WO2020203954A1

WO2020203954A1 - Decorative material and resin composition for forming surface protective layer

Info

Publication number: WO2020203954A1
Application number: PCT/JP2020/014497
Authority: WO
Inventors: 古田　哲; 脩後藤; 真友子小紫; 孝遠藤; 俊之坂井
Original assignee: 大日本印刷株式会社
Priority date: 2019-03-29
Filing date: 2020-03-30
Publication date: 2020-10-08
Also published as: JPWO2020203954A1

Abstract

Provided are a decorative material having superior weather resistance and a resin composition for forming a surface protective layer. The decorative material includes at least a base material and a surface protective layer on an outermost surface. The surface protective layer contains an ultraviolet absorbing agent. The content of the ultraviolet absorbing agent relative to 100 parts by mass of resin that forms the surface protective layer is 1-10 parts by mass inclusive. The content of an ultraviolet absorbing agent having a melting point of 90℃ or higher relative to the total amount of the ultraviolet absorbing agent is greater than or equal to 45 mass%.

Description

Decorative material and resin composition for forming the surface protective layer

The present invention relates to a decorative material and a resin composition for forming the surface protective layer.

Interior members of buildings such as walls, ceilings, floors, exterior members such as exterior walls, roofs, eaves ceilings, fences, gates, various doors such as window frames, entrance doors, handrails, skirts, surrounding edges, window frames , Door frames, fittings such as malls or building members, general furniture such as stools, shelves, desks, kitchen furniture such as dining tables and sinks, or surface veneers such as cabinets for light electrical products and OA equipment are common. Therefore, various members such as a resin member, a wood member, and a metal member are used as adherends, and a decorative material is attached to these adherends, or the decorative material is used as it is. As such a decorative material, a decorative material having a structure having a surface protective layer on a base material, for example, a sheet-shaped decorative material (also referred to as a “decorative sheet”) or the like is used.

When the decorative material is used for outdoor use, problems related to weather resistance such as change in color tone and deterioration of resin will occur due to the influence of ultraviolet rays due to wind and rain and sunlight. Further, even if it is used indoors, the same problem as that of outdoor use occurs in the use exposed to sunlight near a window or the like. As a method for improving the weather resistance of a decorative sheet used in such an application, it is common to add an ultraviolet absorber as a weather resistant agent into the surface protective layer of the decorative material.

However, there is a problem that the ultraviolet absorber tends to bleed out from the surface protective layer over time. When the UV absorber bleeds out, the appearance of the surface of the decorative material is spoiled, such as stickiness, and the bleed-out UV absorber is gradually lost due to outflow due to rain, etc., and the UV absorber in the surface protective layer over time. As the concentration decreases, there arises a problem that the weather resistance decreases. Under such circumstances, in order to eliminate the bleed-out of the ultraviolet absorber, for example, an electron beam curable resin containing an electron beam reaction type ultraviolet absorber selected from a specific benzotriazole compound or the like is used as a main component. A decorative sheet having a cured layer of resin has been proposed (for example, Patent Document 1). According to the decorative sheet described in Patent Document 1, the problem of bleed-out of the ultraviolet absorber can be solved.

Japanese Unexamined Patent Publication No. 2000-117905

By the way, in recent years, decorative materials for outdoor use have come to be used under more severe temperature conditions such that the surface temperature of the decorative materials reaches about 70 ° C as the average temperature rises due to the influence of global warming. Therefore, conventional cosmetic materials cannot cope with it, and the progress of deterioration tends to accelerate year by year. Therefore, it can be said that the conventional design concept itself for suppressing the occurrence of bleed-out of the ultraviolet absorber is appropriate, but it is necessary to review the means for realizing this.

The present invention has been made under such circumstances, and an object of the present invention is to provide a decorative material having excellent weather resistance and a resin composition for forming a surface protective layer.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by the invention relating to the decorative material having the following constitution and the resin composition for forming the surface protective layer.

1. 1. A decorative material having at least a surface protective layer on the base material and the outermost surface.
The surface protective layer contains an ultraviolet absorber and
The content of the ultraviolet absorber with respect to 100 parts by mass of the resin forming the surface protective layer is 1 part by mass or more and 10 parts by mass or less.
The content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more with respect to the total amount of the ultraviolet absorber.
Cosmetic material.
2. The decorative material according to 1 above, wherein the ultraviolet absorber having a melting point of 90 ° C. or higher has a hydroxyphenyltriazine structure.
3. 3. The decorative material according to 1 or 2 above, wherein the ultraviolet absorbers contained in the surface protective layer all have a hydroxyphenyltriazine structure.
4. The decorative material according to any one of 1 to 3 above, wherein the surface protective layer is a cured product of a curable resin composition containing a curable resin and an ultraviolet absorber.
5. The decorative material according to any one of 1 to 4 above, wherein the surface protective layer further contains a light stabilizer.
6. The decorative material according to any one of 1 to 5 above, further comprising a decorative layer, an adhesive layer, a resin layer and a primer layer in this order from the base material side between the base material and the surface protective layer.
7. The decorative material according to any one of 1 to 6 above, further comprising an adherend via an adhesive layer on a surface of the base material opposite to the surface having the surface protective layer.
8. JIS Z0208: 1976 moisture permeability is not more than 0.75g ^/ m 2 · 24h or more 45g ^/ m 2 · 24h, which is measured in accordance with moisture permeability test method (cup method) for moisture-proof packaging material as defined in the above The decorative material according to any one of 1 to 6.
9. It contains a resin constituting the surface protective layer and an ultraviolet absorber containing an ultraviolet absorber having a melting point of 90 ° C. or higher, and the content of the ultraviolet absorber with respect to 100 parts by mass of the resin is 1 part by mass or more and 10 parts by mass or less. A resin composition for forming a surface protective layer, wherein the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more with respect to the total amount of the ultraviolet absorber.

According to the present invention, it is possible to provide a decorative material having excellent weather resistance and a resin composition for forming a surface protective layer.

It is a schematic cross-sectional view which shows one Embodiment of the decorative material of this invention. It is a schematic cross-sectional view which shows one Embodiment of the decorative material of this invention. It is a schematic cross-sectional view which shows one Embodiment of the decorative material of this invention.

[Cosmetic material]
Hereinafter, the decorative material of the present invention will be described. In addition, in this specification, the numerical values relating to "greater than or equal to", "less than or equal to" and "..." relating to the description of the numerical range are numerical values that can be arbitrarily combined, and the numerical values of Examples are numerical values that can be used for the upper and lower limits of the numerical range. Is.

The decorative material of the present invention is a decorative material having at least a surface protective layer on the base material and the outermost surface, and the surface protective layer contains an ultraviolet absorber, and the surface protective layer contains 100 parts by mass of the resin forming the surface protective layer. The content of the ultraviolet absorber is 1 part by mass or more and 10 parts by mass or less, and the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more with respect to the total amount of the ultraviolet absorber. It is a thing. By forming the surface protective layer constituting the decorative material of the present invention as a layer containing an ultraviolet absorber having a melting point of 90 ° C. or higher at the above-mentioned predetermined content, the decorative material is subjected to a harsh environment, especially under harsh temperature conditions. Even when used, bleed-out of the UV absorber is suppressed and excellent weather resistance can be obtained.

Regarding the fact that the bleed-out of the UV absorber is likely to occur under harsh temperature conditions, the mechanism of the bleed-out is not clear, but the UV absorber liquefies due to the temperature rise of the cosmetic material and leaks from the surface protective layer. It is speculated that this may occur. When the UV absorber liquefies, it becomes easier to bleed out from the surface protective layer, and as the occurrence of bleed-out progresses, the amount of UV absorber held by the cosmetic material itself decreases, and the weather resistance deteriorates. Conceivable. Furthermore, even if the liquefied UV absorber stays in the surface protective layer, once the temperature condition at which the cosmetic material is used falls below the melting point of the UV absorber, it liquefies once and the neighboring UV absorbers aggregate. Since it hardens in the state, it exists in a lump form in the surface protective layer, and the good dispersed state of the ultraviolet absorber in the surface protective layer is lost, resulting in a decrease in weather resistance.

The temperature conditions that the cosmetic material is exposed to during use rise and fall repeatedly throughout the day, and as a result, the UV absorber liquefies, bleeds out, partially agglomerates, and this coagulates. The cycle of being present in a lump is repeated, and as a result of bleeding out, the ultraviolet absorber that has come out from the inside of the cosmetic material to the outermost surface of the cosmetic material is washed away by the rain and gradually disappears from the surface of the cosmetic material. It is considered that the weather resistance is lowered by the amount of the disappeared ultraviolet absorber, and the progress of deterioration of the cosmetic material is further promoted. The decorative material of the present invention further suppresses the bleed-out of the ultraviolet absorber and exhibits excellent weather resistance even in such a usage environment.

The configuration of the decorative material of the present invention will be described with reference to FIGS. 1 and 2.
FIG. 1 is a schematic cross-sectional view showing the layer structure of the decorative material of the present invention, showing that the decorative material 10 of the present invention has a base material 1 and a surface protective layer 2.
Further, FIG. 2 is a schematic cross-sectional view showing one aspect of a preferable layer structure of the decorative material of the present invention, in which the base material 1 and the surface protective layer 2 provided on the outermost surface are sequentially arranged from the base material side. It is shown that it has a decorative layer 3 composed of a fully colored layer 31 and a pattern layer 32, an adhesive layer A4, a resin layer 5, and a primer layer 6.
Hereinafter, each layer constituting the decorative material of the present invention will be described in more detail.

(Base material 1)
As the base material, those usually used as a base material for decorative materials can be adopted without limitation, and for example, a base material made of paper, non-woven fabric or woven fabric, resin, wood, metal, non-metal inorganic material or the like is typical. Listed in. The thickness of the base material is also not particularly limited, and a film, sheet, or plate-like form can be appropriately used as desired, but usually, the film or sheet is about 20 to 200 μm, and the plate is 500 μm or more. A film of about 10 cm is used.

