 135 [μm]) was obtained. The biomass degree of the decorative sheet is 80%.
On the primer layer side of the decorative sheet, MDF (Medium density fiberboard) is applied using, for example, an adhesive BA-10L manufactured by Eva Japan Coating Resin Co., Ltd. and a curing agent BA-11B manufactured by Japan Coating Resin Co., Ltd. A decorative material can be obtained by laminating them together.
In Example 1, as a substrate, a colored substrate layer (thickness: 55 [μm]) formed of a resin composition containing biomass-derived polyethylene ("Green Polyethylene" manufactured by Braskem) to which an inorganic substance was added. was used. This biomass-derived polyethylene is a resin obtained by blending biomass-derived high-density polyethylene and biomass-derived low-density polyethylene. Calcium carbonate and titanium oxide were blended as inorganic substances so that the specific gravity of the colored substrate layer was 1.2. This resin was subjected to Ruder lamination to obtain a colored substrate layer. The biomass degree of the colored substrate layer thus formed is 80%.
In the transparent resin layer (thickness: 60 [μm]) formed of a resin composition containing biomass-derived polyethylene ("green polyethylene" manufactured by Braskem), as in the colored base layer, However, a transparent resin layer to which no inorganic substance was added was used. This biomass-derived polyethylene was obtained by blending biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) so that the ratio (high-density polyethylene/low-density polyethylene) was 80/20. Resin. This resin was Ruder-laminated to obtain a transparent resin layer.

(Example 2)
A decorative sheet of Example 2 was obtained in the same manner as in Example 1, except that calcium carbonate was blended as an inorganic substance so that the specific gravity of the colored base layer was 0.97.

(Example 3)
A decorative sheet of Example 3 was obtained in the same manner as in Example 1 except that calcium carbonate and titanium oxide were blended as inorganic substances so that the specific gravity of the colored base layer was 1.5.

(Example 4)
A decorative sheet of Example 4 was obtained in the same manner as in Example 1 except that calcium carbonate and titanium oxide were blended as inorganic substances so that the specific gravity of the colored base layer was 1.0.

(Example 5)
A decorative sheet of Example 5 was obtained in the same manner as in Example 1, except that the transparent resin layer was formed using polypropylene derived from fossil fuel.

(Example 6)
Biomass-derived high-density polyethylene (SHC7260) and biomass-derived low-density polyethylene (SPB681) are blended so that the ratio (high-density polyethylene/low-density polyethylene) is 100/0, and the resin is Ruder-laminated. A decorative sheet of Example 6 was obtained in the same manner as in Example 1, except that a transparent resin layer was obtained in this way.

(Comparative example 1)
A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that calcium carbonate and titanium oxide were added as inorganic substances so that the specific gravity was 0.96.

(Comparative example 2)
A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1, except that titanium oxide was blended as an inorganic substance so as to have a specific gravity of 0.95.

(Comparative Example 3)
A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that calcium carbonate and titanium oxide were added as inorganic substances so that the specific gravity was 1.6.

(Performance evaluation, evaluation results)
For the decorative sheets of Examples 1 to 5 and the decorative sheets of Comparative Examples 1 to 3, respectively, "concealability", "productivity of colored thermoplastic resin layer (colored base layer)", and "printability" were evaluated. evaluated. As the evaluation method, the method described below was used.

<Concealability>
The decorative sheet was subjected to a hiding property test described in JIS6921 wallpaper.
Judgment was made according to the criteria for the hiding property of JIS6921, and grade 4 was graded as "⊚", grade 3 as "○", and grade 2 as "Δ".

<Productivity of Colored Thermoplastic Resin Layer>
Regarding the decorative sheet, the degree of defects such as film-forming property such as surface condition, presence or absence of fish eyes, presence or absence of thickness unevenness, and the like was visually evaluated. A case where there was almost no defect was rated as "⊚", a case where there was a defect but had no effect on production was rated as "◯", and a case where there was a defect that affected production was rated as "x". When the number of defective spots was about 1 to 2 per square meter, it was judged as "good".

<Printability>
For the decorative sheet, the presence or absence of poor ink adhesion, the presence or absence of thermal wrinkles during drying, and the like were visually evaluated. "◎" indicates that there is no inferiority to current decorative sheet printability; bottom.

