JP7310219B2 - decorative material - Google Patents

Description

The present invention relates to a decorative material.

BACKGROUND ART As a surface decorative material used for floor surfaces of furniture, houses, etc., a decorative material made of laminated vinyl chloride resin sheets is used.
Decorative materials made of vinyl chloride resin are made by laminating a vinyl chloride base layer as a base material and a transparent vinyl chloride resin sheet placed on the surface side of the base material using a hot-melt lamination method called doubling. formed by

The doubling-type vinyl chloride resin decorative material can provide sufficient strength with two vinyl chloride resin sheets, is inexpensive, has excellent workability and lamination strength, and has excellent properties unique to vinyl chloride resin. Due to its flame retardancy, it is widely used as a decorative material for decorating the surfaces of building interior and exterior materials such as flooring and wall materials and furniture.
For example, Patent Documents 1 and 2 have proposed doubling-type decorative materials made of vinyl chloride resin.

JP-A-2000-127306 JP-A-2008-973

However, in the doubling-type vinyl chloride resin decorative material of Patent Documents 1 and 2, the transparent vinyl chloride resin sheet on the surface side discolors over time due to the desalting reaction of the vinyl chloride resin, and the design property deteriorates. I had a problem.

In order to solve the above problem, it is conceivable to change the transparent vinyl chloride resin sheet on the surface side to another resin layer. For example, as in claim 3 of Japanese Patent Application No. 2017-190955 filed by the present applicant, if the resin sheet on the front side is an acrylic resin sheet, the above problem can be resolved.
However, in the case of the configuration of claim 3 of Japanese Patent Application No. 2017-190955, the processability is greatly reduced due to the large difference in physical properties between the vinyl chloride resin sheet and the acrylic resin sheet. Specifically, the elongation rate of the decorative material is lowered, and the decorative material is likely to break during processing.

As a result of intensive research, the present inventors have completed a decorative material made of vinyl chloride resin that suppresses discoloration due to desalting reaction while maintaining the excellent workability of vinyl chloride.
An object of the present invention is to provide the following [1].
[1] A decorative material having a surface resin layer on a vinyl chloride substrate layer, wherein the surface resin layer contains at least one of the following (i) and (ii).
(i) vinyl chloride resins and chlorine-free resins (ii) copolymers of vinyl chloride monomers and chlorine-free monomers

ADVANTAGE OF THE INVENTION According to the present invention, it is possible to provide a decorative material made of a vinyl chloride resin that can suppress discoloration due to a desalting reaction while maintaining the excellent workability of vinyl chloride, and that can have good design properties over a long period of time. .

1 is a cross-sectional view showing an embodiment of the decorative material of the present invention; FIG.

[Cosmetic materials]
The decorative material of the present invention has a surface resin layer on a vinyl chloride substrate layer, and the surface resin layer contains at least one of the following (i) and (ii).
(i) vinyl chloride resins and chlorine-free resins (ii) copolymers of vinyl chloride monomers and chlorine-free monomers

FIG. 1 is a cross-sectional view showing one embodiment of the decorative material 100 of the present invention.
A decorative material 100 of FIG. 1 has a surface resin layer 20 on a vinyl chloride base layer 10 . Further, the decorative material 100 of FIG. 1 has a pattern layer 30 between the vinyl chloride base material layer 10 and the surface resin layer 20 . The decorative material 100 of FIG. 1 also has a protective coat layer 40 on the surface resin layer 20 .

<Surface resin layer>
The surface resin layer protects the vinyl chloride base material layer and the pattern layer formed as necessary, and provides sufficient strength to the decorative material by being laminated with the vinyl chloride base material layer described later.