Examples of the paper base material include kraft paper, titanium paper, linter paper, sulfate paper, glassin paper, parchment paper, resin impregnated paper, thin paper, Japanese paper and the like. The base material of the non-woven fabric or woven fabric is composed of, for example, inorganic fibers such as glass fiber, alumina fiber, silica fiber and carbon fiber, and organic fiber of various synthetic resins such as polyester resin, acrylic resin, polyethylene resin and polypropylene resin. Examples thereof include non-woven fabrics or woven fabrics, and base materials such as composites thereof.

Examples of the resin include polypropylene, polyethylene, polyolefin-based thermoplastic elastomers, polyolefin resins such as ionomer, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid. Polypolymers, polyester resins such as polyester thermoplastic elastomers, polymethyl (meth) acrylates, polybutyl (meth) acrylates, methyl (meth) acrylate-butyl (meth) acrylate copolymers and other acrylic resins, polyester resins, polycarbonate resins , Acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as “ABS resin”), a resin base material made of a thermoplastic resin such as a vinyl chloride resin can be mentioned.
In the specification of the present application, for example, the notations such as "(meth) acrylate" and "(meth) acrylic acid" are "acrylate or methacrylic acid (or methacrylate)" and "acrylic acid or methacrylic acid (or), respectively. Methacrylic acid) ”is an abbreviation that means.

Examples of the wood include a wood base material made of wood of various tree species such as cedar, cypress, pine, oak, lauan, teak, and rubber tree. The wood base material may be in the form of a film or sheet called a veneer, or in the form of a single plate, plywood, laminated wood, particle board, fiberboard or the like.
Examples of the metal include iron, aluminum, copper, tin, titanium, and a metal base material made of an alloy containing at least one of these metals (for example, carbon steel, stainless steel, duralumin, brass, bronze, etc.).
Examples of non-metallic inorganic materials include cement, gypsum, calcium silicate, ceramics, and various ceramics.

The base material may be colored or uncolored (transparent), and when it is colored, the mode of coloring is not particularly limited and may be transparently colored. It may be opaque coloring (concealed coloring), and these may be arbitrarily selected.

When the base material is colored, the colorants include, for example, inorganic pigments such as titanium white, antimony white, iron black, yellow lead, titanium yellow, petal pattern, cadmium red, ultramarine blue, and cobalt blue; quinacridone red, Organic pigments or dyes such as isoindolinone yellow, phthalocyanine blue, nickel-azo complex, azomethine azo black pigment, perylene black pigment; metal pigment consisting of scaly foil pieces such as aluminum and brass; titanium dioxide coated mica, basic Examples thereof include colorants such as pearl luster (pearl) pigments composed of scaly foil pieces such as lead carbonate. For example, when the surface hue of the adherend to which the decorative sheet is attached varies, it is desired to conceal the surface hue and improve the stability of the color tone of the decorative layer provided as desired, such as a white pigment. Inorganic pigments may be used.

In the case of coloring the resin, any means such as addition to the resin (kneading, kneading), formation by applying a coating film of a paint containing the resin and a colorant, and the like can be adopted. In the case of coloring paper, non-woven fabric, or woven fabric, it can be carried out by any means such as mixed extraction with pulp or fiber material, formation of a coating film, or a combination thereof.
In the case of coloring wood, it can be carried out by either dyeing with a dye, forming a coating film, or a combination thereof. In the case of coloring gold, in addition to forming a coating film, a decoloring method for forming a metal oxide film on the surface by using an anodizing method or the like can be adopted. Further, in the case of a non-metallic inorganic material, it can be carried out by either means of forming a coating film or adding it to a base material, or a combination thereof.

Additives may be added to the base material, if necessary. Examples of the additive include an inorganic filler such as calcium carbonate and clay, a flame retardant such as magnesium hydroxide, an antioxidant, a lubricant, a foaming agent, an antioxidant, an ultraviolet absorber, a light stabilizer and the like. The blending amount of the additive is not particularly limited as long as it does not impair the processing characteristics and the like, and can be appropriately set according to the required characteristics and the like.

From the viewpoint of improving the weather resistance of the cosmetic material of the present invention, it is preferable to use a weather resistant agent such as an ultraviolet absorber and a light stabilizer among the above additives.
As the ultraviolet absorber, an ultraviolet absorber generally used for cosmetic materials can be used without particular limitation, and either an organic substance or an inorganic substance can be used. For example, examples of the organic substance-based ultraviolet absorber include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, a hydroxyphenyltriazine-based ultraviolet absorber, and the like. As the light stabilizer, a light stabilizer generally used for cosmetic materials can be used without particular limitation, and examples thereof include hindered amine-based light stabilizers such as piperidinyl sebacate-based light stabilizers. Further, these ultraviolet absorbers and light stabilizers may have a reactive functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group or an allyl group in the molecule. Examples of the inorganic ultraviolet absorber include titanium dioxide, ferric oxide, zinc oxide, cerium oxide, zirconium oxide and the like having an average particle size of 380 nm or less, preferably 100 nm or less, which is the shortest wavelength of visible light. ..
These ultraviolet absorbers, weather resistant agents such as light stabilizers, and various other additives can be used alone or in combination of two or more.

In the present invention, the above-mentioned base materials can be used alone or in combination of two or more. It may be a combination of a plurality of paper base materials, a paper base material and a fiber base material, a paper base material and a resin base material, a fiber base material and a resin base material, a paper base material and a fiber base material and a resin base material. It may be a combination with a material. Further, the resin base material may be composed of either a single layer of the above resin or a plurality of layers made of the same or different resins.
In the present invention, as the base material, a resin base material is preferable among the above-mentioned base materials from the viewpoint of facilitating the moisture permeability of the decorative sheet described later within a predetermined range and improving the long-term adhesion as well as the workability. As, polypropylene, polyethylene, polyolefin-based thermoplastic elastomer, polyolefin resin such as ionomer, and vinyl chloride resin are preferable.

More specifically, the polyolefin resin includes homopolymers of olefins such as ethylene, propylene and butene; various copolymers such as block copolymers of ethylene-propylene and random copolymers; at least one of ethylene and propylene. And a copolymer with at least one other olefin such as butene, penten, hexene; a copolymer of at least one of ethylene and propylene and at least one other monomer such as vinyl acetate and vinyl alcohol; And so on.
Among the above, polyethylene-based resins containing ethylene as a constituent unit and polypropylene-based resins containing propylene as a constituent unit are preferable, and polypropylene is preferable, from the viewpoint of easily keeping the moisture permeability within a predetermined range, which will be described later, and improving construction suitability and long-term adhesion. Based resin is preferable.

More specifically, the polyethylene-based resin may be a homopolymer of ethylene, that is, polyethylene, or ethylene and other comonomer copolymerizable with ethylene (for example, propylene, 1-butene, 1-). It may be a copolymer with α-olefin such as hexene and 1-octene, vinyl acetate, vinyl alcohol, etc.). Examples of polyethylene include high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (VLDPE), and ultra-high-density polyethylene (UHMWPE). ), Cross-linked polyethylene (PEX) and the like. These polyethylene-based resins may be used alone or in combination of two or more.

The polypropylene-based resin may be a homopolymer of propylene, that is, polypropylene, or propylene and another comonomer copolymerizable with propylene (for example, ethylene, 1-butene, 1-hexene, 1-octene, etc.). Α-Olefin; vinyl acetate, vinyl alcohol, etc.) may be a copolymer. These polypropylenes may be used alone or in combination of two or more.

When a homopolymer of propylene (polypropylene) is used, the moisture permeability of the base material can be adjusted by adjusting the crystallinity. In general, the higher the crystallinity, the lower the moisture permeability of the polypropylene resin. When the above polypropylene resin having a thickness in the range of 40 μm or more and 200 μm or less is used as a base material, the crystallinity is preferably 30% or more, more preferably 40% or more, and the upper limit is preferably 80% or less. It is preferably 70% or less.
Further, when a propylene homopolymer (polypropylene) is used, the moisture permeability of the base material can be adjusted by adjusting the mass ratio of the isotactic polypropylene and the atactic polypropylene. In general, the moisture permeability of the base material can be reduced by adding the isotactic polypropylene as compared with the case where the ratio of the atactic polypropylene in the polypropylene is 100% by mass. In this case, the mass ratio of the atactic polypropylene to the isotactic polypropylene is preferably 0/100 to 20/80 in consideration of the ease of adjusting the moisture permeability.

Further, as the vinyl chloride resin, a homopolymer of a vinyl chloride monomer, that is, a polyvinyl chloride or a copolymer obtained by copolymerizing a vinyl chloride monomer and a monomer copolymerizable with the vinyl chloride monomer is also used. be able to.
Examples of monomers copolymerizable with vinyl chloride monomer include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acids such as methyl acrylate and butyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate; butyl malate and Maleic acid esters such as diethyl malate; Fumaric acid esters such as dibutyl fumarate and diethyl fumarate; Vinyl ethers such as vinyl methyl ether, vinyl butyl ether and vinyl octyl ether; Vinyl cyanide such as acrylonitrile and methacrylonitrile Olefins such as ethylene, propylene, butylene and styrene; Dienes such as isoprene and butadiene; Vinylidene halides other than vinyl chloride such as vinylidene chloride and vinyl bromide, vinyl halides; Allyl phthalates such as diallylphthalate. , Etc. can be mentioned. These monomers may be used alone or in combination of two or more.

The average degree of polymerization of the vinyl chloride resin is preferably 500 to 4000, more preferably 700 to 3900, and more preferably 1000 to 3800, from the viewpoint that the moisture permeability described later can be easily kept within a predetermined range and the long-term adhesion is improved as well as the workability. More preferred. When the average degree of polymerization is within the above range, excellent mechanical strength and moldability can also be obtained. In this specification, the average degree of polymerization is the average degree of polymerization measured in accordance with JIS K6721.