Table 1 shows the results of evaluating various performances using the method described above. The decorative sheets of Examples 1 to 6 exhibited substantially excellent performance in all evaluation tests. On the other hand, the decorative sheets of Comparative Examples 1 to 3 exhibited insufficient performance in at least some of the evaluation tests.

(Tenth embodiment)
The configuration of the cosmetic material 10 will be described below with reference to FIG.
The decorative material 10 includes a decorative sheet 1 and a base material 9, as shown in FIG. A specific configuration of the decorative sheet 1 will be described later.
Note that the configuration of the decorative material 10 in the tenth embodiment is the same as that of the above-described first embodiment except for the configuration of the decorative sheet 1, so the description of the configuration other than the decorative sheet 1 will be omitted.

(Configuration of decorative sheet)
The decorative sheet 1 includes a colored substrate layer (colored thermoplastic resin layer) 2, a pattern layer 3, a surface protective layer 6, and a primer layer 8, as shown in FIG.

<Colored substrate layer>
The colored substrate layer 2 is a resin layer formed using a thermoplastic resin, and is a colored resin layer formed from a resin composition containing polyethylene derived from biomass (derived from plants).
The composition of the colored substrate layer 2 will be described in detail below.
(Polyethylene derived from biomass)
In the tenth embodiment, the biomass-derived polyethylene is obtained by polymerizing a monomer containing biomass-derived ethylene. Ethylene derived from biomass is not particularly limited, and ethylene produced by a conventionally known method can be used. Since biomass-derived ethylene is used as a raw material monomer, the polymerized polyethylene is biomass-derived.
The raw material monomer for polyethylene does not have to contain 100% by mass of biomass-derived ethylene.

The monomer, which is a raw material for biomass-derived polyethylene, may further contain at least one of fossil fuel-derived ethylene and fossil fuel-derived α-olefin, and may further contain a biomass-derived α-olefin.

Although the number of carbon atoms of the α-olefin is not particularly limited, those having 3 to 20 carbon atoms can usually be used, preferably butylene, hexene, or octene. This is because butylene, hexene, or octene can be produced by polymerization of ethylene, which is a raw material derived from biomass. In addition, by containing such an α-olefin, the polymerized polyethylene has an alkyl group as a branched structure, so that it can be made more flexible than a simple linear polyethylene.

By using ethylene, which is a raw material derived from biomass, it is theoretically possible to manufacture from 100% biomass-derived components.

The biomass-derived ethylene concentration in the polyethylene (hereinafter sometimes referred to as “biomass degree”) is a value obtained by measuring the biomass-derived carbon content by radioactive carbon (C14) measurement. Since carbon dioxide in the atmosphere contains a certain proportion of C14 (105.5 pMC), the C14 content in plants that grow by taking in carbon dioxide in the atmosphere, such as corn, is also about 105.5 pMC. It is known. It is also known that fossil fuels contain almost no C14. Therefore, by measuring the ratio of C14 contained in the total carbon atoms in polyethylene, the ratio of biomass-derived carbon can be calculated. In the tenth embodiment, the biomass-derived carbon content Pbio can be obtained as follows, where PC14 is the content of C14 in polyethylene.
Pbio (%) = PC14/105.5 x 100

In the tenth embodiment, theoretically, if all biomass-derived ethylene is used as the raw material of polyethylene, the biomass-derived ethylene concentration is 100%, and the biomass degree of biomass-derived polyethylene is 100. In addition, the biomass-derived ethylene concentration in the fossil fuel-derived polyethylene produced only from fossil fuel-derived raw materials is 0%, and the biomass degree of the fossil fuel-derived polyethylene is 0.

In the tenth embodiment, the biomass-derived polyethylene and the decorative sheet containing the polyethylene need not have a biomass degree of 100.

In the tenth embodiment, the method for polymerizing the biomass-derived ethylene-containing monomer is not particularly limited, and a conventionally known method can be used. The polymerization temperature and polymerization pressure should be appropriately adjusted according to the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited, and a conventionally known apparatus can be used. An example of a method for polymerizing a monomer containing ethylene is described below.

Polymerization methods for ethylene polymers and copolymers of ethylene and α-olefins vary depending on the type of polyethylene desired, such as high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and direct It can be appropriately selected depending on the difference in density and branching of linear low density polyethylene (LLDPE) or the like. For example, using a multi-site catalyst such as a Ziegler-Natta catalyst or a single-site catalyst such as a metallocene catalyst as a polymerization catalyst, by any method of gas phase polymerization, slurry polymerization, solution polymerization, and high pressure ion polymerization, It is preferable to carry out in one stage or in multiple stages of two or more stages.