The surface resin layer must contain at least one of (i) and (ii) below.
(i) vinyl chloride resins and chlorine-free resins (ii) copolymers of vinyl chloride monomers and chlorine-free monomers

By including at least one of (i) and (ii) in the surface resin layer, it is possible to obtain a decorative material capable of suppressing discoloration of the surface resin layer due to desalting reaction while maintaining excellent workability of vinyl chloride. be able to. In addition, since the surface resin layer contains at least one of the above (i) and (ii), the amount of the plasticizer to be added can be reduced, and problems due to bleeding out of the plasticizer (deterioration of the appearance of the decorative material, deterioration of the physical properties of the decorative material, etc.) can be suppressed.

The vinyl chloride resin (i) above includes homopolymers of vinyl chloride monomers.
The vinyl chloride resin preferably has an average degree of polymerization of 500 to 4,000, more preferably 700 to 3,900, and even more preferably 1,000 to 3,800. When the average degree of polymerization is within the above range, the balance between mechanical strength and workability (moldability) can be easily improved.
As used herein, the average degree of polymerization is an average degree of polymerization measured according to JIS K6721.

Examples of the chlorine-free resin (i) include one or more selected from polyester resins, (meth)acrylic resins, polystyrene and urethane resins. Among these resins, polyester-based resins are preferable because they tend to maintain the processability of vinyl chloride resins and also reduce the amount of the plasticizer to be added, which will be described later. In addition, (meth)acrylic resins are preferable because of their excellent weather resistance. (Meth)acrylic resin means both methacrylic resin and acrylic resin.

When the surface resin layer (i) contains a vinyl chloride resin and a chlorine-free resin, the content of the chlorine-free resin is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. It is preferably 3 to 20 parts by mass, and even more preferably 5 to 15 parts by mass.
By setting the content to 1 part by mass or more, the desalting reaction of vinyl chloride can be easily suppressed. Further, by setting the content to 1 part by mass or more, it is possible to easily reduce the amount of the plasticizer to be added, which will be described later.
In addition, by setting the content to 30 parts by mass or less, it is possible to easily suppress a large difference in physical properties from the vinyl chloride base material layer described later, and the processability of the decorative material is reduced. can be easily suppressed.

The copolymer (ii) preferably has an average degree of polymerization of 500 to 4,000, more preferably 700 to 3,900, and still more preferably 1,000 to 3,800. When the average degree of polymerization is within the above range, the balance between mechanical strength and workability (moldability) can be easily improved.

Examples of the chlorine-free monomer constituting the copolymer (ii) include one or more selected from (meth)acrylic monomers and styrene monomers. Among these, styrene monomers are preferable because they tend to maintain processability of the vinyl chloride resin, tend to reduce the amount of the plasticizer to be added, and are excellent in hydrolysis resistance.

The surface resin layer may contain a vinyl chloride stabilizer. By combining the vinyl chloride stabilizer with the chlorine-free resin (i) or the copolymer (ii), a higher desalting reaction inhibitory effect can be expected.
Any vinyl chloride stabilizer can be used as long as it does not inhibit the effects of the present invention. One or more of metals such as barium, zinc, calcium and cadmium; metal soap containing; organotin compounds; and the like. Among these, barium and zinc are preferred alone or in combination.
The vinyl chloride stabilizer can be contained in the surface resin layer in an appropriate amount within a range that does not impair the effects of the present invention.

When the surface resin layer (ii) contains a copolymer of a vinyl chloride monomer and a chlorine-free monomer, the content of the structural unit derived from the vinyl chloride monomer in the copolymer is 100 parts by mass. The content of structural units derived from chlorine-free monomers during coalescence is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and even more preferably 5 to 15 parts by mass. .
By setting the content to 1 part by mass or more, the desalting reaction of vinyl chloride can be easily suppressed. Further, by setting the content to 1 part by mass or more, it is possible to easily reduce the amount of the plasticizer to be added, which will be described later.
In addition, by setting the content to 30 parts by mass or less, it is possible to easily suppress a large difference in physical properties from the vinyl chloride base material layer described later, and the processability of the decorative material is reduced. can be easily suppressed.

