JP6977294B2 - Decorative sheet and decorative material using it - Google Patents

Description

The present invention relates to a decorative sheet and a decorative material using the same.

Interior or exterior materials for buildings such as walls, ceilings, floors, entrance doors, window frames, doors, handrails, skirting boards, surrounding edges, fittings or building materials such as malls, kitchens, furniture or light electrical products, etc. In general, metal members such as steel plates, resin members, and wood members are used as adherends for surface decorative plates of cabinets such as OA equipment, interior materials or exterior members of vehicles, and decorative sheets are used for these adherends. The one that is pasted together is used. The decorative sheet attached to the adherend has a problem that the weather resistance of the decorative sheet is lowered when it is exposed to ultraviolet rays in sunlight or illuminating rays for a long time, and the designability is impaired accordingly. .. For example, if it is used for exterior members such as entrance doors, window frames, fittings such as doors, etc. that are used in an environment exposed to direct sunlight, cracks and peeling may occur and it may not be able to withstand long-term use. there were.

In order to solve such a problem, in a decorative sheet having a base material, a pattern printing layer, a transparent resin layer, a primer layer and a surface protective layer, a triazine-based ultraviolet absorber and a light stabilizer are contained in the primer layer and the surface protective layer. A decorative sheet having improved weather resistance has been proposed (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2008-238444

However, the decorative sheet described in Patent Document 1 can maintain a certain degree of weather resistance (weather resistance up to about 600 hours using an ultra-accelerated weather resistance test device), but was used as a surface protective layer. The triazine-based ultraviolet absorber bleeds out (also referred to as bleed out migration), and it is difficult to maintain better weather resistance from the viewpoint of long-term durability. In order to improve the weather resistance, it is necessary to use a larger amount of UV absorber, but if it is used in a large amount, a bleed-out problem will occur, so the occurrence of bleed-out can be prevented and long-term weather resistance can be obtained. Has been a long-standing challenge.

The present invention has been made under such circumstances, and an object of the present invention is to provide a decorative sheet having better weather resistance and design, and a decorative material using the same.

As a result of diligent research to solve the above problems, the present inventor has decided to properly use the ultraviolet absorbers used for these resin layers when using the ultraviolet absorbers for the front surface side resin layer and the back surface side resin layer. It has been found that a decorative sheet having more excellent weather resistance and design can be obtained and the above-mentioned problems can be solved.

[1] A decorative sheet having a back surface side resin layer and a front surface side resin layer, wherein the front surface side resin layer is made of a cured product of a curable resin composition containing a metal oxide-based ultraviolet shielding agent, and the back surface side resin. A decorative sheet whose layer contains an organic UV absorber.
[2] The decorative sheet according to the above [1], which further has a base resin layer, and has a base resin layer, a back surface side resin layer, and a front surface side resin layer in this order.
[3] The decorative sheet according to the above [1] or [2], which has a decorative layer between the back surface side resin layer and the base material resin layer.
[4] The decorative sheet [5] adherend according to any one of the above [1] to [3], which has a recess on the surface of the front surface side resin layer opposite to the surface of the back surface side resin layer side. A decorative material having the decorative sheet according to any one of the above [1] to [4].

According to the present invention, it is possible to provide a decorative sheet having excellent weather resistance and designability, and a decorative material using the decorative sheet.

It is a schematic diagram which shows the cross section of the example of the decorative sheet of this invention. It is a schematic diagram which shows the cross section of the example of the decorative sheet of this invention. It is a schematic diagram which shows the cross section of an example of the decorative material of this invention.

[Cosmetic sheet]
The decorative sheet of the present invention is a decorative sheet having a back surface side resin layer and a front surface side resin layer, and the front surface side resin layer is made of a cured product of a curable resin composition containing a metal oxide-based ultraviolet shielding agent. The back surface side resin layer contains an organic ultraviolet absorber.
The configuration of the decorative sheet of the present invention will be described with reference to FIGS. 1 and 2. FIG. 1 is a schematic view showing a cross section of an example of a decorative sheet 10 of the present invention, and FIG. 2 is a schematic view showing a cross section of an example of a decorative sheet having a back surface side resin layer 2 and a front surface side resin layer 1. Further, it is a schematic diagram showing a cross section of an example of a decorative sheet having a base material resin layer 3 and having a base material resin layer 3, a back surface side resin layer 2 and a front surface side resin layer 1 in this order.
Hereinafter, each layer constituting the decorative sheet of the present invention will be described.

(Surface side resin layer)
The surface-side resin layer of the decorative sheet of the present invention needs to be made of a cured product of a curable resin composition containing a metal oxide-based ultraviolet shielding agent. A curable resin composition containing a metal oxide-based ultraviolet shielding agent used for the surface-side resin layer will be described below. As the resin component of the curable resin composition, an ionizing radiation curable resin, a two-component curable resin and a thermosetting resin can be used. Among these resins, an ionizing radiation curable resin is preferably used from the viewpoints of heat resistance, scratch resistance, and suppression of bleed-out of metal oxide-based ultraviolet shielding agents, and a combination of a plurality of these resins is used, for example. The ionizing radiation curable resin and the thermosetting resin can be used in combination. Further, it may be a so-called hybrid type in which a curable resin and a thermoplastic resin are used in combination.

