JP2020163576A - Decorative material - Google Patents

Abstract

To provide a decorative material made from a polyvinyl chloride resin having suppressed discoloration due to desalination reaction while maintaining excellent processability of vinyl chloride.SOLUTION: The decorative material has a vinyl chloride substrate 10 layer having thereon a surface resin layer 20, wherein the surface resin layer 20 includes (i) a vinyl chloride resin and a chlorine-free resin, or, (ii) a copolymer of vinyl chloride and a chlorine-free compound.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative material.

As a surface decorative material used for the floor surface of furniture and houses, a decorative material made of laminated vinyl chloride resin sheets is used.
The decorative material made of vinyl chloride resin is a heat-melt laminating method called doubling, in which a vinyl chloride base material layer as a base material and a transparent vinyl chloride resin sheet arranged on the surface side of the base material are bonded together. Is formed.

The doubling type decorative material made of vinyl chloride resin can be given sufficient strength by two vinyl chloride resin sheets, is inexpensive, has excellent workability and laminating strength, and is excellent peculiar to vinyl chloride resin. Since it has flame retardancy, it is widely used as a decorative material for decorating the interior and exterior materials of buildings such as floor materials and wall materials and the surface of furniture and the like.
As the doubling type decorative material made of vinyl chloride resin, for example, Patent Documents 1 and 2 have been proposed.

Japanese Unexamined Patent Publication No. 2000-127306 Japanese Unexamined Patent Publication No. 2008-973

However, in the doubling type vinyl chloride resin decorative materials of Patent Documents 1 and 2, the transparent vinyl chloride resin sheet on the surface side is discolored with time due to the desalting reaction of the vinyl chloride resin, and the design is deteriorated. There was 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, it is considered that the above problem can be solved by using an acrylic resin sheet as the resin sheet on the front surface side as in claim 3 of Japanese Patent Application No. 2017-190955 filed by the present applicant.
However, in the case of the configuration of claim 3 of Japanese Patent Application No. 2017-190955, the processability is significantly 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 decreases, and it becomes easy to break during processing.

As a result of diligent research, the present inventors have completed a decorative material made of vinyl chloride resin, which suppresses discoloration due to desalting reaction while maintaining excellent processability 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 base material layer, wherein the surface resin layer contains at least one of the following (i) and (ii).
(I) Vinyl chloride resin and chlorine-free resin (ii) Copolymer of vinyl chloride monomer and chlorine-free monomer

According to the present invention, it is possible to provide a decorative material made of vinyl chloride resin, which can suppress discoloration due to desalting reaction and improve designability over a long period of time while maintaining excellent processability of vinyl chloride. ..

It is sectional drawing which shows one Embodiment of the decorative material of this invention.

[Cosmetic material]
The decorative material of the present invention has a surface resin layer on a vinyl chloride base material layer, and the surface resin layer contains at least one of the following (i) and (ii).
(I) Vinyl chloride resin and chlorine-free resin (ii) Copolymer of vinyl chloride monomer and chlorine-free monomer

FIG. 1 is a cross-sectional view showing an embodiment of the decorative material 100 of the present invention.
The decorative material 100 of FIG. 1 has a surface resin layer 20 on the vinyl chloride base material 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. Further, the decorative material 100 of FIG. 1 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 to be formed as needed, and has a role of imparting sufficient strength to the decorative material by laminating with the vinyl chloride base material layer described later.

The surface resin layer needs to contain at least one of the following (i) and (ii).
(I) Vinyl chloride resin and chlorine-free resin (ii) Copolymer of vinyl chloride monomer and chlorine-free monomer

By including at least one of the above (i) and (ii) in the surface resin layer, a decorative material capable of suppressing discoloration of the surface resin layer due to the desalting reaction while maintaining excellent processability of vinyl chloride can be obtained. be able to. Further, when the surface resin layer contains at least one of the above (i) and (ii), the amount of the plasticizer added described later can be reduced, and the problem due to the bleed-out of the plasticizer (deterioration of the appearance of the decorative material, It is possible to suppress deterioration of the physical properties of the decorative material).

Examples of the vinyl chloride resin (i) mentioned above include homopolymers of vinyl chloride monomers.
The average degree of polymerization of the vinyl chloride resin is preferably 500 to 4000, more preferably 700 to 3900, and even more preferably 1000 to 3800. When the average degree of polymerization is within the above range, the balance between mechanical strength and processability (formability) can be easily improved.
In the present specification, the average degree of polymerization is the 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, polyester resins are preferable because they can easily maintain the processability of vinyl chloride resins and can easily reduce the amount of plasticizer added, which will be described later. Further, the (meth) acrylic resin is preferable because it has excellent weather resistance. The (meth) acrylic resin means both a methacrylic resin and an acrylic resin.