<<Plasticizer>>
The surface resin layer may contain a plasticizer in order to improve workability.
The plasticizer is not particularly limited as long as it is compatible with vinyl chloride resins. Examples include dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate ( DIDP), phthalate plasticizers such as diundecyl phthalate (DUP); adipic acid plasticizers such as dibutyl adipate; phosphoric acid plasticizers such as tributyl phosphate, tricresyl phosphate, and triphenyl phosphate; trimellitic acid-based plasticizers such as tributyl acid and trioctyl trimellitate; various known polyester-based plasticizers such as adipic acid-based polyesters; citric acid esters such as acetyltributyl citrate and acetyltrioctyl citrate; . These plasticizers may be used alone or in combination of two or more.

The content of the plasticizer in the surface resin layer is preferably 20% by mass or less, more preferably 5 to 15% by mass, and 5 to 10% by mass of the total solid content of the surface resin layer. is more preferred.
A normal soft vinyl chloride resin sheet contains more than 20% by mass of plasticizer, but as described above, since the surface resin layer contains components other than vinyl chloride, the content of plasticizer can be suppressed, Problems due to bleeding out of the agent can be suppressed.

<< light stabilizer >>
The surface resin layer may contain a light stabilizer in order to suppress the desalting reaction of vinyl chloride.
The light stabilizer is preferably a hindered amine light stabilizer, such as 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl (meth) Acrylates, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(1-octyloxy-2,2 ,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4- piperidinyl) sebacate, 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidinyl)amino]-6-(2-hydroxyethylamine)-1 ,3,5-triazine), tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis-(1,2,2,6 ,6-pentamethyl-4-piperidyl)-2-(3,5-di-t-butyl-4-hydroxy-benzyl)-2-n-butylmalonate and the like.
An appropriate amount of the light stabilizer can be contained in the surface resin layer within a range that does not impair the effects of the present invention.

The surface resin layer may be colorless and transparent, or may be colored with a coloring agent. Moreover, the coloring of the surface resin layer may be either colored transparent or colored opaque.
When the pattern layer is formed between the vinyl chloride substrate and the surface resin layer, the surface resin layer is preferably colorless and transparent or colored and transparent, more preferably colorless and transparent.
The type and content of the colorant to be added to the surface resin layer can be made according to the type and content of the colorant to be added to the vinyl chloride base material layer, which will be described later.

When the surface resin layer is colorless and transparent, the total light transmittance according to JIS K7361-1:1997 is preferably 70% or more, more preferably 80% or more.
When the surface resin layer is colorless and transparent, the haze of JIS K7136:2000 is preferably 10% or less, more preferably 6% or less.

The thickness of the surface resin layer is preferably 20 to 200 μm, more preferably 30 to 150 μm, even more preferably 40 to 100 μm.

<<Physical properties of the surface resin layer>>
Referring to JIS K6732, the surface resin layer preferably has an elongation at break of 50% or more, more preferably 100% or more, at a test speed of 50 mm/min.
The surface resin layer preferably has a tensile modulus of 200 to 3000 MPa, more preferably 500 to 2500 MPa at a test speed of 50 mm/min, referring to JIS K6732.

<Vinyl chloride base layer>
The vinyl chloride base material layer has a role of imparting sufficient strength to the decorative material by being laminated with the surface resin layer described above.
The vinyl chloride base material layer and the surface resin layer can be laminated by, for example, thermal lamination or dry lamination via an adhesive layer.

Examples of the vinyl chloride resin contained in the vinyl chloride base material layer include homopolymers of vinyl chloride monomers and copolymers of vinyl chloride monomers and other monomers.
Since the vinyl chloride base material layer is located on the back side of the decorative material, even if it is discolored by the desalting reaction, it does not easily affect the design. Therefore, from the viewpoint of processability of the decorative material, the vinyl chloride resin contained in the vinyl chloride base material layer is preferably a homopolymer of a vinyl chloride monomer. From the same point of view, it is preferable that the resin component constituting the vinyl chloride base material layer does not substantially contain resins other than vinyl chloride resin. "Substantially free" means that it is 1% by mass or less, preferably 0.1% by mass or less, more preferably 0.01% by mass or less, based on the total resin components of the vinyl chloride substrate layer, More preferably, it is 0.001% by mass or less.