In the present embodiment, when a vinyl chloride resin is used, it is preferable to add a plasticizer from the viewpoint of easily keeping the moisture permeability within the above range, improving the long-term adhesion as well as the workability, and improving the workability. ..
The plasticizer is not particularly limited as long as it is compatible with vinyl chloride resin. For example, dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP). ), Diundesyl phthalate (DUP) and other phthalate plasticizers; dibutyl adipate and other adipic acid plasticizers; tributyl phosphate, tricredyl phosphate, triphenyl phosphate and other phosphoric acid plasticizers; trimellitic acid Trimeritic acid-based plasticizers such as tributyl 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 can be mentioned. Among them, phthalic acid-based plasticizers, adipic acid-based plasticizers, and polyester-based plasticizers are preferable from the viewpoint of improving the long-term adhesion as well as the workability and the ease of keeping the moisture permeability within the above range. , Phthalic acid-based plasticizers and polyester-based plasticizers are more preferable. In addition, these plasticizers may be used alone or in combination of two or more.

The content of the plasticizer may be appropriately adjusted and used according to the desired moisture permeability, and it cannot be said unconditionally, but usually, the additive of the plasticizer is increased and the moisture permeability of the vinyl chloride resin is increased. There is a tendency. In consideration of this point, it is preferably 15 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 25 parts by mass or more, and the upper limit is preferably 50 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin. , More preferably 45 parts by mass or less, still more preferably 35 parts by mass or less. By setting the content of the plasticizer within the above range, it becomes easy to adjust the moisture permeability to a desired range, and it is possible to improve the long-term adhesion as well as the construction suitability. Further, when the content of the plasticizer is 20 parts by mass or more, the vinyl chloride resin can be made flexible and the workability can be improved, while when it is 50 parts by mass or less, the bleed-out of the plasticizer is suppressed. , It becomes easy to stably adjust the moisture permeability to a desired range, and it is possible to improve the long-term adhesion as well as the construction suitability.

In particular, from the viewpoint of making it easier to adjust the moisture permeability to a desired range and improving the long-term adhesion as well as the workability, for example, when a phthalate ester plasticizer is used, the content thereof is relative to 100 parts by mass of the vinyl chloride resin. It is preferably 25 parts by mass or more, more preferably 30 parts by mass or more, further preferably 35 parts by mass or more, and the upper limit is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, still more preferably 40 parts by mass. It is as follows. When a polyester plasticizer is used, its content is preferably 15 parts by mass or more, more preferably 18 parts by mass or more, and further preferably 20 parts by mass or more with respect to 100 parts by mass of the vinyl chloride resin. The upper limit is preferably 35 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 25 parts by mass or less.

The shape of the base material is not particularly limited and may be appropriately selected as desired. For example, a flat plate shape, a curved surface shape, or a non-flat plate shape having corners or the like may be used. It may be. Although flat plate-shaped (also referred to as "sheet-shaped") decorative material is shown in FIGS. 1 and 2, the shape of the decorative material of the present invention is not limited to this. Considering the ease of manufacturing, use, and processing of the decorative material, the flat plate shape is preferable.
The thickness of the base material is preferably 20 μm or more, more preferably 30 μm or more, still more preferably 40 μm or more, in consideration of surface characteristics such as abrasion resistance, weather resistance, and scratch resistance, processing characteristics, and ease of handling. The upper limit is preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 150 μm or less.

The base material is physically prepared on one or both sides of the base material, such as an oxidation method or an unevenness method, in order to improve the interlayer adhesion between the base material and the other layers and to strengthen the adhesiveness with various adherends. Surface treatment such as surface treatment or chemical surface treatment can be applied.
Examples of the oxidation method include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, an ozone-ultraviolet treatment method and the like, and examples of the unevenness method include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of the base material, but in general, the corona discharge treatment method is preferably used from the viewpoints of the effect and operability of the surface treatment.
Further, in order to improve the interlayer adhesion between the base material and other layers, strengthen the adhesiveness with various adherends, etc., for example, a primer layer (“easy adhesion” described later) is applied to at least one surface of the base material. A treatment such as forming a "layer") may be performed.

(Surface protection layer 2)
The surface protective layer is a layer provided over the entire surface of the decorative material of the present invention so as to cover the base material, and is a layer that protects the decorative material of the present invention.
The surface protective layer needs to contain the ultraviolet absorber in a content of 1 part by mass or more and 10 parts by mass or less with respect to 100 mass by mass of the resin constituting the surface protective layer, and is based on the total amount of the ultraviolet absorber. The content of the ultraviolet absorber having a melting point of 90 ° C. or higher is required to be 45% by mass or higher. In the present invention, excellent weather resistance cannot be obtained unless a specific ultraviolet absorber, which is an ultraviolet absorber having a melting point of 90 ° C. or higher, is contained in the above content.

As the ultraviolet absorber used for the surface protective layer, any ultraviolet absorber having a melting point of 90 ° C. or higher can be used without particular limitation, and any organic or inorganic ultraviolet absorber can be used. ..
For example, examples of the organic-based ultraviolet absorber include an ultraviolet absorber exemplified as those that can be used for the above-mentioned base material, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a hydroxyphenyltriazine-based ultraviolet ray. Absorbents are preferred, with hydroxyphenyltriazine-based UV absorbers being preferred.
As the inorganic ultraviolet absorber, an ultraviolet absorber exemplified as being usable for the above-mentioned base material, that is, titanium dioxide having an average particle size of 380 nm or less, preferably 100 nm or less, more preferably 50 nm or less, and second oxide. Examples thereof include iron, zinc oxide, cerium oxide, and zirconium oxide.
However, an organic ultraviolet absorber is preferable from the viewpoint of the transparency of the surface protective layer, the dispersibility in the transparent protective layer, and the processability of the decorative sheet.

The hydroxyphenyltriazine-based ultraviolet absorber is an ultraviolet absorber having a hydroxyphenyltriazine structure. From the viewpoint of steric hindrance, the hydroxyphenyltriazine structure has a molecular structural property that it bleeds out from the surface protective layer and is difficult to come off, and has a melting point of 90 ° C. or higher, so that bleed-out due to liquefaction occurs. Since it is unlikely to occur and remains in a good dispersed state in the surface protective layer, excellent weather resistance can be obtained.
In the present invention, by using a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of 90 ° C. or higher, it is possible to suppress the occurrence of bleed-out due to liquefaction that may occur during the use of the decorative material and maintain excellent weather resistance. ..

The melting point of the ultraviolet absorber used for the surface protective layer is preferably 95 ° C. or higher, more preferably 100 ° C. or higher, still more preferably 100 ° C. or higher, from the viewpoint of further suppressing the occurrence of bleed-out due to liquefaction and improving weather resistance. It is 105 ° C. or higher. The upper limit is not particularly limited, but from the viewpoint of solubility in the coating solution, it is preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
In the present specification, the melting point of the ultraviolet absorber is "the temperature at which liquefaction begins". Specifically, the ultraviolet absorber is placed in a glass container and allowed to stand in an oven for 1 hour. If liquefaction started when the temperature was set to a predetermined temperature, the predetermined temperature was set as the melting point.

More specifically, as the hydroxyphenyltriazine-based ultraviolet absorber, those represented by the following general formula (1) are preferably mentioned.

In the general formula (1), R ¹¹ is a divalent organic group or a single bond, R ¹² is a monovalent organic group, an ester group represented by -C (= O) OR ¹⁵ , -OC (=). O) The acyloxy group represented by R ¹⁶ or the organoloxy group represented by —OR ¹⁷ , and R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independently hydrogen atoms or monovalents, respectively. It is an organic group, X is an oxygen atom or a single bond, and n ₁₁ and n ₁₂ are independently integers of 1 to 5. Further, when there are a plurality of R ¹³ and R ¹⁴ , they may be the same or different.

The divalent organic group R ^11, an alkylene group, an aliphatic hydrocarbon group, an alkenylene group is preferably exemplified, from the viewpoint of weather resistance, an alkylene group is more preferable. The number of carbon atoms of these aliphatic hydrocarbon groups is preferably 1 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 4 or less. The alkylene group and the alkenylene group may be linear, branched or cyclic, but linear or branched is preferable.

As the monovalent organic group of R ¹² , an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like are preferably mentioned, and an alkyl group is more preferable. The number of carbon atoms of the alkyl group is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less. The alkyl group or alkenyl group may be linear, branched or cyclic, but linear or branched is preferable, and branched is more preferable.

Examples of the monovalent organic group of R ¹³ and R ¹⁴ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and an aromatic hydrocarbon group such as an aryl group and an arylalkyl group can be used. Preferably, an aryl group is preferred.

The alkyl group of the monovalent organic group of R ¹³ and R ¹⁴ preferably has 20 or less carbon atoms, more preferably 12 or less, further preferably 4 or less, and particularly preferably 2 or less. That is, as the monovalent alkyl group of R ¹³ and R ^14, a methyl group and an ethyl group are particularly preferable. Further, in consideration of availability, a methyl group is preferable.

The number of carbon atoms of the aryl groups of R ¹³ and R ¹⁴ is preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and further preferably 10 or less. The number of carbon atoms of the arylalkyl group is preferably 7 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and further preferably 10 or less.

Examples of the monovalent organic group of R ¹⁵ , R ¹⁶ and R ¹⁷ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and an aliphatic hydrocarbon such as an alkyl group and an alkenyl group. Groups are preferred, alkyl groups are more preferred. When R ¹⁵ , R ¹⁶ and R ¹⁷ are an alkyl group or an alkenyl group, the number of carbon atoms is preferably 2 or more, more preferably 4 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, further preferably. Is 12 or less.

The groups of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ described above have substituents such as halogen atoms, hydroxyl groups, amino groups, and alkyl groups having 1 to 4 carbon atoms. May be.

Further, n ₁₁ and n ₁₂ are independently integers of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. When n ₁₁ and n ₁₂ are integers of 2 or more, the plurality of R ¹³ and R ¹⁴ may be the same or different, and are preferably the same from the viewpoint of availability.