When the surface resin layer contains (i) vinyl chloride resin and chlorine-free resin, the content of the chlorine-free resin is 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, 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 added, which will be described later.
Further, by setting the content to 30 parts by mass or less, it is possible to easily suppress that the physical properties are significantly different from the vinyl chloride base material layer described later, and the processability of the decorative material is lowered. Can be easily suppressed.

The average degree of polymerization of the copolymer of (ii) is preferably 500 to 4000, more preferably 700 to 3900, and even more preferably 1000 to 3800. When the average degree of polymerization is within the above range, the balance between mechanical strength and processability (formability) can be easily improved.

Examples of the chlorine-free monomer constituting the copolymer of (ii) above include one or more selected from (meth) acrylic monomer and styrene monomer. Among these, the styrene monomer is preferable because it is easy to maintain the processability of the vinyl chloride resin, it is easy to reduce the amount of the plasticizer added, which will be described later, and it is 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 of (i) or the copolymer of (ii), a higher desalting reaction suppressing effect can be expected.
As the vinyl chloride stabilizer, one or more of metals such as barium, zinc, calcium and cadmium can be used as long as they do not interfere with the effects of the present invention; one or more of the metals. Metal soaps containing cadmium; organotin compounds; and the like. Of these, barium and zinc alone or in combination are preferred.
The vinyl chloride stabilizer can be contained in the surface resin layer in an appropriate amount as long as the effect of the present invention is not impaired.

When the surface resin layer contains (ii) a copolymer of a vinyl chloride monomer and a chlorine-free monomer, the copolymer weight is equal to 100 parts by mass of the content of the structural unit derived from the vinyl chloride monomer in the copolymer. The content of the structural unit derived from the chlorine-free monomer in the coalescence is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, and further 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 added, which will be described later.
Further, by setting the content to 30 parts by mass or less, it is possible to easily suppress that the physical properties are significantly different from the vinyl chloride base material layer described later, and the processability of the decorative material is lowered. Can be easily suppressed.

<< Plasticizer >>
The surface resin layer may contain a plasticizer in order to improve processability.
The plasticizer is not particularly limited as long as it is compatible with the vinyl chloride resin. For example, dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (Plasticizer) DIDP), phthalic acid-based plasticizers such as diundecyl phthalate (DUP); adipic acid-based plasticizers such as dibutyl adipate; phosphoric acid-based plasticizers such as tributyl phosphate, tricredil phosphate, triphenyl phosphate; Trimerit Trimeritic acid-based plasticizers such as tributyl acid and trioctyl trimellitic acid; various known polyester-based plasticizers such as adipic acid-based polyester; citric acid esters such as acetyltributylcitrate and acetyltrioctylcitrate; and the like. .. 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 even more preferable.
A normal soft vinyl chloride resin sheet contains a plasticizer exceeding 20% by mass, but as described above, since the surface resin layer contains a component other than vinyl chloride, the content of the plasticizer can be suppressed and plasticizer is used. The problem caused by the bleed-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.
As the light stabilizer, a hindered amine-based light stabilizer is preferable, for example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl-4-piperidinyl (meth). Aacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyl oshiki-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.
The light stabilizer can be contained in an appropriate amount in the surface resin layer as long as the effect of the present invention is not impaired.

The surface resin layer may be colorless and transparent, or may be colored with a colorant. Further, the surface resin layer may be colored transparent or opaque.
When a pattern layer is formed between the vinyl chloride base material and the surface resin layer, the surface resin layer is preferably colorless and transparent or colored and transparent, and more preferably colorless and transparent.
The type and content of the colorant added to the surface resin layer can be based on the type and content of the colorant added to the vinyl chloride base material layer described later.

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

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

<< Physical properties of surface resin layer >>
For the surface resin layer, referring to JIS K6732, the elongation at the breaking point at a test speed of 50 mm / min is preferably 50% or more, and more preferably 100% or more.
For the surface resin layer, referring to JIS K6732, the tensile elastic modulus at a test speed of 50 mm / min is preferably 200 to 3000 MPa, more preferably 500 to 2500 MPa.