As the biomass-derived polyethylene, an ethylene polymer or an ethylene/α-olefin copolymer may be used alone, or two or more of them may be used in combination.

(Resin composition containing biomass-derived polyethylene)
In the tenth embodiment, the resin composition contains polyethylene as a main component. The resin composition contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 95% by mass, more preferably 25 to 75% by mass, based on the total resin composition. If the concentration of biomass-derived ethylene in the resin composition is 5% by mass or more, it is possible to reduce the amount of fossil fuel used compared to conventional methods, and to realize a carbon-neutral decorative sheet.

The above resin composition may contain two or more types of polyethylene having different degrees of biomass, and the concentration of biomass-derived ethylene in the resin composition as a whole may be within the above range.

The above resin composition may further contain a fossil fuel-derived polyethylene obtained by polymerizing a monomer containing a fossil fuel-derived ethylene and at least one of a fossil fuel-derived ethylene and an α-olefin. That is, in the tenth embodiment, the resin composition may be a mixture of biomass-derived polyethylene and fossil fuel-derived polyethylene. The mixing method is not particularly limited, and conventionally known methods can be used for mixing. For example, dry blending or melt blending may be used.

According to a tenth embodiment, the resin composition contains 5% by mass or more, preferably 5 to 95% by mass, more preferably 25 to 75% by mass of biomass-derived polyethylene. The resin composition may contain a mixture of biomass-derived polyethylene and, for example, fossil fuel-derived polyethylene. The concentration of ethylene should be 5 mass % or more, preferably 5 to 95 mass %, more preferably 25 to 75 mass %.

Various additives other than polyethylene, which is the main component, may be added to the resin composition produced in the production process of the resin composition as long as the characteristics are not impaired. Additives include, for example, plasticizers, ultraviolet stabilizers, anti-coloring agents, matting agents, deodorants, flame retardants, weathering agents, antistatic agents, thread friction reducing agents, slip agents, release agents, anti- Oxidizing agents, ion exchange agents, color pigments, and the like can be added. These additives are added in an amount of preferably 1 to 20% by mass, preferably 1 to 10% by mass, based on the total resin composition.
(inorganic matter)
The colored base material layer 2 contains an inorganic substance, and the specific gravity of the colored base material layer 2 is 0.97 or more and 1.5 or less.
As inorganic substances, for example, any one or more of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides can be applied.

As described above, the colored substrate layer 2 contains biomass-derived ethylene in an amount of 5% by mass or more, preferably 5 to 90% by mass, more preferably 25 to 75% by mass, most preferably 5% by mass or more of the entire colored substrate layer 2. comprises 40-75%. If the concentration of biomass-derived ethylene in the colored substrate layer 2 is 5% by mass or more, the amount of fossil fuel used can be reduced compared to the conventional case, and a carbon-neutral decorative sheet can be realized.

Further, an inorganic substance is added to the colored base material layer 2 so that the specific gravity is 0.97 or more and 1.5 or less. By adding an inorganic substance to the colored base material layer 2 so that the specific gravity is 0.97 or more and 1.5 or less, the concealability of the colored base material layer 2 can be enhanced.

The colored substrate layer 2 includes, as biomass-derived polyethylene, biomass-derived high-density polyethylene and biomass-derived low-density polyethylene, biomass-derived high-density polyethylene and fossil fuel-derived polyethylene, and fossil fuel. Any of those containing high-density polyethylene derived from biomass and low-density polyethylene derived from biomass may be used, and the biomass degree of the entire colored base material layer 2 is in the range of 10% or more and 90% or less. good.
The biomass-derived high-density polyethylene refers to polyethylene having a density exceeding 0.94. In addition, biomass-derived low-density polyethylene refers to polyethylene having a density of 0.94 or less.
The colored substrate layer 2 is composed of biomass-derived high-density polyethylene and low-density polyethylene (which may be biomass-derived or fossil fuel-derived) at a ratio of 95:5 as biomass-derived polyethylene. Brent in the range of ~70:30 is good. If the content of the low-density polyethylene is low, the film-forming stability is poor, and if the content of the low-density polyethylene is high, the film becomes too soft.