<Ionizing radiation curable resin>
The ionizing radiation curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and has an ionizing radiation curable functional group. Here, the ionizing radiation curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group is preferably mentioned. Be done. In addition, in this specification, "(meth) acryloyl group" means "acryloyl group or methacryloyl group". 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, but other than that, Electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays are also included.
As the ionizing radiation curable resin, specifically, a polymerizable monomer or a polymerizable oligomer conventionally used as an ionizing radiation curable resin can be appropriately selected and used.

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.
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.
From the viewpoint of improving processing characteristics, scratch resistance and weather resistance, the number of functional groups is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, further preferably 2 or more and 4 or less, and particularly preferably 2 or more and 3 or less. These polyfunctional (meth) acrylate monomers may be used alone or in combination of two or more. Further, it may be used as a composition in which one or more of these polyfunctional (meth) acrylate monomers and one or more of the polymerizable oligomers described below are mixed. By preparing a composition in which both are mixed, the crosslink density of the cured product, the molecular weight between crosslinks, and the like can be adjusted, and various physical properties of the cured product can be adjusted.

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. Examples thereof include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, acrylic (meth) acrylate oligomers and the like.
Further, as the polymerizable oligomer, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer, and a silicone (meth) acrylate-based oligomer having a polysiloxane bond in the main chain. , Aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resin having many reactive groups in small molecules, or in molecules such as novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers and the like having cationically polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination of two or more. From the viewpoint of improving processing properties, scratch resistance and weather resistance, urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, Acrylic (meth) acrylate oligomers are preferable, urethane (meth) acrylate oligomers and polycarbonate (meth) acrylate oligomers are more preferable, and urethane (meth) acrylate oligomers are even more preferable.

The number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less, more preferably 6 or less, still more preferably 4 or less, particularly preferably 4 or less, from the viewpoint of improving processing characteristics, scratch resistance and weather resistance. 3 or less is preferable.
The weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, more preferably 3,000 or more and 7,000 or less, from the viewpoint of improving processing characteristics, scratch resistance and weather resistance. More preferably, it is 3,500 or more and 6,000 or less. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

In the present invention, a monofunctional (meth) acrylate may be appropriately used in combination with the polyfunctional (meth) acrylate or the like for the purpose of reducing the viscosity thereof, as long as the object of the present invention is not impaired. .. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

In the present invention, the ionizing radiation curable resin preferably contains a polymerizable oligomer from the viewpoint of improving processing characteristics, scratch resistance and weather resistance. The content of the polymerizable oligomer in the ionizing radiation curable resin is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and particularly preferably 100% by mass.

<Two-component curable resin>
When a two-component curable resin is used for the surface-side resin layer, the two-component curable resin may be, for example, a vinyl chloride-vinyl acetate copolymer system, a polyester-based, urethane-based, acrylic-based or other polymer polyol alone, or a mixture thereof. On the other hand, the one to which a curing agent is added immediately before use is used. As the curing agent, polyhydric isocyanate is preferable, and for example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, and 4,4'-diphenylmethane diisocyanate; 1,6-hexamethylene diisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and other aliphatic (or alicyclic) isocyanates; Alternatively, a multimer, for example, an adduct of tolylene diisocyanate, a trimer of tolylene diisocyanate, or the like can also be used. The polymer polyol is preferably polyester polyol, for example, poly (ethylene adipate), poly (butylene adipate), poly (neopentyl adipate), poly (hexamethylene adipate), poly (butylene azelaate), poly (butylene ceva). Kate), polycaprolactone, etc. are used. Further, an acrylic polymer polyol can also be preferably used.

<Thermosetting resin>
When a thermosetting resin is used for the surface side resin layer, an epoxy resin, an unsaturated polyester resin, a diallyl phthalate resin, a urea resin, a melamine resin and the like can be exemplified as the thermosetting resin.

<Thermoplastic resin>
When a thermoplastic resin is mixed and used in the surface-side resin layer, a thermoplastic resin that can be used in the base resin layer described later can be used.