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

Examples of the vinyl chloride resin contained in the vinyl chloride base material layer include a homopolymer of a vinyl chloride monomer and a copolymer of a vinyl chloride monomer and another monomer.
Since the vinyl chloride base material layer is located on the back side of the decorative material, it does not easily affect the design even if the color changes due to the desalting reaction. 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 the vinyl chloride monomer. From the same viewpoint, it is preferable that the resin component constituting the vinyl chloride base material layer does not substantially contain a resin other than the vinyl chloride resin. The term "substantially free" means that it is 1% by mass or less of the total resin component of the vinyl chloride base material layer, preferably 0.1% by mass or less, and more preferably 0.01% by mass or less. 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 colorant. Further, the vinyl chloride base material layer may be colored transparent or opaque.
The vinyl chloride base material layer may adopt the above-mentioned color, but is preferably opaque in color from the viewpoint of hiding the color of the adherend. Further, by making the vinyl chloride base material layer colored and opaque, it is possible to make the discoloration of the vinyl chloride base material layer due to the desalting reaction less noticeable.
In order to make the vinyl chloride base material opaque, the vinyl chloride base material preferably contains a vinyl chloride resin and a colorant.

Examples of the colorant include white pigments such as titanium oxide, inorganic pigments such as iron black, chrome yellow, petals, cadmium red, ultramarine blue, and cobalt blue; and organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue. Dyes; metal pigments made of scaly foil pieces such as aluminum, silver, and brass; colorants such as titanium dioxide-coated mica and pearl pigments made of scaly foil pieces such as basic lead carbonate.
Among these, a white pigment such as titanium oxide, which easily hides the color of the adherend and does not easily impair the hue of the pattern layer, is preferable.

The content of the colorant is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and further preferably 5 parts by mass or more with respect to 100 parts by mass of the resin constituting the vinyl chloride base material layer. The upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, still 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 similar to 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, and more preferably 15% by mass or more and 40% by mass or less of the total solid content of the surface resin layer. ..

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

<< Physical properties of vinyl chloride base material >>
For the vinyl chloride base material layer, referring to JIS K6732, the elongation at the breaking point at a test speed of 50 mm / min is preferably 50% or more, and more preferably 100% or more.
For the vinyl chloride base material layer, referring to JIS K6732, the tensile elastic modulus at a test speed of 50 mm / min is preferably 200 to 3000 MPa, more preferably 500 to 2500 MPa.

When the break point elongation of the surface resin layer is S1 and the break point elongation of the vinyl chloride base material layer is S2, S1 / S2 is preferably 0.5 to 2.0, preferably 0.7 to 1.5. Is more preferable. By setting S1 / S2 in the above range, the processability can be improved.
Further, when the tensile elastic modulus of the surface resin layer is E1 and the tensile elastic modulus of the vinyl chloride base material layer is E2, E1 / E2 is preferably 0.5 to 2.0, and 0.7 to 1 It is more preferably .5. By setting E1 / E2 in the above range, the processability can be improved.

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

The pattern layer may be formed in the entire in-plane of the decorative material or may be formed in a part of the in-plane of the decorative material when the decorative material is viewed in a plan view. The pattern layer can be formed by printing, for example. 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 cyan, magenta, yellow, and black process colors and white, and also by multicolor printing with special colors, which is performed by preparing plates of the individual colors that make up the pattern. Can be formed.
The pattern of the pattern layer includes wood grain, cork tone, fiber tone, stone grain tone, letters, numbers, figures, symbols, landscapes, people, animals, characters, etc., as long as it is a pattern used in normal printing. There are no particular restrictions.

The ink used for forming the pattern layer (ink for forming the pattern layer) is a binder resin mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, or the like. Is used.
The binder resin is not particularly limited. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin. , Petroleum resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fibrin derivative, rubber resin and the like. These resins can be used alone or in admixture 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, and even 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 in the above range.

<Protective coat layer>
The decorative material preferably has a protective coat layer on the surface resin layer for the purpose of improving scratch resistance, adjusting gloss, and the like.