The vinyl chloride base material layer may be colorless and transparent, or may be colored with a coloring agent. Moreover, the coloring of the vinyl chloride base material layer may be either colored transparent or colored opaque.
The vinyl chloride base material layer may employ the above-mentioned color, but from the viewpoint of concealing the color of the adherend, it is preferably colored and opaque. Further, by making the vinyl chloride base material layer opaque in color, it is possible to make the discoloration due to the desalting reaction of the vinyl chloride base material layer inconspicuous.
In order to make the vinyl chloride base layer colored and opaque, the vinyl chloride base layer preferably contains a vinyl chloride resin and a colorant.

Coloring agents include, for example, white pigments such as titanium oxide; inorganic pigments such as iron black, yellow lead, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; Dyes; metal pigments made of scale-like foils such as aluminum, silver and brass; colorants such as pearl luster (pearl) pigments made of scale-like foils such as titanium dioxide-coated mica and basic lead carbonate.
Among these, white pigments such as titanium oxide are preferred because they easily conceal the color of the adherend and do not easily impair the hue of the pattern layer.

The content of the coloring agent is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and even more preferably 5 parts by mass or more with respect to 100 parts by mass of the resin constituting the vinyl chloride base layer. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less.

The vinyl chloride base material layer may contain a plasticizer in order to improve processability. Examples of the plasticizer include those exemplified as the plasticizer for the surface resin layer.
The content of the plasticizer in the vinyl chloride base material layer is preferably more than 10% by mass and 50% by mass or less, more preferably 15% by mass or more and 40% by mass or less, based on the total solid content of the surface resin layer. .

The thickness of the vinyl chloride substrate layer is preferably 20 to 200 μm, more preferably 30 to 150 μm, even more preferably 40 to 100 μm.

<<Physical Properties of Vinyl Chloride Base Layer>>
The vinyl chloride substrate layer preferably has an elongation at break of 50% or more, more preferably 100% or more at a test speed of 50 mm/min, according to JIS K6732.
The vinyl chloride substrate layer preferably has a tensile modulus of 200 to 3000 MPa, more preferably 500 to 2500 MPa at a test speed of 50 mm/min, according to JIS K6732.

When the elongation at break of the surface resin layer is S1 and the elongation at break of the vinyl chloride base layer is S2, S1/S2 is preferably 0.5 to 2.0, more preferably 0.7 to 1.5. is more preferable. By setting S1/S2 within the above range, the processability can be improved.
Further, when E1 is the tensile modulus of the surface resin layer and E2 is the tensile modulus of the vinyl chloride base layer, E1/E2 is preferably 0.5 to 2.0, more preferably 0.7 to 1 0.5 is more preferred. By setting E1/E2 within the above range, processability can be improved.

<Pattern layer>
The decorative material preferably has a pattern layer in order to improve design.
The pattern layer may be formed between the vinyl chloride substrate layer and the surface resin layer, may be formed on the surface resin layer, or may be formed at the two locations described above.
From the viewpoint of easily improving the durability of the pattern layer, the pattern layer is preferably formed between the vinyl chloride base material layer and the surface resin layer.

The pattern layer may be formed on the entire surface of the decorative material when viewed from above, or may be formed on a part of the surface of the decorative material. The pattern layer can be formed, for example, by printing. The pattern layer may be a single layer as shown in FIG. 1, or may be formed from two or more layers.

The pattern layer can be formed by multicolor printing with the addition of white, process colors of cyan, magenta, yellow, and black, and also by multicolor printing with special colors, which is performed by preparing individual color plates that make up the pattern. can be formed.
The patterns in the pattern layer include woodgrain, cork, fiber, stone, letters, numbers, figures, symbols, landscapes, people, animals, and characters. There are no particular restrictions.