The method for producing the colored base material layer 2 is not particularly limited, and it can be produced by a conventionally known method. In the tenth embodiment, it is preferable to form by calendar molding.

In addition, the colored substrate layer 2 may optionally contain, for example, a coloring agent, a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, and an antibacterial agent. , an antifungal agent, an antifriction agent, a light scattering agent, and a luster adjusting agent.
The thickness of the colored base material layer 2 is preferably in the range of 40 [μm] to 200 [μm], more preferably 51 [μm] to 200 [μm], and 55 [μm]. It is more preferable to be at least 100 [μm] or less. This is because, when the thickness of the colored base layer 2 is 40 [μm] or more, it is possible to absorb the irregularities and steps of the underlying floor material, etc., and improve the finish of the decorative sheet 1. Due to something. Further, when the thickness of the colored base layer 2 is 200 [μm] or less, the manufacturing cost of the decorative sheet 1 can be reduced without forming the colored base layer 2 thicker than necessary. due to that.

In the tenth embodiment, biomass-derived polyethylene was described as the biomass-derived resin constituting the colored substrate layer 2, but the present invention is not limited to this. For example, instead of the biomass-derived polyethylene described above, biomass-derived polypropylene, biomass-derived polybutylene, or the like may be used. That is, in the tenth embodiment, a wide range of biomass-derived polyolefins can be used as the biomass-derived resin constituting the colored base material layer 2 .

<Pattern layer>
The pattern layer 3 is laminated on one surface (the upper surface in FIG. 1) of the colored base material layer 2, and is a layer for adding a pattern for imparting design. The design layer 3 may be omitted if the coloring of the colored base material layer 2 can be used instead.
The pattern layer 3 is formed using printing ink, paint, or the like. The printing ink, paint, or the like that forms the pattern layer 3 is formed by dissolving or dispersing a coloring agent such as a dye or pigment in a suitable diluent solvent together with a suitable binder resin.

The printing ink, paint, or the like that forms the pattern layer 3 is applied using, for example, various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.
As the binder resin, for example, it is possible to use urethane-based resin, acrylic-based resin, vinyl chloride-based resin, polyimide-based resin, nitrocellulose, etc., or a mixture thereof, but is not limited to these. do not have.
Any pattern can be used as the pattern. For example, wood grain patterns, stone grain patterns, texture patterns, abstract patterns, geometric patterns, characters, symbols, single-color solid colors, etc., or combinations thereof can be used. It is possible. In addition, in order to improve the concealability of the decorative sheet 1, a concealing layer may be provided between the pattern layer 3 and the colored substrate layer 2. The concealing layer is formed, for example, using opaque printing ink or paint containing a large amount of opaque pigment such as titanium dioxide or iron oxide.

The thickness of the pattern layer 3 is preferably in the range of 1 [μm] to 10 [μm]. This is because when the pattern layer 3 has a thickness of 1 [μm] or more, clear printing is possible. Further, when the thickness of the pattern layer 3 is 10 [μm] or less, the printing workability in manufacturing the decorative sheet 1 is improved, and the manufacturing cost can be suppressed.
In addition, in order to impart various functions to the pattern layer 3, for example, an extender, a plasticizer, a dispersant, a surfactant, a tackifier, an adhesion aid, a desiccant, a curing agent, a curing accelerator and a curing agent are added. Functional additives such as retardants may be added.
In addition, the pattern layer 3 includes, for example, a solid colored base layer for concealing the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern for adding a design. It is good also as a structure which has a pattern pattern layer.

<Surface protective layer>
The surface protective layer 6 is laminated on one surface (the upper surface in FIG. 1) of the pattern layer 3, and provides the decorative sheet 1 with functions such as weather resistance, scratch resistance, stain resistance, and design. It is a layer provided to provide
Moreover, the surface protective layer 6 is formed using, for example, an acrylic resin composition.
In addition, the surface protective layer 6 may optionally contain weathering agents, plasticizers, stabilizers, fillers, dispersants, coloring agents such as dyes and pigments, solvents, ultraviolet absorbers, heat stabilizers, and light stabilizers. , anti-blocking agents, catalyst scavengers, colorants, light scattering agents, gloss modifiers, and other additives. Moreover, the surface protective layer 6 may contain functional additives such as an antibacterial agent and an antifungal agent, if necessary.