<Metal oxide UV shielding agent>
The surface-side resin layer needs to contain a metal oxide-based ultraviolet shielding agent. By using a metal oxide-based UV shielding agent, the UV absorber is less likely to bleed out and stays in the surface-side resin layer for a longer period of time than when an organic UV absorber is used, so that it has weather resistance. Can be made good. The reason for selecting the metal oxide-based ultraviolet shielding agent as the material for shielding the ultraviolet rays added to the surface-side resin layer is as follows.
That is, in general, regardless of whether it is an ultraviolet absorber or an ultraviolet shielding agent, as long as a foreign substance having no compatibility or chemical bond with the resin layer is mixed in the resin layer, there is a tendency for the resin layer to move to the surface over time to some extent. There is. However, the metal oxide-based UV shielding agent having a relatively large size with an average particle size of about 1 nm to 380 nm passes through between the resin layer constituent molecules and the resin more than the organic UV absorber having a smaller size. The speed of transition from the inside of the layer to the outside becomes small. Therefore, when the same amount is added, the metal oxide-based UV shielding agent tends to be more difficult to bleed out than the organic UV absorber.
In addition, metal oxides used in UV shielding agents are generally chemically stable, so they are less likely to decompose or deteriorate when exposed to sunlight, oxygen, wind and rain, than organic UV absorbers, which are organic compound molecules. There is a tendency. Therefore, the material on the outermost surface that has migrated to the outside is immediately lost, and the metal oxide-based ultraviolet shielding agent that is relatively difficult to bleed out and is chemically stable in the surface-side resin that is in contact with light, wind and rain, and oxygen. Select and add.
On the other hand, metal oxide-based UV shielding agents generally have lower transparency than organic UV absorbers, and tend to be colored bluish by Rayleigh scattering. Organic UV absorbers tend to be yellowish, which is the complementary color of blue, as a result of absorbing part of the blue to purple light that is close to the UV band, but they are more transparent than metal oxide UV shields. .. Therefore, if a metal oxide-based ultraviolet shielding agent is also added to the resin layer on the back surface side, the weather resistance of the decorative sheet is improved, but instead, the design of the decorative sheet due to the generation of cloudiness and bluish tint is improved. It causes the disadvantage of decline.
Therefore, in the present invention, among the ultraviolet absorbers or ultraviolet shielding agents added in the layer, the metal oxide-based ultraviolet shielding agent which is hard to bleed out to the surface side resin layer and has excellent weather resistance is clouded. An organic ray absorber having excellent transparency is added to the resin layer on the back surface side in order to add a bluish tint to the extent that it does not hinder the appearance design and to compensate for the lack of weather resistance.
Since the organic ultraviolet absorber bleeding out from the back surface side resin layer stays in the front surface side resin layer, it is incident in the front surface side resin layer until it penetrates the front surface side resin layer and escapes to the outside. Continues to function to attenuate the amount of UV light. Since the surface resin layer is a cured product of the curable resin composition, the movement of the organic ultraviolet absorber is slowed down by the network structure of the molecules of the surface resin layer formed by cross-linking or polymerization, and bleed-out is also suppressed. Further, while the organic ultraviolet absorber is present in the resin layer on the back surface side, the resin layer on the front surface side protects the organic ultraviolet absorber from the influence of ultraviolet rays, moisture, oxygen, etc. from the outside, so that the organic ultraviolet absorber itself Deterioration and deterioration are also suppressed.
Since the hue of the organic ultraviolet absorber is yellow, which corresponds to the hue of the metal oxide-based ultraviolet shielding agent and the complementary color, the decorative sheet for observing with the light transmitted through both the front surface side resin layer and the back surface side resin layer. Since the coloring is offset to some extent, the deterioration of the design appearance of the decorative sheet is improved.

The metal oxide-based ultraviolet shielding agent is not particularly limited as long as it is a metal oxide having an ultraviolet absorbing ability and / or an ultraviolet shielding ability. To give an example of a metal oxide-based ultraviolet shielding agent, titanium oxide, zinc oxide, iron oxide, cerium oxide, zirconium oxide and bismuth oxide can be preferably used. In order to impart UV shielding performance to the surface resin layer with these metal oxide-based UV shielding agents,
(1) The metal oxide-based ultraviolet shielding agent is atomized, mixed in the surface-side resin layer, and dispersed inside the layer.
(2) A thin film of a metal oxide-based ultraviolet shielding agent is deposited and laminated on the front surface, the back surface, or both front and back surfaces of the front surface side resin layer by using a vacuum vapor deposition method, a sputtering method, or the like.
There are two forms, but usually, the form in which the particles of (1) are mixed and dispersed may be adopted. Hereinafter, this form will be described in detail.
Among the above-mentioned materials for the metal oxide-based ultraviolet shielding agent, zinc oxide can be used to further improve the weather resistance. As the particle size of the metal oxide-based ultraviolet shielding agent used, one having an average primary particle size of 1 nm or more and 380 nm or less, preferably 5 nm or more and less than 200 nm, and more preferably 8 nm or more and less than 100 nm can be used. By using a metal oxide-based ultraviolet shielding agent having an average primary particle size within this range, transparency to visible light can be ensured, the design of the decorative sheet is not adversely affected, and weather resistance is also improved. It can be good. Here, the average primary particle diameter is a value that can be obtained as the mass average value D50 in the particle size distribution measurement by the laser optical diffraction method.

From the viewpoint of selecting a metal oxide-based ultraviolet shielding agent having a low photocatalytic activity in consideration of weather resistance, it is preferable that the metal oxide-based ultraviolet shielding agent is surface-treated to suppress the photocatalytic activity. As the surface treatment, for example, those which have been surface-treated with an inorganic metal hydrous oxide and whose surface is covered with inorganic hydrous oxide fine particles are preferable. Preferred examples of the inorganic metal hydrous oxide include alumina, silica, titania, zirconia, tin oxide, antimony oxide, zinc oxide and the like. Further, titanium oxide whose surface has not been treated or titanium oxide whose surface has been surface-treated with the above-mentioned inorganic metal-containing hydroxide is used as a silane coupling agent, a titanate coupling agent, a coupling agent such as an aluminum coupling agent, or a silicone oil. , A surface treatment with a fluorine-based oil or the like to make the surface hydrophobic or lipophilic is also preferable. In the present invention, a metal oxide-based ultraviolet shielding agent that has been subjected to the above surface treatment alone or a combination of a plurality of surface treatments can be used.