The protective coat layer preferably contains a cured product of a resin composition containing a curable resin.
As the curable resin, in addition to a thermosetting resin such as a two-component curable resin, an ionization radiation curable resin or the like is preferably used, and a combination of a plurality of these types, for example, an ionization radiation curable resin and a thermosetting resin. It may be 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.
As the curable resin, an ionizing radiation curable resin is preferable from the viewpoint of increasing the crosslink density of the resin constituting the protective coat layer and obtaining surface characteristics such as better scratch resistance and weather resistance, and it is easy to handle. From the viewpoint of the above, an electron beam curable resin is 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 crosslinked and cured by irradiation with ionizing radiation, and a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group is preferably mentioned. Be done. Further, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, ultraviolet rays (UV) or electron beams (EB) are used. Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays are also included.
Specifically, the ionizing radiation curable resin can be appropriately selected and used from the polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth) acrylate-based 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 the polyfunctional (meth) acrylate monomer include a (meth) acrylate monomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group. An acrylate monomer having an acryloyl group is preferable from the viewpoint of obtaining surface properties such as better scratch resistance and weather resistance.
From the viewpoint of obtaining surface properties such as better 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 as follows. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

Examples of the polymerizable oligomer include (meth) acrylate oligomers having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional groups. For example, urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer, acrylic (meth) acrylate oligomer and the like can be mentioned.
Further, as the polymerizable oligomer, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group on the side chain of the polybutadiene oligomer, and a silicone (meth) acrylate-based oligomer having a polysiloxane bond on the main chain. In molecules such as aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resins having many reactive groups in small molecules, novolak type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. There are oligomers and the like having cationically polymerizable functional groups.

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

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

As the ionizing radiation curable resin, a monofunctional (meth) acrylate can be appropriately used in combination with the above-mentioned polyfunctional (meth) acrylate or the like for the purpose of reducing the viscosity thereof. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

The ionizing radiation curable resin preferably contains a polymerizable oligomer from the viewpoint of improving surface properties such as scratch resistance and weather resistance. 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, further preferably 95% by mass or more, still more preferably 100% by mass.

The curable resin composition constituting the protective coat layer preferably contains an ultraviolet absorber. Since the protective coat layer contains the ultraviolet absorber, the ultraviolet absorber is stably retained in the protective coat layer, so that excellent weather resistance can be obtained even in a harsh environment.
Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and the like, which are exemplified as ultraviolet absorbers that can be contained in the colored substrate. Among these, benzophenone-based ultraviolet absorbers are used. 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-based light stabilizer is preferable, and a hindered amine-based light stabilizer exemplified as a light stabilizer that can be used for a coloring substrate can be used. From the viewpoint of weather resistance, decanedioic acid (sebacic acid) Derived hindered amine light stabilizers are preferred.

The content of the ultraviolet absorber in the protective coat layer is preferably 0.1 part by mass or more, more preferably 0.2 parts by mass or more, and more preferably 0.3, with respect to 100 parts by mass of the curable resin constituting the protective coat layer. More than parts by mass is more preferable, and more than 0.5 parts by mass is even more preferable. The upper limit is preferably 20 parts by mass or less, more preferably 10 parts by mass or less.
The content of the light stabilizer in the protective coat layer is preferably 0.1 part by mass or more, more preferably 0.5 part 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, further preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less. When the contents of the ultraviolet absorber and the light stabilizer in the protective coat layer are within the above ranges, an excellent addition effect can be obtained without bleeding out.

The thickness of the protective coat layer is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, from the viewpoint of improving surface characteristics such as scratch resistance and weather resistance. Further, 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, still more preferably 8 μm or less.

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

<Embossing>
The decorative material may have embossing from the surface resin layer side to the vinyl chloride base material layer side.
Examples of the method of embossing the decorative material include an embossing method by heating and pressurizing. The embossing method by heating and pressurizing is a method in which the decorative material is heated and softened, pressed by an embossing plate to form an uneven pattern on the embossing plate, cooled, and fixed.
The embossed pattern includes a wood grain pattern, a stone grain pattern, a cloth pattern, a satin finish, a sand grain, a hairline, and a perforated groove.

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

<Use of decorative materials>
The decorative material of the present invention can be used as it is, as a laminated body bonded to an adherend, or by subjecting the decorative material or the laminated body to a predetermined molding process or the like for various purposes.
For various purposes, it is laminated on a flat plate of various materials, a plate material such as a curved plate, or a substrate such as a sheet (or film), and is used as a building material for interior and exterior, for example, a cabinet for furniture and kitchen products, various counters, and a desk. , Doors and other residential building materials.