<Primer layer>
The primer layer 8 is a layer serving as a base, and is a layer for improving adhesion and corrosion resistance between the colored substrate layer 2 and the substrate 9 .
Further, the primer layer 8 is laminated on the other surface (the lower surface in FIG. 1) of the colored base material layer 2 .
Furthermore, the primer layer 8 is formed using, for example, a polyester-based resin, an organic additive, a pigment, or the like.
In addition, the primer layer 8 may contain an antirust pigment for the purpose of improving corrosion resistance.
The thickness of the primer layer 8 is, for example, within the range of 1 [μm] or more and 10 [μm] or less.
<Specific gravity of entire decorative sheet>
The overall specific gravity of the decorative sheet 1 is preferably 0.97 or more and 1.5 or less. More preferably, the specific gravity is 0.99 or more and 1.4 or less. By doing so, for example, it is possible to form the decorative sheet 1 having a concealing property equivalent to that of a structure formed using polyethylene derived from fossil fuel.
<Total thickness of entire decorative sheet>
The thickness of the entire decorative sheet 1 is preferably 50 [μm] or more and 200 [μm] or less. More preferably, it is 70 [μm] or more and 150 [μm] or less. By doing so, for example, it is possible to form the decorative sheet 1 having a concealing property equivalent to that of a structure formed using polyethylene derived from fossil fuel.

The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications are possible according to the design and the like as long as they do not deviate.

(Effect of the tenth embodiment)
With the decorative sheet 1 of the tenth embodiment, the effects described below can be achieved.
(1) The colored substrate layer 2 is a resin layer formed of a resin composition containing biomass-derived ethylene, contains 5% by mass or more of biomass-derived ethylene, and further contains an inorganic substance. The layer 2 has a specific gravity of 0.97 or more and 1.5 or less.
Therefore, even in a configuration using biomass-derived polyethylene, which is a plant-derived material, for example, the colored base layer 2 having the same degree of concealability as a configuration formed using polyethylene derived from fossil fuels. can be formed.

As a result, it is possible to provide the decorative sheet 1 capable of suppressing deterioration of concealability even when formed using biomass-derived polyethylene, which is a plant-derived material.
In addition, the colored base material layer 2 can be made to have a concealing property by adding an inorganic material without providing a separate layer for concealing, so that a decorative sheet having a single-layer structure can be obtained. Therefore, it is possible to reduce the amount of resin compared to conventional multi-layered films having concealability, thereby contributing to the realization of a carbon-neutral society.

(2) The colored substrate layer 2 may contain, as the biomass-derived polyethylene, a biomass-derived high-density polyethylene and a biomass-derived low-density polyethylene.
As a result, it becomes possible to form the colored base material layer 2 having further flexibility.

(3) The colored substrate layer 2 contains biomass-derived high-density polyethylene and biomass-derived low-density polyethylene as biomass-derived polyethylene, and has a biomass degree of 10% or more and 90% or less. may
As a result, it becomes possible to form the colored base material layer 2 having further flexibility.

Further, with the decorative material 10 of the tenth embodiment, it is possible to obtain the effects described below.
(4) The base material 9 and the decorative sheet 1 laminated on at least one surface of the base material 9 are provided.
As a result, it is possible to provide the decorative material 10 capable of suppressing a decrease in concealability even when formed using biomass-derived polyethylene, which is a plant-derived material.

The decorative materials of Examples 1 to 7 and the decorative materials of Comparative Examples 1 to 3 will be described below with reference to the tenth embodiment.

(Example 1)
After applying corona discharge treatment to one side of the base material, a pattern layer printed with urethane-based printing ink and a surface protective layer mainly composed of an acrylic resin composition are formed on one side of the base material. They were laminated in this order. Further, after the other surface of the substrate was subjected to corona discharge treatment, a primer layer (thickness: 1 to 2 [μm]) made of a polyester urethane resin was formed on the other surface of the substrate. Thus, a decorative sheet of Example 1 (total thickness: 110 [μm]) was obtained. The biomass degree of the decorative sheet is 70%. On the primer layer side of the decorative sheet, MDF (Medium density fiberboard) is applied using, for example, an adhesive BA-10L manufactured by Eva Japan Coating Resin Co., Ltd. and a curing agent BA-11B manufactured by Japan Coating Resin Co., Ltd. A decorative material can be obtained by laminating them together.
In Example 1, the substrate is formed of a resin composition containing biomass-derived high-density polyethylene ("Green polyethylene" manufactured by Braskem) and biomass-derived low-density polyethylene, and an inorganic material is added to the colored substrate. A layer (thickness: 100 [μm]) was used. Calcium carbonate and titanium oxide were blended as inorganic substances so that the specific gravity of the colored substrate layer was 1.1. This resin was subjected to Ruder lamination to obtain a colored substrate layer. The biomass degree of the colored substrate layer thus formed is 70%.