Typical hydroxyphenyltriazine-based ultraviolet absorbers having a melting point of 90 ° C. or higher are represented by the following chemical formula (2), that is, in the above general formula (1), R ¹¹ is an ethylene group and R. It is preferably exemplified that ¹² is an acyloxy group represented by —OC (= O) R ¹⁶ (R ¹⁶ is a 3-heptyl group), and R ¹³ and R ¹⁴ are hydrogen atoms. This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercially available product (“ADEKA STUB LA-46 (product number)”, melting point: 106 ° C., manufactured by ADEKA Corporation).

Typical hydroxyphenyltriazine-based ultraviolet absorbers having a melting point of 90 ° C. or higher are represented by the following chemical formula (3), that is, in the above general formula (1), R ¹¹ is a single bond and R. It is preferably exemplified that ¹² is an isooctyl group, R ¹³ and R ¹⁴ are phenyl groups, and n ₁₁ and n ₁₂ are 1. This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercially available product (“Tinuvin 1600 (product number)”, melting point: 120 ° C., manufactured by BASF).

Typical hydroxyphenyltriazine-based ultraviolet absorbers having a melting point of 90 ° C. or higher are represented by the following chemical formula (4), that is, in the above general formula (1), R ¹¹ is a single bond and R. It is also preferable that ¹² is a hexyl group and R ¹³ and R ¹⁴ are hydrogen atoms. This hydroxyphenyltriazine-based ultraviolet absorber is available as a commercially available product (“Tinuvin 1577 (product number)”, melting point: 148 ° C., manufactured by BASF).

In the present invention, the ultraviolet absorber used for the surface protective layer has a content of the ultraviolet absorber having a melting point of 90 ° C. or higher in an amount of 45% by mass or more based on the total amount thereof. If the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is less than 45% by mass, excellent weather resistance cannot be obtained. From the viewpoint of improving weather resistance, it is preferably 55% by mass or more, more preferably 65% by mass or more, further preferably 75% by mass or more, and even more preferably 80% by mass or more. The upper limit is not particularly limited, and may be 100% by mass, that is, an ultraviolet absorber having a melting point of 90 ° C. or higher.
Further, the ultraviolet absorber having a melting point of 90 ° C. or higher may be used alone or in combination of two or more.

In the present invention, as the ultraviolet absorber that can be used for the surface protective layer, in addition to the above-mentioned ultraviolet absorber having a melting point of 90 ° C. or higher, another ultraviolet absorber, that is, an ultraviolet absorber having a melting point of less than 90 ° C. may be used. It is possible. In this case, an ultraviolet absorber that has been widely used in cosmetic materials can be used without particular limitation, and a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a hydroxyphenyltriazine-based ultraviolet absorber can be used. It can be appropriately selected and used from ultraviolet absorbers such as agents. In this case, as the other ultraviolet absorber, a hydroxyphenyltriazine-based ultraviolet absorber is preferable. That is, when an ultraviolet absorber other than an ultraviolet absorber having a melting point of 90 ° C. or higher is used in combination, it is preferable to use a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of less than 90 ° C. as the other ultraviolet absorber. It is preferable to use a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of 90 ° C. or higher and a hydroxyphenyltriazine-based ultraviolet absorber having a melting point of less than 90 ° C. in combination. The melting point of the hydroxyphenyltriazine-based ultraviolet absorber having a melting point of less than 90 ° C. is preferably 60 ° C. or higher, more preferably 65 ° C. or higher.

The content of the ultraviolet absorber contained in the surface protective layer is 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the above resin constituting the surface protective layer. If it is less than 1 part by mass, the performance as an ultraviolet absorber cannot be sufficiently obtained, while if it is more than 10 parts by mass, bleed-out is likely to occur and the strength of the surface protective layer may be lowered. From the viewpoint of improving weather resistance, the content of the ultraviolet absorber contained in the surface protective layer is preferably 2 parts by mass or more, more preferably 3 parts by mass with respect to 100 parts by mass of the above resin constituting the surface protective layer. As described above, the upper limit is preferably 8 parts by mass or less, more preferably 7 parts by mass or less, and further preferably 6 parts by mass or less. As described above, in the present invention, since the loss of the ultraviolet absorber due to bleed-out can be suppressed, excellent weather resistance can be obtained even if the amount is smaller than the amount normally blended.

The surface protective layer may be made of either a thermoplastic resin or a curable resin, and from the viewpoint of protecting the decorative material of the present invention and obtaining surface properties such as better stain resistance and abrasion resistance, the surface protective layer may be composed of either a thermoplastic resin or a curable resin. A layer made of a curable resin, more specifically, a layer made of a cured product of a curable resin is preferable. Further, the layer may be formed by using a thermoplastic resin and a curable resin in combination.

Examples of the thermoplastic resin include acrylic resin, polyester resin, unsaturated polyester resin, vinyl chloride-vinyl acetate copolymer resin, polyester urethane resin, and thermoplastic (non-crosslinked) urethane resin.

As the curable resin, a curable resin such as a thermosetting resin, a two-component curable resin, or an ionizing radiation curable resin can be used, and the tactile sensation and design can be improved by the physical uneven shape and the visual unevenness. An ionizing thermosetting resin is preferable from the viewpoint of facilitating improvement and further, from the viewpoint of improving the stain resistance and abrasion resistance of the decorative material of the present invention.
The curable resin preferably does not contain cyclohexyl (meth) acrylate as a monomer component. In other words, the surface protective layer preferably does not contain a cured product of cyclohexyl (meth) acrylate. When the curable resin contains cyclohexyl (meth) acrylate as a monomer component, the surface protective layer may become hard and the processability of the decorative material may be deteriorated, which may cause inconvenience in the use of the decorative material having the decorative material. It is possible that there is.

Examples of the thermosetting resin include acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, silicone resin and the like. A curing agent is added to the thermosetting resin as needed.
Examples of the two-component curable resin include a two-component curable urethane resin containing a polyol compound as a main component and an isocyanate compound as a curing agent, a two-component curable epoxy resin, a two-component curable urethane-modified acrylic resin, and a two-component curable polyester resin. Can be mentioned.

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. Here, "(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 protecting the decorative material and further improving the surface properties such as stain resistance and abrasion resistance.
From the same viewpoint as this, 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 or less. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

Examples of such polymerizable monomers include bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate; trimethylol. Propanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Trifunctional or higher (meth) acrylates such as isocyanuric acid-modified tri (meth) acrylates; are preferred.

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, polycaprolactone urethane (meth). ) Acrylate oligomers, polycaprolactone diol urethane (meth) acrylate and the like.
As the polymerizable oligomer, urethane (meth) acrylate oligomer is preferable. That is, the surface protective layer preferably contains a cured product of urethane (meth) acrylate oligomer. The ratio of the cured product of the urethane (meth) acrylate oligomer to the total amount of the resin component contained in the surface protective layer is preferably 60% by mass or more, more preferably 80% by mass or more, and 90% by mass. The above is more preferable, and 100% by mass is even more preferable.
Urethane (meth) acrylate oligomers are obtained, for example, by reacting polyols and organic diisocyanates with hydroxy (meth) acrylates.
From the viewpoint of toughness and flexibility, the urethane (meth) acrylate oligomer preferably has 1 to 6 carbon atoms of the alkylene group derived from the polyol as a raw material, and more preferably 2 to 4 carbon atoms.

From the viewpoint of protecting the decorative material and further improving the surface properties such as stain resistance and abrasion resistance, the number of functional groups of these polymerizable oligomers is preferably 2 or more, and the upper limit is preferably 8 or less. It is preferably 6 or less, more preferably 4 or less, and particularly preferably 3 or less.
From the same viewpoint as this, the weight average molecular weight is preferably 500 or more, more preferably 1,000 or more, and the upper limit is preferably 80,000 or less, more preferably 50,000 or less. As used herein, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.

If desired, the surface protective layer may contain additives other than the above-mentioned UV absorbers, such as weatherproofing agents such as light stabilizers, UV shielding agents, abrasion resistance improving agents, and polymerizations, as long as the object of the present invention is not impaired. Prohibition agents, cross-linking agents, UV absorbers, antistatic agents, adhesive improvers, leveling agents, thixo-imparting agents, coupling agents, plasticizers, defoamers, fillers, blocking inhibitors, lubricants, solvents, etc. Can be added. Above all, it is preferable to contain a weather resistant agent such as a light stabilizer.

The light stabilizer may be appropriately selected from the light stabilizers exemplified as those that can be used for the base material, and the hindered amine-based light stabilizer exemplified as the one that can be preferably used is 4-benzoyloxy-. 2,2,6,6-tetramethylpiperidine, 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. Be done.
Among these, 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- Hindered amine-based photostabilizer derived from decanedic acid (sebacic acid) such as 4-piperidinyl) sebacate, hindered amine having a reactive functional group such as 1,2,2,6,6-pentamethyl-4-piperidinyl (meth) acrylate A light stabilizer is preferable.
Further, among the above, a hindered amine-based light stabilizer having a (meth) acryloyl group and a light stabilizer having a reactive functional group such as a vinyl group or an allyl group other than the (meth) acryloyl group suppress bleed-out. It is more preferable because it is easy to do.

The thickness of the surface protective layer is preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, from the viewpoint of protecting the decorative material of the present invention and obtaining more excellent weather resistance. The upper limit is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 8 μm or less.

The decorative material of the present invention may further have at least one layer selected from a decorative layer, an adhesive layer A, a resin layer and a primer layer, depending on the desired performance. These layers are usually provided between the above-mentioned base material and the surface protection layer, and it is preferable to have all the above-mentioned layers in consideration of the improvement of weather resistance and the improvement of design. Further, from the same viewpoint as this, as shown in FIG. 2, the decorative material of the present invention further comprises a decorative layer, an adhesive layer A, and a resin between the base material and the surface protective layer from the base material side. It is preferable to have the layer and the primer layer in this order, that is, the decorative material of the present invention preferably has the base material, the decorative layer, the adhesive layer A, the resin layer, the primer layer and the surface protective layer in this order.
Hereinafter, these layers will be described.