The content of the metal oxide-based ultraviolet shielding agent contained in the surface-side resin layer is usually 0.2 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin constituting the surface-side resin layer. In addition, a curable resin composition containing a metal oxide-based ultraviolet shielding agent is preferably added so as to have a mass of 1 part by mass or more and 25 parts by mass or less, and more preferably 5 parts by mass or more and 20 parts by mass or less. It is preferable to adjust it. By setting the content of the metal oxide-based ultraviolet shielding agent contained in the surface-side resin layer within the above range, the designability can be improved without deteriorating the transparency of the surface-side resin layer. And the weather resistance can be improved.

On the surface side resin layer, as an additive, an organic ultraviolet absorber, a light stabilizer, an abrasion resistance improver, a polymerization inhibitor, a cross-linking agent, an infrared absorber, and an antistatic agent, as long as the object of the present invention is not impaired. Agents, adhesiveness improvers, leveling agents, thixophilic imparting agents, coupling agents, plasticizers, defoaming agents, fillers, antiblocking agents, lubricants, solvents and the like can be added. Among the above additives, it is preferable to use a light stabilizer for the surface-side resin layer from the viewpoint of further improving the weather resistance of the decorative sheet of the present invention.

The thickness of the surface-side resin layer is preferably 1.5 μm or more and 20 μm or less, more preferably 2 μm or more and 15 μm or less, and further preferably 3 μm or more and 10 μm or less, from the viewpoint of improving processing characteristics, scratch resistance and weather resistance.

(Resin layer on the back side)
The back surface side resin layer is a layer provided on the back surface side of the front surface side resin layer. Here, the surface side of the surface-side resin layer constitutes the surface of the decorative sheet. In the decorative sheet of the present invention, the resin layer on the back surface side needs to contain an organic ultraviolet absorber. By including the organic ultraviolet absorber in the back surface side resin layer, the ultraviolet rays that have passed through the front surface side resin layer can be absorbed by the back surface side resin layer. Therefore, the weather resistance of the decorative sheet can be further improved. The resin layer on the back surface side of the decorative sheet of the present invention may be one layer or multiple layers. For example, it may have at least one of a primer layer for improving the adhesion with other layers and a transparent resin layer for protecting the decorative layer when it is provided.

<Resin constituting the back surface resin layer>
As the resin constituting the back surface side resin layer, an ionizing radiation curable resin, a two-component curable resin, a thermosetting resin and a thermoplastic resin can be used. As the ionizing radiation curable resin, the two-component curable resin, the thermosetting resin, and the thermoplastic resin, the resin used for the surface-side resin layer described above can be used. In particular, when the back surface side resin layer is used as the primer layer, it is preferable to use an ionizing radiation curable resin, a two-component curable resin, or a thermosetting resin as the resin constituting the primer layer. When the back surface side resin layer is a transparent resin layer, it is preferable to use a thermoplastic resin as the resin constituting the transparent resin, for example, a polyolefin resin such as polypropylene or polyethylene, a polyester resin, a polycarbonate resin, or an acrylonitrile-butadiene. -A styrene resin (hereinafter, also referred to as "ABS resin"), an acrylic resin, a vinyl chloride resin, or the like is used.
By containing the organic ultraviolet absorber in the back surface resin layer, it is possible to absorb the ultraviolet rays that have passed through the front surface resin layer and prevent the organic ultraviolet absorber contained in the back surface resin layer from bleeding out. Can be done. It is preferable that at least one of the primer layer and the transparent resin layer contains an organic ultraviolet absorber.

For the resin layer on the back surface side, a resin composition in which a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, a light stabilizer and the like are appropriately mixed in addition to the organic ultraviolet absorber is used.

<Organic UV absorber>
The organic ultraviolet absorber used for the resin layer on the back surface side is not particularly limited, and examples thereof include a triazine-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and the like, and a triazine-based ultraviolet absorber. Is preferable. More specifically, among the triazine-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet rays in which three hydroxyphenyl groups, alkoxyphenyl groups, and one organic group selected from organic groups containing these groups are linked to the triazine ring. The absorbent is more preferable, and since the hydroxyphenyltriazine-based ultraviolet absorber represented by the following general formula (1) has a branched structure, it is expected that bleed-out will be difficult, and it is further preferable from the viewpoint of weather resistance.

In the general formula (1), R ¹¹ is a divalent organic group, R ¹² is an ester group represented by −C (= O) OR ^{15 , and R 13} , R ¹⁴ and R ¹⁵ are independent of each other. It is a monovalent organic group, and n ₁₁ and n ₁₂ are independently integers of 1 to 5.