Examples of the adherend include wood single boards made of various woods such as cedar, cypress, pine, and lauan, wood plywood, particle boards, wood fiber boards such as MDF (medium density fiberboard), and three-dimensional shaped articles. Wood members used as, etc .; Plates and steel plates such as iron and aluminum, three-dimensional articles, or metal members used as sheets, etc .; Ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, ALC (lightweight cellular concrete) ) Ceramic members used as plate materials such as non-ceramic ceramic materials such as plates and three-dimensional shaped articles; polyolefin resins such as acrylic resin, polyester resin, polystyrene resin, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin , Phenolic resin, vinyl chloride resin, cellulose resin, plate materials such as rubber, three-dimensional shaped articles, resin members used as sheets and the like. In addition, these members can be used alone or in combination of two or more.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.
1. 1. Evaluation 1-1. Discoloration (color difference before and after desalting reaction (ΔE))
A single-layer film composed of only the surface resin layer used in the decorative materials of Examples and Comparative Examples was prepared. The monolayer film was irradiated with an electron beam (pressurized voltage: 165 KeV, 3Mrad (30 kGy)) and then heated in an oven at 60 ° C. for 2 weeks to carry out a desalting reaction promotion test. The L ^* value, a ^* value, and b ^* value of the Lab color system before and after the desalting reaction promotion test were measured, and the color difference (ΔE) was calculated.

1-2. Processability With reference to JIS K6732, the elongation at break point (%) at 25 ° C. of the decorative materials obtained in Examples and Comparative Examples was measured at a test speed of 50 mm / min. The one having a breaking point elongation of 120% or more was designated as "A", the one having a breaking point elongation of 80% or more and less than 120% was designated as "B", and the one having a breaking point elongation of less than 80% was designated as "C".

2. Materials The following films 1 to 4 were prepared as the base material 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, break point elongation: 180%, tensile modulus: 1400 MPa)
2: Transparent vinyl chloride film containing polyester resin (thickness: 100 μm, elongation at break point: 150%, tensile elastic modulus: 2000 MPa, plasticizer content: 10% by mass) (polyester resin with respect to 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 elastic modulus: 1200 MPa, plasticizer content: 10% by mass)
4: Transparent acrylic film (thickness: 50 μm, elongation at break: 40%, tensile modulus: 1400 MPa)

3. 3. Preparation of decorative material [Example 1]
On the vinyl chloride base material layer (the film 1 above), a pattern layer consisting of a wood grain pattern having a thickness of 3 μm was formed on the entire surface by gravure printing.
Next, the surface resin layer (the film 2) was superposed on the pattern layer, and the surface resin layer (the film 2) was heat-laminated on the pattern layer using a thermal roll machine.
Next, a urethane acrylate-based ionizing radiation-curable resin composition was gravure-coated on the surface resin layer (the film 2), and then irradiated with an electron beam under the conditions of 165 keV and 3 Mrad (30 kGy). A protective coat layer (thickness 5 μm) was formed by cross-linking and curing the coating film.
Next, embossing was performed from the protective coat layer side to obtain a decorative sheet of Example 1. In the embossing process, a wood grain conduit pattern having a depth of about 70 μm was provided.

[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 the desalting reaction while maintaining the excellent processability of vinyl chloride.

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

Claims (8)

A decorative material having a surface resin layer on a vinyl chloride base material layer, wherein the surface resin layer contains at least one of the following (i) and (ii).
(I) Vinyl chloride resin and chlorine-free resin (ii) Copolymer of vinyl chloride monomer and chlorine-free monomer The decorative material according to claim 1, wherein the surface resin layer contains (i) a vinyl chloride resin and a chlorine-free resin, and contains a polyester-based resin as the chlorine-free resin. The surface resin layer contains (i) vinyl chloride resin and chlorine-free resin, and the content of the chlorine-free resin is 1 to 30 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. , The decorative material according to claim 1. The decorative material according to claim 1, wherein the surface resin layer contains (ii) a copolymer of a vinyl chloride monomer and a chlorine-free monomer, and contains a styrene monomer as the chlorine-free monomer. The surface resin layer contains (ii) a copolymer of a vinyl chloride monomer and a chlorine-free monomer, and the content of a structural unit derived from the vinyl chloride monomer in the copolymer is 100 parts by mass. The decorative material according to claim 1, wherein the content of the structural unit derived from the chlorine-free monomer in the copolymer is 1 to 30 parts by mass. The decorative material according to any one of claims 1 to 5, wherein at least one of the vinyl chloride base material layer and the surface resin layer contains a plasticizer. The decorative material according to any one of claims 1 to 6, further comprising a pattern layer. The decorative material according to any one of claims 1 to 7, which has a protective coat layer on the surface resin layer.