(Decorative layer 3)
The decorative material of the present invention can have a decorative layer. The decorative layer is a layer that imparts a design such as a color or a pattern to the decorative material of the present invention to improve the design.
In the decorative material of the present invention, the decorative layer may be a layer composed of only the fully colored layer 31 provided between the base material and the surface protective layer and provided so as to cover the entire surface thereof. It may be a layer composed of only a pattern layer 32 provided so as to form a pattern so as to cover a part thereof, or a fully colored layer 31 and a pattern layer 32 are combined as shown in FIG. It may be a layer. From the viewpoint of expressing higher design, the decorative layer is preferably a layer composed of a pattern layer and a fully colored layer. In this case, the decorative material of the present invention preferably has a base material, a fully colored layer, and a pattern layer in this order, and the pattern layer may be one layer or two or more layers.

The pattern given by the decorative layer may be selected as desired without any particular limitation. For example, a stone imitating the surface of a rock such as a wood grain pattern, a marble pattern (for example, a travertin marble pattern), or a cliff surface of a granite plate. Mesh pattern, cloth pattern imitating cloth grain or cloth-like pattern, leather (leather grain) pattern expressing leather grain, tiled pattern, brickwork pattern, hairline, perforated groove, satin finish, grain, letters, Examples include symbols, geometric patterns, and other patterns such as parquet and patchwork that combine these. Further, as a pattern in which these are combined, for example, an artificial stone in which crushed stone of a stone material such as marble is mixed with white cement, hardened, and polished to finish like marble, that is, a pattern like so-called artificial marble can be mentioned.
Although the demands of consumers for designs change depending on the fashion and the like, the wood grain pattern is preferable as the pattern of the decorative material of the present invention because the wood grain pattern is still popular. The wood grain pattern includes a grain pattern, a board pattern, a heather pattern, a wood grain pattern, and the like, but any of them may be used.

A resin composition containing at least a binder resin and a colorant such as a pigment and a dye is preferably used for forming the decorative layer, and other components used as desired, such as a matting agent, an extender pigment, and a stable material. An appropriate mixture of an agent, an ultraviolet absorber, a light stabilizer, a solvent and the like can be used. That is, the decorative layer is a layer containing at least a binder resin and a colorant such as a pigment and a dye, and is also a layer that can contain the above-mentioned components that can be used as desired.

The binder resin is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, polyester resin, alkyd resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate common weight. Resins such as coalesced resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, nitrocellulose resin (nitrated cotton), and cellulose acetate resin are preferable. Further, for example, a curable resin such as a two-component curable resin using various polyols such as acrylic polyol as a main agent and various isocyanates as a curing agent may be used. These can be used alone or in combination of two or more.

Examples of the colorants such as pigments and dyes that can be used in the decorative layer include the same colorants as the pigments and dyes that can be used for the above-mentioned base material, and among these, depending on the desired pattern. It may be selected as appropriate.

Further, in the present invention, from the viewpoint of further improving the design, the decorative layer preferably contains a matting agent among the above-mentioned other components used as desired.
Matters include inorganic fillers such as silica, clay, heavy calcium carbonate, light calcium carbonate, precipitated barium sulfate, calcium silicate, synthetic silicate, and fine silicate powder; acrylic resin, urethane resin, nylon. Examples thereof include an organic filler such as a resin, a polypropylene resin, or a urea-based resin.

Since the decorative layer contains a matting agent, the decorative layer has a lower gloss, so that it is possible to express a design having a visual unevenness due to the difference in gloss.
For example, with respect to the wood grain pattern exemplified as a preferable pattern, the wood grain pattern has a lower gloss (matte or low gloss) conduit portion, a higher gloss (glossy or high gloss) spring material portion, and a higher gloss autumn material. There is a part (shining part) and the like. In the decorative layer, a combination of a plurality of pattern layers such as a pattern layer forming a lower glossy conduit portion, a pattern layer forming a higher glossy spring material portion, and a pattern layer forming a higher gloss autumn material portion. Therefore, it is possible to form a pattern with high design. Further, in this case, for example, by not including the matting agent in the entire coloring layer or by reducing the content thereof from the pattern layer, it is possible to increase the gloss difference from the pattern layer and improve the design. Is.

The volume average particle diameter of these matting agents is preferably 0.5 to 25 μm, more preferably 1 to 15 μm, and even more preferably 3 to 10 μm.
The content of the matting agent in the decorative layer with respect to 100 parts by mass of the binder resin is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, still more preferably 2 parts by mass or more, and the upper limit is It is usually 100 parts by mass or less, preferably 50 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less. When the content of the matting agent is within the above range, the decorative layer can be visually recognized as a lower gloss layer, so that it is possible to improve the visual unevenness due to the gloss difference, and the resin composition. The coating performance is improved without the thixotropic property becoming extremely high, and as a result, the design property is improved.

The decorative layer may contain a weather resistant agent such as an ultraviolet absorber and a light stabilizer from the viewpoint of improving the weather resistance. Examples of the ultraviolet absorber and the light stabilizer include those that can be contained in the base material and the surface protective layer, and may be appropriately selected from these according to the desired performance.

The thickness of the decorative layer may be appropriately selected according to the desired pattern, preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is preferably 15 μm or less, more preferably. It is 10 μm or less, more preferably 8 μm or less.

(Resin layer)
The resin layer is a layer provided between the surface protection layer and the base material layer, and by providing the resin layer, improvement of surface characteristics such as stain resistance and abrasion resistance of the decorative material of the present invention can be expected. .. When the decorative material of the present invention has a decorative layer, the resin layer is provided between the decorative layer and the surface protective layer to provide a layer having a function of protecting the decorative layer.

As the resin constituting the resin layer, for example, polyolefin resin, polyester resin, acrylic resin, polycarbonate resin, polyurethane resin, polystyrene resin, vinyl chloride resin, vinyl acetate resin and the like are preferably mentioned. Of these, polyolefin resins and polyester resins are preferable, and polyolefin resins are even more preferable, from the viewpoint of improving surface characteristics. Examples of the polyolefin resin include resins exemplified as those that can form a base sheet, and polypropylene resin is particularly preferable.
Further, among the above, polyolefin resin and vinyl chloride resin are preferable, and polyolefin resin is more preferable, from the viewpoint of improving surface characteristics, easily keeping moisture permeability within a predetermined range, and improving workability and long-term adhesion. A polyethylene resin containing ethylene as a constituent unit, a polypropylene resin containing propylene as a constituent unit are preferable, and a polypropylene resin is preferable. These polyolefin resins and vinyl chloride resins are the same as those described above as the resin of the resin base material.

The resin layer is preferably transparent from the viewpoint of making the decorative layer more clearly visible. Here, the term "transparent" includes not only colorless and transparent but also colored transparent and translucent. When colored, the colorant preferably includes a colorant exemplified as a colorant that can be used for the above-mentioned decorative layer, and it is preferable to use a colorant having a color similar to that of the decorative layer.

The resin layer may be blended with additives, if necessary. For example, those exemplified as additives that can be blended in the above-mentioned base material and the surface protective layer, among them, ultraviolet absorbers, light stabilizers and the like. It is preferable to use a weather resistant agent. The amount of the additive added is not particularly limited and can be appropriately set according to the required characteristics and the like.

The thickness of the resin layer is preferably 10 μm or more and 150 μm or less, more preferably 30 μm or more and 120 μm or less, and further preferably 50 μm or more and 100 μm or less from the viewpoint of protecting the decorative layer and improving the surface characteristics. Further, from the viewpoint of protecting the decorative layer and obtaining excellent surface properties, it is preferable to make the decorative layer thicker than the base material.

Like the base material, the resin layer can be subjected to surface treatment such as physical surface treatment or chemical surface treatment on one or both sides thereof in order to improve the interlayer adhesion with the other layers.
Further, in order to improve the interlayer adhesion between the resin layer and the other layer, a treatment such as forming a primer layer on one side or both sides of the resin layer may be performed. This primer layer will be described later.

(Adhesive layer A)
The adhesive layer A is a layer provided between the surface protective layer and the base material layer, and when the resin layer is provided, it is preferable from the viewpoint of improving the adhesion between the resin layer and the base material or the decorative layer. It is a layer to be provided.

Examples of the adhesive used for the adhesive layer A include urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, rubber-based adhesives, etc. Among them, urethane-based adhesives are used in terms of adhesive strength. preferable. As the urethane-based adhesive, for example, an adhesive using a two-component curable urethane resin containing various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol and a curing agent such as the above-mentioned various isocyanate compounds. Can be mentioned. In addition, acrylic-polyester-vinyl acetate resin and the like are also suitable adhesives that easily develop adhesiveness by heating and can maintain adhesive strength even when used at high temperatures.

The thickness of the adhesive layer A is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and 2 μm or more and 10 μm from the viewpoint of efficiently improving the adhesion between the resin layer and the base material or the decorative layer. The following is more preferable.

(Primer layer 6)
The primer layer is a layer provided mainly for improving the interlayer adhesion of each layer constituting the decorative material of the present invention, and is also called an easy-adhesion layer. As shown in FIG. 2, for example, by providing the resin layer between the resin layer and the surface protective layer, the interlayer adhesion of these layers can be improved. FIG. 2 shows a mode in which the primer layer is provided between the decorative layer and the surface protective layer, but the present invention is not limited to this, and for example, it can be provided between the base material and the decorative layer. Further, when an adherend described later is further provided, a primer layer (also referred to as “back surface primer layer”) is provided on the surface of the base material opposite to the surface on which the surface protective layer is provided from the viewpoint of improving adhesion. You can also do it.

A resin composition containing at least a binder resin is preferably used for forming the primer layer, and other components used as desired, such as an extender pigment, a stabilizer, an ultraviolet absorber, a light stabilizer, and a solvent, are appropriately used. A mixture can be used. That is, the primer layer is a layer containing at least a binder resin, and is also a layer that can contain the above-mentioned components that can be used as desired.

As the binder resin used for forming the primer layer, the same binder resin that can be used for forming the above-mentioned decorative layer can be exemplified, and it may be appropriately selected from these as desired.