Examples of the divalent organic group of R ¹¹ include an aliphatic hydrocarbon group such as an alkylene group and an alkaneylene group, and an alkylene group is preferable from the viewpoint of weather resistance, and the carbon number thereof is preferably 1 or more and 20 or less. 1 or more and 12 or less are more preferable, 1 or more and 8 or less are further preferable, and 1 or more and 4 or less are particularly preferable. The alkylene group and the alkenylene group may be linear, branched or cyclic, but the linear or branched group is preferable.
Examples of the alkylene group having 1 or more and 20 or less carbon atoms include a methylene group, a 1,1-ethylene group, a 1,2-ethylene group, a 1,3-propylene, a 1,2-propylene and a 2,2-propylene group. Various propylene groups (hereinafter, "various" means linear, branched, and those containing isomers thereof), various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, Various octylene groups, various nonylene groups, various decylene groups, various undecylene groups, various dodecylene groups, various tridecylene groups, various tetradecylene groups, various pentadecylene groups, various hexadecylene groups, various heptadecylene groups, various octadecylene groups, various nonadecilene groups, various icosilene groups. The group is mentioned.

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. Aryl groups are preferred. Of these, a phenyl group is preferable as the monovalent organic group of ^{R 13} and R ^14.
The aryl group preferably has 6 or more and 20 or less carbon atoms, more preferably 6 or more and 12 or less carbon atoms, and more preferably 6 or more and 10 or less carbon atoms, for example, a phenyl group, various methylphenyl groups, and various ethylphenyl groups. Groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups and the like can be mentioned. The arylalkyl group preferably has 7 or more and 20 or less carbon atoms, more preferably 7 or more and 12 or less carbon atoms, and more preferably 7 or more and 10 or less carbon atoms, for example, a benzyl group, a phenethyl group, and various phenylpropyl groups. Groups, various phenylbutyl groups, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, various hexylbenzyl groups and the like can be mentioned.

The monovalent organic group R ^15, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aryl alkyl group, and an alkyl group, an aliphatic hydrocarbon group, an alkenyl group preferably an alkyl group Is more preferable. That is, as R ¹² , an alkyl ester group and an alkenyl ester group are preferable, and an alkyl ester group is more preferable.
The alkyl group preferably has 1 or more and 20 or less carbon atoms, more preferably 2 or more and 16 or less, and further preferably 6 or more and 12 or less, such as a methyl group, an ethyl group, various propyl groups, various butyl groups, and various types. Pentyl group, various hexyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups. , Various nonadesyl groups and various icosyl groups.
As the alkenyl group, an alkenyl group having preferably 2 or more and 20 or less carbon atoms, more preferably 3 or more and 16 or less, still more preferably 6 or more and 12 or less, for example, a vinyl group, various propenyl groups, various butenyl groups, various pentenyl groups, Various hexenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, various hexadecenyl groups, various heptadecenyl groups, various octadecenyl groups, various nonadesenyl groups. Examples include groups and various icosenyl groups.

More specifically, as the hydroxyphenyltriazine compound represented by the general formula (1), R ¹¹ is an alkylene group having 1 or more and 20 or less carbon atoms, and R ^{12 and R 15 are alkyl groups having 1 or more and 20 or less carbon atoms.} It is an alkyl ester group as a group, R ¹³ and R ¹⁴ are aryl groups having 6 or more carbon atoms _{and 20 or less carbon atoms, and a hydroxyphenyltriazine compound having n 11} and n ₁₂ of 1 is preferable, and R ¹¹ has 1 or more carbon atoms and 12 carbon atoms. The following alkylene groups, R ¹² and R ¹⁵ are alkyl ester groups having 2 or more and 16 or less carbon atoms, and R ¹³ and R ¹⁴ are aryl groups having 6 or more and 12 or less carbon atoms, and n ₁₁ And _{a hydroxyphenyltriazine compound having n 12} of 1 is more preferable, R ¹¹ is an alkylene group having 1 or more and 8 or less carbon atoms, and R ¹² and R ¹⁵ are alkyl groups having 6 or more and 12 or less carbon atoms. R ¹³ and R ¹⁴ are aryl groups having 6 or more and 10 or less carbon atoms, hydroxyphenyltriazine compounds having _{n 11} and n ₁₂ ^{of 1 are more preferable, and R 11} is an alkylene group having 1 or more and 4 or less carbon atoms. , R ¹² and R ¹⁵ are ester groups which are alkyl groups having 8 carbon atoms, R ¹³ and R ¹⁴ are phenyl groups, and _{hydroxyphenyl triazine compounds having n 11} and n ₁₂ of 1 are particularly preferable.

As the hydroxyphenyltriazine compound represented by the general formula (1), more specifically, an ester group ^{represented by the following chemical formula (2) in which R 11} is an ethylene group and R ¹² and R ^{15 are isooctyl groups.} , R ¹³ and R ¹⁴ are phenyl groups, and n ₁₁ and n ₁₂ are 1 hydroxyphenyltriazine compounds, ie 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4, 6-Bis (4-phenylphenyl) -1,3,5-triazine is preferable, and this hydroxyphenyltriazine compound is available as a commercially available product ("TINUVIN479", manufactured by BASF), for example.

These organic ultraviolet absorbers can be used alone or in combination of two or more. Further, the organic ultraviolet absorber may have, for example, a reactive functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group and an allyl group.

The back surface side resin layer may be one layer or multiple layers, but the content of the organic ultraviolet absorber is the resin component 100 constituting the back surface side resin layer in the back surface side resin layer. It is preferably 0.4 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 18 parts by mass or less, and more preferably 3 parts by mass or more and 16 parts by mass or less. preferable. With such a content, the weather resistance and designability of the decorative sheet can be improved.