The ink used to form the pattern layer (ink for forming the pattern layer) is obtained by appropriately mixing a binder resin with a pigment, a coloring agent such as a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like. is used.
The binder resin is not particularly limited, and examples include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, and alkyd resins. , petroleum-based resins, ketone resins, epoxy-based resins, melamine-based resins, fluorine-based resins, silicone-based resins, cellulose derivatives, rubber-based resins, and the like. These resins can be used alone or in combination of two or more.

The thickness of the pattern layer is preferably 0.1 to 5.0 μm, preferably 0.5 to 4.5 μm, more preferably 1.0 to 4.0 μm. When the pattern layer is formed of two or more layers, the total thickness of each pattern layer is preferably within the above range.

<Protective coat layer>
The decorative material preferably has a protective coating layer on the surface resin layer for purposes such as improving scratch resistance and adjusting luster.

The protective coat layer preferably contains a cured product of a resin composition containing a curable resin.
As the curable resin, in addition to thermosetting resins such as two-component curable resins, ionizing radiation curable resins and the like are preferably used. A so-called hybrid type, in which a resin is used in combination, or a curable resin and a thermoplastic resin are used in combination, may be used.
As the curable resin, an ionizing radiation curable resin is preferable from the viewpoint of increasing the cross-linking density of the resin constituting the protective coating layer and obtaining surface properties such as superior scratch resistance and weather resistance, and is also easy to handle. From this point of view, electron beam curable resins are more preferable.

<<Ionizing radiation curable resin>>
The ionizing radiation-curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and has an ionizing radiation-curable functional group. Here, the ionizing radiation-curable functional group is a group that is cross-linked and cured by irradiation with ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as a (meth)acryloyl group, a vinyl group, and an allyl group. be done. In addition, ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.
As the ionizing radiation-curable resin, specifically, it is possible to appropriately select and use from polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation-curable resins.

As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth)acrylate monomer is particularly preferable. As used herein, "(meth)acrylate" means "acrylate or methacrylate".
Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group, Acrylate monomers having an acryloyl group are preferred from the viewpoint of obtaining surface properties such as better scratch resistance and weather resistance.
From the viewpoint of obtaining better surface properties such as scratch resistance and weather resistance, the number of functional groups is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 3. It is below. These polyfunctional (meth)acrylates may be used alone or in combination.

Polymerizable oligomers include, for example, (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least (meth)acryloyl groups as the functional groups. Examples thereof include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.
Furthermore, as polymerizable oligomers, there are also highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain. , Aminoplast resin modified aminoplast resin with many reactive groups in a small molecule (meth)acrylate oligomer, or novolac type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having cationic polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination. Urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate from the viewpoint of obtaining better surface properties such as scratch resistance and weather resistance. Acrylate oligomers and acrylic (meth)acrylate oligomers are preferred, and urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred.

From the viewpoint of obtaining better surface properties such as scratch resistance and weather resistance, the number of functional groups of these polymerizable oligomers is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and still more preferably. 4 or less, more preferably 3 or less.

The weight-average molecular weight of these polymerizable oligomers is preferably 2,500 or more, more preferably 3,000 or more, and even more preferably 3,500 or more, from the viewpoint of obtaining better surface properties such as scratch resistance and weather resistance. . Moreover, as an upper limit, 15,000 or less are preferable, 12,500 or less are more preferable, and 11,000 or less are still more preferable. Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

For the ionizing radiation-curable resin, a monofunctional (meth)acrylate can be appropriately used together with the polyfunctional (meth)acrylate and the like for the purpose of decreasing the viscosity. These monofunctional (meth)acrylates may be used alone or in combination.