The thickness of the primer layer is preferably 0.1 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is preferably 10 μm or less, more preferably 8 μm, from the viewpoint of efficiently improving the interlayer adhesion. Below, it is more preferably 5 μm or less.

(Characteristics of decorative material)
Decorative material of the present invention, it is preferred moisture permeability is not more than 0.75g ^/ m 2 · 24h or more 45g ^/ m 2 · 24h. Here, the moisture permeability has a decorative material composed of an adhesive layer B described later and another layer other than the adherend, that is, at least a base material and a surface protective layer, preferably a decorative layer and an adhesive layer A. It is the moisture permeability of a decorative material having another layer such as a resin layer and a primer layer. By having such moisture permeability, it is further excellent in construction suitability, long-term adhesion, process suitability, and weather resistance (particularly, suppression of appearance change when exposed to ultraviolet rays in sunlight).
Specifically, by setting the moisture permeability of the decorative material within the above range, the initial adhesion strength in the construction process is improved, so that the end face of the decorative material is peeled off due to insufficient initial adhesion strength during construction. Since the occurrence of so-called springback can be suppressed, the construction efficiency is improved. On the other hand, in the case of a decorative material in which the adherend is provided via the adhesive layer B, deterioration of the adhesive layer B for mainly providing the adherend can be suppressed, so that peeling due to the deterioration can be suppressed. , Peeling does not occur even after long-term use, and long-term adhesion is improved. That is, by setting the moisture permeability of the decorative material of the present invention within a specific range, the construction suitability is improved by improving the initial adhesion strength in the construction process, and the long-term adhesion that does not cause peeling even after long-term use is improved. be able to.
The effect of long-term adhesion by setting the moisture permeability within the above range is that the content of the total ultraviolet absorber with respect to 100 parts by mass of the resin in the surface protective layer is 1 part by mass or more and 10 parts by mass or less, and ultraviolet rays. It is obtained when the content of the ultraviolet absorber having a melting point of 90 ° C. or higher with respect to the total amount of the absorbent is 45% by mass or more. In other words, when the surface protective layer does not have the above-mentioned structure, even if the moisture permeability is in the above range, the base material and the adhesive layer are affected by the action of ultraviolet rays due to the breakage of the molecular chain of the resin or the photochemical reaction. It deteriorates, which causes a decrease in mechanical strength in the vicinity of the adhesive interface and an increase in moisture permeability of the decorative material, so that long-term adhesion cannot be improved.
On the other hand, even if the total content of the UV absorber contained in the surface protective layer and the content ratio of the UV absorber having a melting point of 90 ° C. or higher to the total amount of the UV absorber are optimized within the above range, the moisture permeability of the decorative material If There exceeding 45g / m 2 · ^24h, in addition to reduction in long-term adhesion, tends to decrease weathering resistance of changes in appearance. The reasons for this are "as the moisture permeability of the cosmetic material increases, the permeability of the UV absorber contained in the cosmetic material also increases, so that the UV absorber tends to bleed out" and "for a long period of time." It is conceivable that the amount of reduction of the ultraviolet absorber in the cosmetic material increases with outdoor exposure, and the durability of the cosmetic material to ultraviolet rays gradually decreases. "

To be more specific for a more obtained effect to the moisture permeability in the above range, the moisture permeability is at 0.75g / m 2 · ^24h or more, makeup via the adhesive layer was stuck adherend When the material is used, the occurrence of poor adhesion due to poor curing of the adhesive used for the adhesive layer is suppressed, so that the initial adhesive strength is improved and the workability is improved. The effect of improving the initial adhesion strength is that the decorative sheet is formed through an adhesive layer formed of a urethane resin-based adhesive such as a moisture-curable and hot-melt type urethane resin-based adhesive, which requires moisture especially during initial bonding. It appears prominently when attached to an adherend. On the other hand, when the moisture permeability is less than 45g / m 2 · ^24h, during prolonged use, moisture in the air, weather, further deterioration of the substrate due to the influence of ultraviolet by solar radiation, the adhesive used on the adhesive layer Since deterioration due to hydrolysis of the above can be suppressed, peeling between the decorative sheet and the adherend is less likely to occur, and long-term adhesion that does not cause peeling even after long-term use is improved. The effect of improving the long-term adhesion strength is obtained through an adhesive layer formed of a urethane resin-based adhesive such as a moisture-curable and hot-melt type urethane resin, which has a property of being deteriorated by hydrolysis due to moisture. Is remarkably expressed when is attached to the adherend. Therefore, by setting the moisture permeability within the above range, the decorative sheet of the present invention can simultaneously improve the construction suitability due to the high initial adhesion strength in the construction process and the long-term adhesion that does not cause peeling even after long-term use. it can.

From the viewpoint of improving the long-term adhesion with construction suitability, moisture permeability, 1.2g ^/ m 2 · 24h or more, more preferably 1.5g ^/ m 2 · 24h, more preferably 2.5g ^/ m 2 · 24h or more , even more preferably at 4.5g ^/ m 2 · 24h or more, preferably 40g ^/ m 2 · 24h or less as the upper limit, more preferably 35g ^/ m 2 · 24h or less, even more preferably not more than 30g ^/ m 2 · 24h , even more preferably at most 20g ^/ m 2 · 24h.
In the present invention, as described above, the moisture permeability can be adjusted mainly by the type of the material constituting the base material, and when having the resin layer, the type of the material constituting the resin layer and the like.

In the present invention, by having the above-mentioned predetermined range of moisture permeability, a surface protective layer is provided at least on the base material and the outermost surface, and preferably, a decorative layer and an adhesive layer A are provided between the base material and the surface protective layer. The initial adhesive strength of the adhesive layer B that adheres the decorative material having the resin layer and the primer layer in order to the adherend is improved, and due to moisture in the air from the surface protective layer side of the decorative material, wind and rain, etc. It suppresses the prevention of deterioration. Therefore, when the decorative material of the present invention has the adherend 11 and the adhesive layer B12, it goes without saying that the effect obtained by having the moisture permeability in the predetermined range is taken into consideration, but the transparency in the predetermined range is taken into consideration. Humidity means the moisture permeability of the decorative material having a layer structure excluding the adherend 11 and the adhesive layer B12.

(Manufacturing method of decorative material)
Regarding the method for producing a decorative material of the present invention, which is one of the preferred embodiments of the decorative material of the present invention, a base material, a decorative layer composed of a fully colored layer and a pattern layer, and an adhesive layer shown in FIG. The manufacturing method thereof will be described by taking as an example a decorative material having A, a resin layer, a primer layer and a surface protective layer in this order.

The decorative material of the present invention provides, for example, a step of providing a fully colored layer and a pattern layer on a base material to form a decorative layer, a step of forming a resin layer, a step of forming a primer layer, and a step of coating the primer layer. As described above, it can be produced by sequentially going through the steps of forming the surface protective layer.

In the step of forming the decorative layer, first, the resin composition used for forming the entire colored layer is applied onto the base material to form the desired overall colored layer, and then the resin composition used for forming the pattern layer is applied. To form a pattern layer. The resin composition is applied by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, or a comma coating method, preferably a gravure printing method.

When the surface treatment is applied to the base material, it may be performed before forming the entire colored layer, and when the primer layer is provided, it may be performed before forming the entire colored layer. Further, when the back surface primer layer is provided on the surface (back surface) opposite to the surface on which the decorative layer of the base material is provided, it may be provided before or after the formation of the decorative layer.

In the step of providing the resin layer, after the decorative layer is formed, an adhesive is applied onto the decorative layer as needed to form the adhesive layer A, and then the resin composition constituting the resin layer is extruded and laminated. , Dry lamination, wet lamination, thermal lamination, etc., can be bonded and pressure-bonded to form a laminate.

Next, in the step of forming the primer layer so as to cover the resin layer, the resin composition used for forming the primer layer may be applied to the surface of the resin layer to form the primer layer, and the coating method is to apply the decorative layer. It may be appropriately selected and adopted from the method of applying the resin composition to be formed.

To form the surface protective layer, a curable resin composition containing a liquid uncured product of a curable resin, which is used for forming the surface protective layer, is applied to the entire surface of the decorative material and cured if necessary. To do.
As a method for applying the uncured resin composition containing the liquid uncured material, any of the known methods exemplified as the method for applying the resin composition of the decorative layer may be adopted.
Further, the curing method of the uncured resin composition containing the liquid uncured product of the curable resin may be selected according to the type of the curable resin contained in the uncured resin composition. For example, when the uncured resin composition is a resin composition containing a liquid uncured product of a thermosetting resin, it may be cured by performing a heat treatment according to the thermosetting resin to be used.

When an uncured resin composition containing a liquid uncured product of an ionizing radiation resin is used, the uncured resin layer formed by coating the uncured resin composition is irradiated with ionizing radiation such as an electron beam or ultraviolet rays. It may be a cured product. Here, when an electron beam is used as the ionizing radiation, the accelerating voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but the uncured resin layer can usually be cured at an accelerating voltage of about 70 to 300 kV. preferable. The irradiation dose is preferably an amount at which the crosslink density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
The electron beam source is not particularly limited, and for example, a cockloft Walton type, a bandegraft type, a resonance transformer type, an insulated core transformer type, or various electron beam accelerators such as a linear type, a dynamitron type, and a high frequency type are used. be able to.
When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. The ultraviolet source is not particularly limited, and for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or the like is used.

Further, after forming the surface protective layer, it is also possible to impart an uneven shape by heat and pressure molding with an embossed plate, if necessary. By forming the uneven shape, a tactile sensation is imparted, and the design of the decorative material of the present invention is improved. Further, for example, when a wood grain pattern is formed by a decorative layer, it is possible to express an excellent design with a high texture by synchronizing the conduit portion in the wood grain pattern with the concave and convex concave portions.

The conditions for heat and pressure molding may be appropriately adjusted according to the type of the curable resin to be used, and are not particularly limited, but usually under temperature conditions of 100 to 200 ° C., the pressure is 0.1 to 9.8 MPa. The time is from 10 seconds to 120 minutes.