The thickness of the back surface side resin layer is not particularly limited, but is preferably 0.1 μm or more and 100 μm or less, more preferably 0.5 μm or more and 80 μm or less, and further preferably 1 μm or more and 100 μm or less. When the thickness of the back surface resin layer containing the organic ultraviolet absorber is within this range, the weather resistance and the design can be improved. In particular, when the back surface resin layer containing an organic ultraviolet absorber is used as a primer layer, the thickness thereof is preferably 1 μm or more and 10 μm or less, more preferably 2 μm or more and 8 μm or less, and further preferably 3 μm or more. It is desirable to make it 6 μm or less from the viewpoint of design.

Further, a light stabilizer can also be used for the resin layer on the back surface side. As the light stabilizer, a hindered amine-based light stabilizer is preferable, for example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidin, 1,2,2,6,6-pentamethyl-4-piperidinyl (meth). ) Alacrylate, bis (2,2,6,6-tetramethyl-4-piperidyl) sevacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sevakate, bis (1-octyl oshiki-2, 2,6,6-Tetramethyl-4-piperidinyl) sevacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sevacate, 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) Examples thereof include 6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxy-benzyl) -2-n-butylmalonate. 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- A hindered amine-based photostabilizer derived from decanedioic acid (sebacic acid) such as 4-piperidinyl) sebacate is preferable.

These light stabilizers can be used alone or in combination of two or more. Further, the organic ultraviolet absorber and the light stabilizer may have, for example, a reactive functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group and an allyl group.

(Base resin layer)
It is preferable that the decorative sheet of the present invention further has a base resin layer, and has a base resin layer, a back surface side resin layer, and a front surface side resin layer in this order. As the base resin used for the base resin layer, those usually used as the base material of the decorative sheet can be adopted without limitation, and a thermoplastic resin is typically used. As the thermoplastic resin, for example, polyolefin resins such as polypropylene and polyethylene, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter, also referred to as “ABS resins”), acrylic resins, vinyl chloride resins and the like are used. To. Among these, polyolefin resin, polyester resin, polycarbonate resin and ABS resin are preferable, and polyolefin resin is particularly preferable, in consideration of processing characteristics. In the present invention, these resins can be used alone or in combination of two or more.

The polyolefin resin is not particularly limited, and is, for example, polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate. Examples thereof include copolymers, ethylene-acrylic acid copolymers, ethylene-propylene-butene copolymers, and polyolefin-based thermoplastic elastomers. Of these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer, and propylene-butene copolymer are preferable.

The base resin layer may be colored, and the mode of coloring is not particularly limited, and may be transparent coloring or opaque coloring (concealment coloring), and these may be arbitrarily selected. ..
The base resin layer preferably contains a white pigment. By containing the white pigment, the ground color of the adherend to which the decorative sheet is attached can be concealed, more excellent designability can be obtained, and the color tone stability of the obtained decorative sheet can be improved.

Examples of the white pigment include titanium oxide (titanium white), white lead, antimony white, titanium dioxide-coated mica, and the like, and these can be used alone or in combination of two or more. In the present invention, titanium oxide (titanium white) is preferable in consideration of concealing property (color development), ease of handling, and the like.
Titanium oxide includes anatase type, brookite type and rutile type, and any of them can be used, but the rutile type is preferable in consideration of excellent concealment (color development) and weather resistance. Since rutile-type titanium oxide has low photocatalytic activity, it is unlikely that a photocatalytic reaction will occur even when used in an environment exposed to direct sunlight, and deterioration of the base material and decorative layer due to the photocatalytic reaction, and other optional layers. Is less likely to occur, and as a result, weather resistance is improved.

The white pigment is preferably surface-treated from the viewpoint of selecting a pigment having low photocatalytic activity in consideration of weather resistance. As the surface-treated white pigment, for example, a pigment that has been surface-treated with an inorganic metal-containing hydroxide and whose surface is covered with inorganic hydroxide-containing fine particles is preferable. Preferred examples of the inorganic metal hydrous oxide include alumina, silica, titania, zirconia, tin oxide, antimony oxide, zinc oxide and the like. Further, titanium oxide whose surface has not been treated or titanium oxide whose surface has been surface-treated with the above-mentioned inorganic metal-containing hydroxide is used as a silane coupling agent, a titanate coupling agent, a coupling agent such as an aluminum coupling agent, or a silicone oil. , A surface treatment with a fluorine-based oil or the like to make the surface hydrophobic or lipophilic is also preferable. In the present invention, a white pigment subjected to the above surface treatment alone or a combination of a plurality of surface treatments can be used.
In the present invention, from the viewpoint of obtaining excellent hiding power, surface treatment with alumina, silica and zinc oxide is preferable, surface treatment with alumina and silica is more preferable, and surface treatment with alumina and silica is particularly preferable.

The average particle size of the primary particles of the white pigment is preferably 0.02 μm or more and 1.5 μm or less, more preferably 0.15 μm or more and 0.5 μm or less, and further preferably 0.1 μm or more and 0.3 μm or less. When the average particle size of the white pigment is within the above range, excellent color development can be obtained, and high concealment and design can be obtained. Here, the average particle size is a value that can be obtained as the mass average value D50 in the particle size distribution measurement by the laser light diffraction method.