(Example 2)
A decorative sheet was obtained in the same manner as in Example 1, except that titanium oxide was blended as an inorganic substance so that the specific gravity of the colored base material layer was 0.97.

(Example 3)
A decorative sheet was obtained in the same manner as in Example 1, except that titanium oxide was blended as an inorganic substance so that the specific gravity of the colored base material layer was 1.5.

(Example 4)
A decorative sheet was obtained in the same manner as in Example 1, except that silica was added as an inorganic substance so that the specific gravity of the colored base material layer was 1.0.

(Example 5)
A decorative sheet of Example 5 was obtained in the same manner as in Example 1, except that the colored base material was formed from a resin composition containing biomass-derived high-density polyethylene and fossil fuel-derived low-density polyethylene.

(Example 6)
A decorative sheet was obtained in the same manner as in Example 1, except that the total thickness of the decorative sheet was 45 [μm].

(Example 7)
A decorative sheet was obtained in the same manner as in Example 1, except that the total thickness of the decorative sheet was 210 [μm].

(Comparative example 1)
A decorative sheet was obtained in the same manner as in Example 1, except that calcium carbonate and titanium oxide were blended as inorganic substances so that the specific gravity of the colored base material layer was 0.96.

(Comparative example 2)
A decorative sheet was obtained in the same manner as in Example 1, except that calcium carbonate was blended as an inorganic substance so that the specific gravity of the colored substrate layer was 0.95.

(Comparative Example 3)
A decorative sheet was obtained in the same manner as in Example 1, except that calcium carbonate and titanium oxide were blended as inorganic substances so that the specific gravity of the colored base material layer was 1.6.

(Performance evaluation, evaluation results)
For the decorative sheets of Examples 1 to 7 and the decorative sheets of Comparative Examples 1 to 3, respectively, "concealability", "productivity of colored thermoplastic resin layer (colored base layer)", "printability", "Processing suitability" was evaluated. As the evaluation method, the method described below was used.

<Concealability>
The decorative sheet was subjected to a hiding property test described in JIS6921 Wallpaper.
Judgment was made according to the criteria for the concealability of JIS6921, and grade 4 was graded as “⊚”, grade 3 as “◯”, grade 2 as “Δ”, and grade 1 as “x”.

<Productivity of Colored Thermoplastic Resin Layer>
Regarding the decorative sheet, the degree of defects such as film-forming property such as surface condition, presence or absence of fish eyes, presence or absence of thickness unevenness, and the like was visually evaluated. A case where there was almost no defect was rated as "⊚", a case where there was a defect but had no effect on production was rated as "◯", and a case where there was a defect that affected production was rated as "x". When the number of defective spots was about 1 to 2 per square meter, it was judged as "good".

<Printability>
For the decorative sheet, the presence or absence of poor ink adhesion, the presence or absence of thermal wrinkles during drying, and the like were visually evaluated. "◎" indicates that there is no inferiority to current decorative sheet printability; bottom.

<Processing suitability>
Regarding the decorative sheet, it was visually judged whether or not abnormalities such as cracks were observed when wrapping was performed. A case where no abnormality could be confirmed was rated as "○", a case where a partial abnormality was confirmed as "△", and a case where overall abnormality was confirmed as "x".

Table 1 shows the results of evaluating various performances using the method described above. The decorative sheets of Examples 1 to 7 exhibited substantially excellent performance in all evaluation tests. In other words, it was confirmed that, in terms of concealability, productivity and physical properties, curing effects similar to those of current decorative sheets can be obtained. On the other hand, the decorative sheets of Comparative Examples 1 to 3 exhibited insufficient performance in at least some of the evaluation tests.