(Use of decorative material)
The decorative material of the present invention is a decorative material having excellent weather resistance, and can be used for various purposes as it is, laminated on an adherend via an adhesive layer B, or subjected to a predetermined molding process or the like. Can be done.
For example, it is laminated on a flat plate of various materials, a plate material such as a curved plate, or an adherend such as a sheet (or film), and is used as an interior member or an outer wall, a roof, an eaves ceiling, a fence of a building such as a wall, a ceiling, or a floor. , Exterior materials such as gates, various doors such as window frames and entrance doors, handrails, skirts, surrounding edges, window frames, door frames, fittings such as moldings, and general members such as cabinets, shelves, desks, etc. It is suitably used as furniture, kitchen furniture such as dining tables and sinks, surface decorative boards for cabinets such as light electrical products and OA equipment, interior members or exterior members of vehicles, and the like. Further, the decorative material of the present invention is preferably used as the above-mentioned various members, especially as a member used in an environment exposed to direct sunlight.

As shown in FIG. 3, the decorative material of the present invention may have an adherend 11 via an adhesive layer B12 on a surface of the base material 1 opposite to the surface having the surface protective layer 2. .. In this case, the base material is in the form of a sheet (or film), that is, the decorative material having the base material, the surface protective layer, the decorative layer provided as needed, the adhesive layer A, the resin layer and the primer layer is a sheet. When it is in the form of (or film), it is easy to be laminated with the adherend via the adhesive layer B.
As described above, when the decorative material of the present invention has the adhesive layer B and the adherend, the moisture permeability of the decorative material of the present invention is the same as that of the adhesive layer B and the adherend. It is the moisture permeability of the decorative material having a layered structure excluding. Therefore, a decorative material having a base material, a surface protective layer, a decorative layer provided as needed, an adhesive layer A, a resin layer, and a primer layer, wherein the base material is a sheet (or a film) (“decorative sheet”). (Also referred to as)) has the above-mentioned predetermined range. Further, regarding the "decorative sheet", the decorative sheet, the adhesive layer B, and the decorative material having the adherend are also referred to as decorative members.

As the adherend, for example, a single wood board made of various kinds of wood such as cedar, cypress, pine, and lauan, a wood plywood, a particle board, a wood fiber board such as MDF (medium density fiberboard), and a three-dimensional shape article. 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 materials used for non-ceramic ceramic materials such as plates and ceramic members used as three-dimensional 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.

The adhesive used for the adhesive layer B is not particularly limited, and known adhesives can be used. For example, a moisture-curable adhesive, an anaerobic curable adhesive, a dry-curable adhesive, and a UV-curable adhesive can be used. Adhesives such as mold adhesives, heat sensitive adhesives (for example, hot melt type adhesives), and pressure sensitive adhesives are preferable. A moisture-curable adhesive and a heat-sensitive adhesive are preferable in consideration of compatibility with the decorative material of the present embodiment having a predetermined water vapor permeability, ease of handling, and the like. In particular, the heat-sensitive adhesive is preferable in that the molten liquid adhesive layer is cooled and solidified, and at the same time, the adhesive force rises to a saturated state. Further, when the moisture-curable adhesive is used in combination with the decorative material of the present embodiment, it can be exposed to an appropriate amount of moisture in the construction process, so that the initial adhesion strength of the adhesive used for the adhesive layer can be obtained. On the other hand, since it does not come into contact with excessive moisture, a decrease in adhesiveness due to deterioration due to hydrolysis is suppressed, and as a result, it becomes easy to obtain better construction suitability and long-term adhesiveness. It is also preferable in terms of ease of handling.

Examples of the resin used for the adhesive constituting the adhesive layer B include acrylic resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, and polyester. Examples thereof include resins and polyamide resins, and these can be used alone or in combination of two or more. Further, a two-component curable polyurethane-based adhesive or a polyester-based adhesive using an isocyanate compound or the like as a curing agent can also be applied.
Further, an adhesive may be used for the adhesive layer B. As the pressure-sensitive adhesive, an acrylic-based, urethane-based, silicone-based, rubber-based, or other pressure-sensitive adhesive can be appropriately selected and used.

A moisture-curable adhesive, which is one of the adhesives preferably used in the present embodiment, and which has a urethane resin resin, contains a prepolymer having an isocyanate group at the molecular terminal as an essential component. .. The prepolymer is usually a polyisocyanate prepolymer having one or more isocyanate groups at both ends of the molecule, and is in the state of a solid thermoplastic resin at room temperature. As such a polyisocyanate prepolymer, for example, a solid polyester polyol which is crystalline at room temperature is used as a polyol component, and a polyisocyanate composed of 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, or the like is used as a polyisocyanate component. Can be mentioned.

The adhesive layer B is made by applying and drying the above resin in a form that can be applied such as a solution or an emulsion by a means such as a gravure printing method, a screen printing method, or a reverse coating method using a gravure plate. Can be formed.
The thickness of the adhesive layer B is not particularly limited, but from the viewpoint of obtaining excellent adhesiveness, it is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less, and further preferably 10 μm or more and 30 μm or less.

The decorative material having an adherend can be arbitrarily cut, and the surface and the end of the wood can be arbitrarily decorated by grooving, chamfering, etc. using a cutting machine such as a router or a cutter. And various uses, for example, interior members of buildings such as walls, ceilings, floors, exterior members such as exterior walls, roofs, eaves ceilings, fences, gates, various doors such as window frames, entrance doors, etc. In addition to fittings or building members such as handrails, skirting boards, surrounding edges, window frames, door frames and moldings, general furniture such as stools, shelves and desks, kitchen furniture such as dining tables and sinks, light electrical products, OA equipment, etc. It is suitably used as a surface decorative board of a cabinet, an interior member of a vehicle, an exterior member, or the like.

[Resin composition for forming a surface protective layer]
The resin composition for forming a surface protective layer of the present embodiment contains a resin constituting the surface protective layer and an ultraviolet absorber containing an ultraviolet absorber having a melting point of 90 ° C. or higher, and the ultraviolet absorber is contained in 100 parts by mass of the resin. The resin composition is characterized in that the content is 1 part by mass or more and 10 parts by mass or less, and the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more with respect to the total amount of the ultraviolet absorber. .. Regarding the resin constituting the surface protective layer, the ultraviolet absorber containing an ultraviolet absorber having a melting point of 90 ° C. or higher, other components that can be contained, the content, etc., contained in the resin composition for forming the surface protective layer of the present embodiment. It is the same as the content described as the resin composition that can be used for forming the surface protective layer of the decorative material.

The resin composition for forming a surface protective layer of the present embodiment suppresses the bleed-out of the ultraviolet absorber and exhibits excellent weather resistance even when the decorative material is used in a harsh environment, especially under harsh temperature conditions. Can be done. In addition, excellent performance can be exhibited in terms of surface characteristics such as stain resistance and wear resistance, which are required for the surface protective layer.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.

(Measuring method)
Regarding the melting points of the UV absorbers used in Examples and Comparative Examples, the UV absorbers were placed in a glass container, allowed to stand in an oven, and liquefied when the oven was kept at a predetermined temperature for 1 hour. If so, the predetermined temperature was taken as the melting point.

(Evaluation method)
1-1. Evaluation of Weather Resistance The appearance of the decorative materials obtained in the Examples and Comparative Examples after the accelerated weather resistance test using a metal halide lamp (MWOM) was carried out for 1200 hours was visually observed from the surface protective layer side, and the decorative materials were evaluated. The appearance was visually evaluated according to the following criteria.
(Evaluation criteria)
1: No change in appearance was confirmed.
2: A slight change in appearance was confirmed, but there was no problem in practical use.
3: A large change in appearance was confirmed.
4: A remarkable change in appearance was confirmed.
1-2. Measurement of Moisture Permeability The cosmetic materials obtained in Examples and Comparative Examples were measured for moisture permeability in accordance with the moisture permeability test method (cup method) for moisture-proof packaging materials specified in JIS Z0208: 1976.
1-3. Evaluation of construction suitability The decorative materials obtained in Examples and Comparative Examples and the adherend (material: polyurethane chloride (PVC)) on a flat plate with a width of 25 mm are combined with a moisture-curable and hot-melt type urethane resin adhesive. (Polyurethane-based prepolymer having an isocyanate group in the molecule, "1308.20 (product name)", manufactured by TAKA) was melted at 120 ° C. and attached via an adhesive layer having a thickness of 50 μm, and the temperature was 23. The adhesive layer is cooled at ° C. and solidified, and left in an environment of 90 ° C. for 1 hour to prepare a sample. In a temperature environment of 25 ° C., a Tencilon universal material tester (“Tencilon RTC-” Using "1250A (product name)", manufactured by Orientec Co., Ltd., a peeling test was conducted under the conditions of tensile speed: 10 mm / min, peeling direction 90 °, and chuck distance: 30 mm, and the peeling strength was measured as the initial adhesive strength. , Evaluated according to the following criteria. If the evaluation is 2 or more, the evaluation of construction suitability is passed.
1: The peeling strength was 1.0 N / mm or more.
2: The peeling strength was 0.5 N / mm or more and less than 1.0 N / mm.
3: The peeling strength was less than 0.5 N / mm.
1-4. Evaluation of long-term adhesion The sample prepared in "1-3. Evaluation of construction suitability" above was left in a moist heat environment of 70 ° C. and 90% RH for 6 weeks, and then tested for Tensiron universal material in a temperature environment of 25 ° C. Using a machine ("Tencilon RTC-1250A (product name)", manufactured by Orientec Co., Ltd.), perform a peeling test under the conditions of tensile speed: 50 mm / min and peeling direction 90 °, measure the peeling strength, and use the following criteria. Evaluated in. If the evaluation is 2 or more, the evaluation of long-term adhesion is passed.
1: The peeling strength was 2.0 N / mm or more.
2: The peeling strength was 1.0 N / mm or more and less than 2.0 N / mm.
3: The peeling strength was less than 1.0 N / mm.
1-5. Processability When a sample is attached (laminated) in preparation in the above "1-3. Evaluation of construction suitability", the floating of the decorative material at the bent part (bending angle: 1 mmR) is visually confirmed, and the following criteria are used. evaluated. If the evaluation is 2 or more, the processing suitability is passed.
1: No floating was confirmed.
2: Floating was hardly confirmed.
3: Floating was confirmed and peeling occurred.