The content of the white pigment in the base material resin layer may be appropriately adjusted depending on whether it is transparently colored or opaquely colored (concealed coloring). For example, 100 parts by mass of the resin constituting the base material resin layer. On the other hand, 1 part by mass or more and 50 parts by mass or less are preferable, 3 parts by mass or more and 40 parts by mass or less are more preferable, 5 parts by mass or more and 30 parts by mass or less are further preferable, and 5 parts by mass or more and 20 parts by mass or less are particularly preferable.

The base resin layer may contain a colorant other than the white pigment. For example, inorganic pigments such as iron black, yellow lead, titanium yellow, petals, cadmium red, ultramarine blue, cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue; scales such as aluminum and brass. Metallic pigments made of foil pieces; colorants such as titanium dioxide-coated mica, pearly pigments made of scaly foil pieces such as basic lead carbonate, and the like can be mentioned.

Additives may be added to the base resin layer, 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 can be appropriately set according to the required characteristics and the like.

The base resin layer may be composed of either a single layer of the above resin or a plurality of layers made of the same type or different types of resin.
The thickness of the base resin layer is preferably 20 μm or more and 150 μm or less, more preferably 25 μm or more and 120 μm or less, further preferably 30 μm or more and 100 μm or less, and particularly preferably 40 μm or more and 80 μm or less, particularly considering the processing characteristics.

Further, the base resin layer has an oxidation method and unevenness on one or both sides thereof in order to improve the interlayer adhesion between the base resin layer and the other layer and to strengthen the adhesiveness with various adherends. A physical surface treatment such as a chemical method or a surface treatment such as a chemical surface treatment can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method and the like, and examples of the unevenness method include sandblasting method and 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 viewpoint of the effect and operability of the surface treatment.
Further, in order to improve the interlayer adhesion between the base resin layer and other layers and to strengthen the adhesiveness with various adherends, a base primer layer and a back surface primer layer are formed on the base resin layer. It may be treated.

(Decorative layer)
From the viewpoint of improving the design, the decorative sheet of the present invention preferably has a decorative layer between the back surface side resin layer and the base material resin layer. The decorative layer may be, for example, a colored layer that covers the entire surface (so-called solid colored layer), or may be a pattern layer formed by printing various patterns using ink and a printing machine. It may be good, or it may be a combination of these. For example, in the case of coloring and concealing the ground color of the adherend, by using a solid coloring layer, it is possible to improve the design while concealing the coloring, and from the viewpoint of further improving the design, solid coloring is possible. The layer and the pattern layer may be combined, and on the other hand, when the ground pattern of the adherend is utilized, only the pattern layer may be provided instead of the solid coloring layer.

As the ink used for the decorative layer, an ink obtained by appropriately mixing a binder with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. is used. Will be done.
The binder is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (mainly polymer). Urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a carbonate bond in the chain and having two or more hydroxyl groups at the end and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-acetic acid. Resins such as vinyl-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, and cellulose acetate resin are preferably mentioned, and these can be used alone or in combination of two or more. In addition to the one-component curing type, for example, curing of isocyanate compounds such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID), and xylylene diisocyanate (XDI). Various types of resins can be used, such as a two-component curable type with an agent.

As the colorant, a white pigment is preferably used from the viewpoint of concealing the ground color of the adherend and improving the design. The content of the white pigment in the decorative layer is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass with respect to 100 parts by mass of the resin constituting the decorative layer. More than 70 parts by mass is more preferable.

In addition, colorants other than white pigments, such as iron black, yellow lead, titanium yellow, petals, cadmium red, ultramarine, cobalt blue, and other inorganic pigments; Organic pigments or dyes such as azomethine azo compounds and perylene compounds; metal pigments made of scaly foil pieces such as aluminum and brass; pearl luster made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate. ) A colorant such as a pigment can also be used.

From the viewpoint of improving the weather resistance, the decorative layer preferably contains a weather resistant agent such as an ultraviolet absorber and a light stabilizer, and more preferably contains a light stabilizer.
Examples of the ultraviolet absorber and the light stabilizer include the ultraviolet absorber and the light stabilizer exemplified as those that can be contained in the resin layer on the back surface side. The content of the ultraviolet absorber and the content of the light stabilizer can be exemplified in the same range as the content in the resin layer on the back surface side from the viewpoint of improving the weather resistance.

When a pattern layer is provided as a decorative layer, the pattern includes a wood grain pattern, a stone pattern that imitates the surface of a rock such as a marble pattern (for example, Travertin marble pattern), a fabric pattern that imitates a cloth grain or a cloth-like pattern, and a tile. There are pasted patterns, brick pile patterns, etc., and there are also patterns such as parquet, patchwork, etc. that combine these patterns. These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing plates of the individual colors that make up the pattern. Will be done.

The thickness of the decorative layer may be appropriately selected according to the desired pattern, but is preferably 0.5 μm or more and 20 μm or less, preferably 1 μm, from the viewpoint of coloring and concealing the ground color of the adherend and improving the design. More preferably 10 μm or less, further preferably 2 μm or more and 5 μm or less.