DESCRIPTION OF SYMBOLS 1... Decorative sheet, 2... Colored base material layer, 3... Pattern layer, 4... Adhesive layer, 5... Transparent resin layer, 6... Surface protection layer, 7... Uneven part, 8... Primer layer, 9... Base material, 10 …Cosmetic materials

Claims (27)

A colored substrate layer, an adhesive layer, and a transparent thermoplastic resin layer are provided in this order,
The colored substrate layer and the transparent thermoplastic resin layer are each a resin layer formed of a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin,
The transparent thermoplastic resin layer contains the biomass-derived olefin, has a density within the range of 0.92 g/cm ³ or more and 0.99 g/cm ³ or less, and a thickness within the range of 55 μm or more and 150 μm or less. and, as the biomass-derived polyolefin, a biomass-derived high-density polyethylene and a biomass-derived low-density polyethylene are blended in a range of 100:0 to 20:80,
A nucleating agent is added to the resin composition forming the transparent thermoplastic resin layer,
The colored base material layer contains the biomass-derived olefin, has a density within the range of 0.92 g/cm ³ or more and 1.12 g/cm ³ or less, and has a thickness within the range of 51 μm or more and 120 μm or less. death,
A decorative sheet provided with a primer layer laminated on the other surface of the colored base layer and formed using a polyester urethane resin. 2. The decorative sheet according to claim 1, wherein the colored substrate layer contains biomass-derived high-density polyethylene and biomass-derived low-density polyethylene as the biomass-derived polyolefin. 1. The colored base material layer contains biomass-derived high-density polyethylene and low-density polyethylene as the biomass-derived polyolefin, and has a biomass content of 10% or more and 90% or less. Item 2. The decorative sheet according to item 2 . 4. The decorative sheet according to any one of claims 1 to 3 , wherein d2>d1 is satisfied, where d1 is the density of the transparent thermoplastic resin layer and d2 is the density of the colored base layer. 5. The decorative sheet according to any one of claims 1 to 4 , wherein t2≦t1 is satisfied, where t1 is the thickness of the transparent thermoplastic resin layer and t2 is the thickness of the colored base layer. . A colored substrate layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are provided in this order,
The colored substrate layer and the transparent thermoplastic resin layer are resin layers each formed of a resin composition containing a biomass-derived polyolefin,
The transparent thermoplastic resin layer contains the biomass-derived polyolefin, has a density within the range of 0.92 g/cm ³ or more and 0.99 g/cm ³ or less, and a thickness within the range of 55 μm or more and 150 μm or less. and, as the biomass-derived polyolefin, a biomass-derived high-density polyethylene and a biomass-derived low-density polyethylene are blended in a range of 100:0 to 20:80,
A nucleating agent is added to the resin composition forming the transparent thermoplastic resin layer,
The surface protective layer is a decorative sheet containing a biomass-derived component. The surface protective layer is a resin layer formed of urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate,
7. The decorative sheet according to claim 6 , wherein at least one of said polyol, said isocyanate compound and said hydroxy(meth)acrylate contains a biomass-derived component. 8. The decorative sheet according to claim 7 , wherein the polyol is a polyester polyol containing a biomass-derived component, a polyether polyol containing a biomass-derived component, or a polycarbonate polyol containing a biomass-derived component. The polyester polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid containing a fossil fuel-derived component, or contains a polyfunctional alcohol containing a fossil fuel-derived component and a biomass-derived component. 9. The decorative sheet according to claim 8 , which is a reaction product with a polyfunctional carboxylic acid. The polyether polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate containing a fossil fuel-derived component, or contains a polyfunctional alcohol containing a fossil fuel-derived component and a biomass-derived component. 9. The decorative sheet according to claim 8 , which is a reaction product with a polyfunctional isocyanate. The polycarbonate polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a biomass-derived component. The decorative sheet according to claim 8 , which is a reactant. The decorative sheet according to any one of claims 7 to 11 , wherein the isocyanate compound is an isocyanate compound containing a biomass-derived component. A colored substrate layer, a pattern layer, an adhesive layer, and a transparent thermoplastic resin layer are provided in this order,
The colored substrate layer and the transparent thermoplastic resin layer are each a resin layer formed of a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin,
The transparent thermoplastic resin layer contains 5% by mass or more of the biomass-derived olefin, has a density within the range of 0.92 g/cm ³ or more and 0.99 g/cm ³ or less, and is within the range of 55 μm or more and 150 μm or less. and as the biomass-derived polyolefin, biomass-derived high-density polyethylene and biomass-derived low-density polyethylene are blended in the range of 100: 0 to 20: 80,