From the viewpoint of improving surface properties such as scratch resistance and weather resistance, the ionizing radiation-curable resin preferably contains a polymerizable oligomer. The content of the polymerizable oligomer in the ionizing radiation-curable resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and even more preferably 100% by mass.

The curable resin composition that constitutes the protective coat layer preferably contains an ultraviolet absorber. When the protective coat layer contains the UV absorber, the UV absorber is stably retained in the protective coat layer, so that excellent weather resistance can be obtained even in severe environments.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, and triazine-based ultraviolet absorbers, which are exemplified as ultraviolet absorbers that can be contained in the colored base material. agents are preferred.

The curable resin composition constituting the protective coat layer preferably contains a light stabilizer from the viewpoint of improving weather resistance. As the light stabilizer, a hindered amine light stabilizer is preferable, and a hindered amine light stabilizer exemplified as a light stabilizer that can be used in a colored base material can be used. Preferred are hindered amine light stabilizers derived from

The content of the ultraviolet absorber in the protective coat layer is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and 0.3 parts by mass with respect to 100 parts by mass of the curable resin constituting the protective coat layer. It is more preferably at least 0.5 parts by mass, and even more preferably at least 0.5 parts by mass. Moreover, as an upper limit, 20 mass parts or less are preferable and 10 mass parts or less are more preferable.
The content of the light stabilizer in the protective coat layer is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and 1 part by mass with respect to 100 parts by mass of the curable resin constituting the protective coat layer. The above is more preferable, and 1.5 parts by mass or more is even more preferable. The upper limit is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less. When the content of the ultraviolet absorber and the light stabilizer in the protective coat layer is within the above range, excellent addition effects can be obtained without bleeding out.

From the viewpoint of improving surface properties such as scratch resistance and weather resistance, the thickness of the protective coating layer is preferably 2 µm or more, more preferably 3 µm or more, and even more preferably 4 µm or more. From the viewpoint of suppressing cracks in the protective coat layer when molding the decorative sheet, the thickness of the protective coat layer is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

<Other layers>
The decorative material may have layers other than those exemplified above. Other layers include a primer layer, an adhesive layer and an antistatic layer.

<Emboss>
The decorative material may have embossing from the surface resin layer side toward the vinyl chloride base layer side.
As a method of embossing the decorative material, there is an embossing method using heat and pressure. The embossing method by heating and pressurization is a method of heating and softening the decorative material, applying pressure with an embossing plate to shape the concave-convex pattern of the embossing plate, cooling, and fixing.
Embossed patterns include wood grain patterns, stone grain patterns, cloth patterns, satin finish, grain patterns, hairlines, and lines and grooves.

The depth of embossing is preferably 10 to 300 μm, more preferably 50 to 200 μm, depending on the thickness of the decorative material.

<Application of decorative material>
The decorative material of the present invention can be used for various purposes as it is, as a laminated body attached to an adherend, or after being subjected to a predetermined molding process or the like to the decorative material or laminated body.
Various applications include flat plates of various materials, plate materials such as curved plates, and substrates such as sheets (or films), which are laminated on substrates such as sheets (or films), building materials for interior and exterior, such as cabinets for furniture and kitchen products, top plates used for various counters and desks. , doors, and other residential building materials.

Examples of adherend materials include wood veneers made of various types of wood such as cedar, cypress, pine, and lauan, wood plywood, particle boards, wood fiber boards such as MDF (medium density fiber board), and other board materials and three-dimensional articles. Wooden members used as such; Plates and steel plates such as iron and aluminum, three-dimensional articles, or metal members used as sheets; Glass, ceramics such as ceramics, non-cement ceramic materials such as gypsum, ALC (lightweight cellular concrete ) Plate materials such as non-ceramic ceramic materials such as plates and ceramic members used as three-dimensional articles; Acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin , phenolic resins, vinyl chloride resins, cellulose resins, plate materials such as rubber, three-dimensional articles, resin members used as sheets, and the like. Moreover, these members can be used individually or in combination of multiple types.