[Example 1]
A decorative layer is formed on one surface of a base material (colored polypropylene resin sheet having a thickness of 60 μm) subjected to double-sided corona discharge treatment using a printing ink made of a two-component curable acrylic-urethane resin, and further, the decorative layer is formed. An adhesive layer A made of a urethane resin-based adhesive having a thickness of 3 μm was formed on the adhesive layer A.
Next, the polypropylene-based resin was heated, melted and extruded on the adhesive layer A by a T-die extruder to form a transparent resin layer having a thickness of 80 μm.

After corona discharge treatment was applied to the surface of the resin layer, a composition composed of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol and hexamethylene diisocyanate were mixed on the resin layer in a mass ratio of 100: 5. The resin composition was applied and dried to form a primer layer having a thickness of 4 μm.
Next, on the primer layer, with respect to 100 parts by mass of the ionizing radiation curable resin composition composed of a trifunctional urethane acrylate oligomer having a weight average molecular weight of 4000, an ultraviolet absorber 1 (trade name: Adecastab LA-46, hydroxyphenyltriazine type) 2 parts by mass of UV absorber, ADEKA Co., Ltd., 2 parts by mass of UV absorber 2 (trade name: Tinuvin1600, hydroxyphenyltriazine-based UV absorber, manufactured by BASF), hindered amine light stabilizer (trade name: Tinuvin123) , BASF) was applied in 3 parts by mass, and an ionizing radiation curable resin composition was cured by irradiating with an electron beam to form a surface protective layer having a thickness of 5 μm. The weather resistance of the obtained decorative material was evaluated by the above method. The evaluation results are shown in Table 1.

[Examples 2 to 6]
The decorative materials of Examples 2 to 6 were prepared in the same manner as in Example 1 except that the types and amounts of the ultraviolet absorbers used in the surface protective layer were as shown in Table 1. The weather resistance of the obtained decorative material was evaluated by the above method. The evaluation results are shown in Table 1.

[Comparative Examples 1 to 5]
Comparative Examples 1 to 5 were prepared in the same manner as in Example 1 except that the types and amounts of the ultraviolet absorbers used in the surface protective layer were as shown in Table 1. The weather resistance of the obtained decorative material was evaluated by the above method. The evaluation results are shown in Table 1.

The UV absorbers in the above table are as follows.
LA-46: Trade name: ADEKA STAB LA-46, manufactured by ADEKA Corporation, hydroxyphenyltriazine-based ultraviolet absorber (compound represented by the above general formula (2)), melting point: 106 ° C.
-Tinuvin 1600: A hydroxyphenyltriazine-based ultraviolet absorber manufactured by BASF (a compound represented by the above general formula (3)), melting point: 120 ° C.
-Tinuvin 479: Made by BASF, hydroxyphenyltriazine-based UV absorber, melting point: 70 ° C.

From the results in Table 1, it was confirmed that the decorative material of the present invention has excellent weather resistance even under extremely strict conditions of conducting an accelerated weather resistance test using a metal halide lamp (MWOM) for 1200 hours.
On the other hand, the decorative materials of Comparative Examples 1 to 4 in which the content of the ultraviolet absorber having a melting point of 90 ° C. or higher with respect to the total amount of the ultraviolet absorber used in the surface protective layer is small, a hydroxyphenyltriazine-based ultraviolet absorber (Tinuvin479) is used. However, it cannot be said that it is excellent in terms of weather resistance. Further, the decorative material of Comparative Example 5 in which the content of the ultraviolet absorber in the surface protective layer is too large has a large amount of the ultraviolet absorber that can be retained in the surface protective layer even if an ultraviolet absorber having a melting point of 90 ° C. or higher is used. Due to the large amount, the cross-linking density of the surface protective layer cannot be sufficiently obtained and sufficient durability cannot be ensured, and the appearance is deteriorated due to the occurrence of bleedout, which can be the starting point of deterioration. It became something that could not be said to be excellent.
From the above results, the decorative material of the present invention has extremely excellent weather resistance under extremely severe conditions in which an accelerated weather resistance test using a metal halide lamp (MWOM) is carried out for 1200 hours even when the amount of the ultraviolet absorber used is relatively small. It was confirmed to have sex.

[Examples 7 to 10]
In Example 1, the decorative materials of Examples 7 to 10 were prepared in the same manner as in Example 1 except that the base material and the resin layer were replaced with those shown in Table 2. In Example 10, the adhesive layer A and the resin layer are not provided.
The weather resistance, construction suitability, long-term adhesion, and processing suitability of the decorative materials of Examples 7 to 10 and Reference Examples 1 and 2 described later were evaluated by the above methods. Moreover, the moisture permeability of the obtained decorative material was measured. The evaluation results and measurement results are shown in Table 2.

[Reference Examples 1 and 2]
In Example 1, the decorative materials of Reference Examples 1 and 2 were prepared in the same manner as in Example 1 except that the base material and the resin layer were replaced with those shown in Table 2. Reference Example 2 does not have the adhesive layer A and the resin layer.

The materials used for the base material and the resin layer in Table 2 and their thicknesses are as follows.
Polyolefin 1: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 80 μm, crystallinity: 70%)
Polyolefin 2: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 60 μm, crystallinity: 50%)
Polyolefin 3: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 60 μm, crystallinity: 40%)
Polyolefin 4: Polypropylene resin sheet (propylene-ethylene random copolymer (ethylene content: 4.5% by mass or less), thickness: 100 μm, crystallinity: 70%)
-PVC1: Polyvinyl chloride resin sheet (thickness: 120 μm)
It is produced by extruding a resin composition obtained by adding 38 parts by mass of a phthalate ester-based plasticizer (Undecyl phthalate (DUP)) as a plasticizer to 100 parts by mass of a polyvinyl chloride resin.
-PVC2: Polyvinyl chloride resin sheet (thickness: 120 μm)
It is produced by extruding a resin composition obtained by adding 33 parts by mass of a phthalate ester-based plasticizer (Undecyl phthalate (DUP)) as a plasticizer to 100 parts by mass of a polyvinyl chloride resin.
-Polyolefin A: Polypropylene resin (thickness: 80 μm)
-Polyolefin B: Polypropylene resin (thickness: 40 μm)
-Polyolefin C: Polypropylene resin (thickness: 100 μm)

From the results of Table 2, the decorative material of the present invention has a predetermined moisture permeability, and thus has excellent coating suitability in addition to excellent weather resistance, and the present embodiment using the decorative material. It was confirmed that the decorative member of No. 1 has excellent long-term adhesion.

Since the decorative material of the present invention has excellent weather resistance, interior members of buildings such as walls, ceilings and floors or exterior members such as outer walls, roofs, eaves ceilings, fences and gates, window frames and entrance doors In addition to various doors such as doors, handrails, skirts, surrounding edges, window frames, door frames, fittings such as moldings or building members, general furniture such as porcelains, shelves, desks, kitchen furniture such as dining tables and sinks, or light electrical products. , OA equipment and the like cabinet surface decorative board, vehicle interior member or exterior member, etc. are suitably used. Further, the decorative material of the present invention is preferably used as the above-mentioned various members, especially as a member used in an environment exposed to direct sunlight.

10: Decorative material 1: Base material 2: Surface protective layer 3: Decorative layer 31: Fully colored layer 32: Pattern layer 4: Adhesive layer A
5: Resin layer 6: Primer layer 11: Adhesive body 12: Adhesive layer B

Claims

A decorative material having at least a surface protective layer on the base material and the outermost surface.
The surface protective layer contains an ultraviolet absorber and
The content of the ultraviolet absorber with respect to 100 parts by mass of the resin forming the surface protective layer is 1 part by mass or more and 10 parts by mass or less.
The content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more with respect to the total amount of the ultraviolet absorber.
Cosmetic material.
The decorative material according to claim 1, wherein the ultraviolet absorber having a melting point of 90 ° C. or higher has a hydroxyphenyltriazine structure.
The decorative material according to claim 1 or 2, wherein all the ultraviolet absorbers contained in the surface protective layer have a hydroxyphenyltriazine structure.
The decorative material according to any one of claims 1 to 3, wherein the surface protective layer is a cured product of a curable resin composition containing a curable resin and an ultraviolet absorber.
The decorative material according to any one of claims 1 to 4, wherein the surface protective layer further contains a light stabilizer.
The decorative material according to any one of claims 1 to 5, further comprising a decorative layer, an adhesive layer A, a resin layer and a primer layer in this order from the base material side between the base material and the surface protective layer.
JIS Z0208: 1976 moisture permeability is not more than 0.75g / m 2 · 24h or more 45g / m 2 · 24h, which is measured in accordance with moisture permeability test method (cup method) for moisture-proof packaging material as defined in, wherein Item 6. The decorative material according to any one of Items 1 to 6.
The decorative material according to any one of claims 1 to 7, further comprising an adherend via an adhesive layer B on a surface of the base material opposite to the surface having the surface protective layer.
The decorative material according to claim 8, wherein the adhesive layer B is composed of a urethane-based adhesive.
The decorative material according to claim 9, wherein the urethane-based adhesive is a moisture-curable adhesive.
The decorative material according to any one of claims 8 to 10, wherein the adherend is a metal member or a resin member.
It contains a resin constituting the surface protective layer and an ultraviolet absorber containing an ultraviolet absorber having a melting point of 90 ° C. or higher, and the content of the ultraviolet absorber with respect to 100 parts by mass of the resin is 1 part by mass or more and 10 parts by mass or less. A resin composition for forming a surface protective layer, wherein the content of the ultraviolet absorber having a melting point of 90 ° C. or higher is 45% by mass or more with respect to the total amount of the ultraviolet absorber.