A nucleating agent is added to the resin composition forming the transparent thermoplastic resin layer,
The colored base material layer contains 5% by mass or more of the biomass-derived olefin and has a density within the range of 0.92 g/cm ³ or more and 1.12 g/cm ³ or less,
The pattern layer is a decorative sheet containing a colorant and a biomass-derived component. The pattern layer is a resin layer containing urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate,
14. The decorative sheet according to claim 13 , wherein at least one of the polyol, the isocyanate compound, and the hydroxy(meth)acrylate contains a biomass-derived component. 15. The decorative sheet according to claim 14 , wherein the polyol is a polyester polyol containing a biomass-derived component, a polyether polyol containing a biomass-derived component, or a polycarbonate polyol containing a biomass-derived component. The polyester polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid containing a fossil fuel-derived component, or contains a polyfunctional alcohol containing a fossil fuel-derived component and a biomass-derived component. 16. The decorative sheet according to claim 15 , which is a reaction product with a polyfunctional carboxylic acid. The polyether polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate containing a fossil fuel-derived component, or contains a polyfunctional alcohol containing a fossil fuel-derived component and a biomass-derived component. 16. The decorative sheet according to claim 15 , which is a reaction product with a polyfunctional isocyanate. The polycarbonate polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a biomass-derived component. The decorative sheet according to claim 15 , which is a reactant. 19. The decorative sheet according to any one of claims 14 to 18 , wherein the isocyanate compound is an isocyanate compound containing a biomass-derived component. A colored substrate layer, a pattern layer, an adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are provided in this order,
The colored substrate layer and the transparent thermoplastic resin layer are each a resin layer formed of a resin composition containing a biomass-derived polyolefin obtained by polymerizing a monomer containing a biomass-derived olefin,
The transparent thermoplastic resin layer contains 5% by mass or more of the biomass-derived olefin, has a density within the range of 0.92 g/cm ³ or more and 0.99 g/cm ³ or less, and is within the range of 55 μm or more and 150 μm or less. and as the biomass-derived polyolefin, biomass-derived high-density polyethylene and biomass-derived low-density polyethylene are blended in the range of 100: 0 to 20: 80,
A nucleating agent is added to the resin composition forming the transparent thermoplastic resin layer,
The colored base material layer contains 5% by mass or more of the biomass-derived olefin and has a density within the range of 0.92 g/cm ³ or more and 1.12 g/cm ³ or less,
The pattern layer contains a coloring agent and a biomass-derived component,
The surface protective layer is a decorative sheet containing a biomass-derived component. The pattern layer is a resin layer containing urethane (meth)acrylate, which is a resin composition containing at least a polyol, an isocyanate compound, and a hydroxy (meth)acrylate,
The surface protective layer is a resin layer formed of the urethane (meth)acrylate,
21. The decorative sheet according to claim 20 , wherein at least one of the polyol, the isocyanate compound, and the hydroxy(meth)acrylate contained in the urethane (meth)acrylate contains a biomass-derived component. 22. The decorative sheet according to claim 21 , wherein the polyol is a polyester polyol containing a biomass-derived component, a polyether polyol containing a biomass-derived component, or a polycarbonate polyol containing a biomass-derived component. The polyester polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional carboxylic acid containing a fossil fuel-derived component, or contains a polyfunctional alcohol containing a fossil fuel-derived component and a biomass-derived component. 23. The decorative sheet according to claim 22 , which is a reaction product with a polyfunctional carboxylic acid. The polyether polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a polyfunctional isocyanate containing a fossil fuel-derived component, or contains a polyfunctional alcohol containing a fossil fuel-derived component and a biomass-derived component. 23. The decorative sheet according to claim 22 , which is a reaction product with a polyfunctional isocyanate. The polycarbonate polyol is a reaction product of a polyfunctional alcohol containing a biomass-derived component and a carbonate containing a fossil fuel-derived component, or a reaction product of a polyfunctional alcohol containing a fossil fuel-derived component and a carbonate containing a biomass-derived component. 23. The decorative sheet according to claim 22 , which is a reactant. 26. The decorative sheet according to any one of claims 21 to 25 , wherein the isocyanate compound is an isocyanate compound containing a biomass-derived component. a substrate;
A decorative material comprising: the decorative sheet according to any one of claims 1 to 26 laminated on at least one surface of the base material.

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