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.
1. Evaluation 1-1. Discoloration (color difference (ΔE) before and after desalting reaction)
A single-layer film consisting of only the surface resin layer used in the decorative materials of Examples and Comparative Examples was prepared. After irradiating the single-layer film with an electron beam (applied voltage: 165 KeV, 3 Mrad (30 kGy)), it was heated in an oven at 60° C. for 2 weeks to conduct a desalting reaction acceleration test. The L ^* value, a ^* value and b ^* value of the Lab color system before and after the desalting reaction acceleration test were measured, and the color difference (ΔE) was calculated.

1-2. Processing Suitability Referring to JIS K6732, the elongation at break (%) at 25°C of the decorative materials obtained in Examples and Comparative Examples was measured at a test speed of 50 mm/min. "A" indicates that the elongation at break is 120% or more, "B" indicates that the elongation at break is 80% or more and less than 120%, and "C" indicates that the elongation at break is less than 80%.

2. Materials Films 1 to 4 below were prepared as the base layer and the surface resin layer used in the decorative materials of Examples and Comparative Examples.
1: White opaque vinyl chloride film (thickness: 120 μm, elongation at break: 180%, tensile modulus: 1400 MPa)
2: Transparent vinyl chloride film containing polyester resin (thickness: 100 μm, elongation at break: 150%, tensile modulus: 2000 MPa, plasticizer content: 10% by mass) (polyester resin for 100 parts by mass of vinyl chloride resin content is 10 parts by mass)
3: Transparent vinyl chloride film (thickness: 100 μm, elongation at break: 150%, tensile modulus: 1200 MPa, plasticizer content: 10% by mass)
4: Transparent acrylic film (thickness: 50 μm, elongation at break: 40%, tensile modulus: 1400 MPa)

3. Production of decorative material [Example 1]
A pattern layer having a wood grain pattern with a thickness of 3 μm was formed on the entire surface of the vinyl chloride base layer (film 1) by gravure printing.
Next, the surface resin layer (film 2 above) was overlaid on the pattern layer, and the surface resin layer (film 2 above) was heat-laminated on the pattern layer using a hot roll machine.
Next, after forming a coating film of a urethane acrylate-based ionizing radiation-curable resin composition on the surface resin layer (film 2 above) by gravure coating, electron beam irradiation was performed under the conditions of 165 keV and 3 Mrad (30 kGy). A protective coating layer (5 μm thick) was formed by cross-linking and curing the coating film.
Then, the decorative sheet of Example 1 was obtained by embossing from the protective coat layer side. In the embossing, a wood grain vessel pattern with a depth of about 70 μm was imparted.

[Comparative Example 1]
A decorative material of Comparative Example 1 was obtained in the same manner as in Example 1, except that the surface resin layer was changed from Film 2 to Film 3.

[Comparative Example 2]
A decorative material of Comparative Example 2 was obtained in the same manner as in Example 1, except that the surface resin layer was changed from Film 2 to Film 4.

From the results in Table 1, it can be confirmed that the decorative material of Example 1 can suppress discoloration due to desalting reaction while maintaining the excellent workability of vinyl chloride.

10: Vinyl chloride base material layer 20: Surface resin layer 30: Pattern layer 40: Protective coat layer 100: Decorative material

Claims (5)

A decorative material comprising a surface resin layer on a vinyl chloride base material layer, the surface resin layer containing the following (i ) .
(i) Polyester resin as vinyl chloride resin and chlorine-free resin The decorative material according to claim 1 , wherein the surface resin layer contains 1 to 30 parts by mass of the chlorine-free resin with respect to 100 parts by mass of the vinyl chloride resin. The decorative material according to claim 1 or 2 , wherein at least one of the vinyl chloride base layer and the surface resin layer contains a plasticizer. The decorative material according to any one of claims 1 to 3 , further comprising a pattern layer. The decorative material according to any one of claims 1 to 4 , which has a protective coating layer on the surface resin layer.