When the decorative sheet of the present invention has a decorative layer, it is preferable that at least one of the base resin layer and the decorative layer contains a white pigment. By using the base resin layer and the decorative layer colored with the white pigment, when the surface hue of the adherend to which the decorative sheet is attached varies, it is easy to conceal the surface hue well, and the design is more excellent. The property can be obtained, and the color stability of the obtained decorative sheet can be improved.

(Adhesive layer)
The decorative sheet used in the present invention may have an adhesive layer, if necessary. In particular, when the decorative sheet of the present invention has a decorative layer, it is effective to provide an adhesive layer when improving the interlayer adhesion between the decorative layer and the resin layer on the back surface side. As the adhesive constituting the adhesive layer, an adhesive usually used in a decorative sheet can be used without limitation.

Examples of the adhesive include urethane-based adhesives, acrylic-based adhesives, epoxy-based adhesives, rubber-based adhesives, and the like, and among them, urethane-based adhesives are preferable in terms of adhesive strength. As the urethane-based adhesive, for example, an adhesive using a two-component curable urethane resin containing various polyol compounds such as a polyether polyol, a polyester polyol, and an acrylic polyol, and a curing agent such as the above-mentioned various isocyanate compounds. Can be mentioned. Further, 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 is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and further preferably 2 μm or more and 10 μm or less from the viewpoint of obtaining sufficient adhesiveness.

(Recess)
The decorative sheet of the present invention preferably has a recess on the surface of the front surface side resin layer opposite to the surface on the back surface side resin layer side (also referred to as "front surface side surface"). By having the concave portion in the decorative sheet of the present invention, a high-class feeling accompanying the improvement of the texture (tactile sensation) can be obtained, and the designability is improved.

The recess may be present on the surface of the front surface side resin layer opposite to the surface of the back surface side resin layer side, and the depth of the recess may be such that it stays in the front surface side resin layer or the back surface. Some may reach to the side resin layer side, and when having a base resin layer, some may reach to the base resin layer. From the viewpoint of obtaining an excellent texture (tactile sensation), not only those that stay in the resin layer on the front surface side, but also those that extend to the resin layer on the back surface side, those that extend to the decorative layer, and those that extend to the base resin layer are combined. Is preferable.

As the pattern of the concave portion, for example, there are a wood grain board conduit groove, a stone board surface unevenness, a cloth surface texture, a satin finish, a grain, a hairline, a perforated groove, and the like. From the viewpoint of improving the design, the pattern of the concave portion is preferably a pattern synchronized with the pattern of the decorative layer. For example, if the pattern layer has a wood grain pattern, selecting the wood grain board conduit groove as the pattern of the recesses and synchronizing the wood grain of the pattern layer with the grain of the recesses will give a more realistic, textured and luxurious feel. A decorative sheet and a decorative material can be obtained.

(Manufacturing method of decorative sheet)
The decorative sheet of the present invention can be manufactured, for example, as follows.
Regarding the method for producing a decorative sheet of the present invention, one of the preferred embodiments of the decorative sheet of the present invention is a base resin layer, a decorative layer, an adhesive layer, a back surface resin layer (transparent resin layer, a primer layer), and a surface surface. The manufacturing method will be described by taking as an example a decorative sheet having side resin layers in order.
The decorative sheet of the present invention is, for example, a step of providing a decorative layer on a base resin layer (1), a step of providing a back surface side resin layer (transparent resin layer, primer layer) on the decorative layer (2), and a step of providing the decorative layer. It can be produced by applying a curable resin composition on the back surface side resin layer and curing it to form a front surface side resin layer (3) in order.

The step (1) is a step of providing a decorative layer on the base resin layer. The decorative layer is formed by applying an ink used for forming the decorative layer on the base resin layer to provide a desired colored layer and a pattern layer. The ink 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. As the base resin layer, it is preferable to use a base resin layer that has been subjected to surface treatment such as corona discharge treatment, if necessary.

The step (2) is a step of providing a back surface side resin layer (transparent resin layer, primer layer) on the decorative layer. The back surface side resin layer (transparent resin layer, primer layer) is formed by applying an adhesive to the base resin layer having the above decorative layer as needed to form an adhesive layer, and then the back surface side resin layer (transparent resin). It is preferable to form a layer (layer, primer layer). As a method for forming the back surface side resin layer, when the back surface side resin layer is formed as a transparent resin layer, it may be formed by adhering and pressure bonding by a method such as extrusion lamination, dry lamination, wet lamination, thermal lamination, etc. can. Further, when the back surface side resin layer is formed as a primer layer, the primer layer may be provided by coating or the like using a resin composition forming the primer layer.

The step (3) is a step of applying the curable resin composition on the back surface side resin layer and curing it to form the front surface side resin layer.
The surface-side resin layer is obtained by applying a curable resin composition, preferably an ionizing radiation curable resin composition, onto the resin layer and curing the resin layer.

The application of the resin composition for forming the surface-side resin layer is preferably a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma coat or the like so that the thickness after curing becomes a predetermined thickness. It is carried out by a known method, more preferably by a gravure coat.

When an ionizing radiation resin composition is used to form the surface-side resin layer, the uncured resin layer formed by applying the resin composition is made into a cured product by irradiating it with ionizing radiation such as electron beam and ultraviolet rays. It becomes the surface side resin layer. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of 70 kV or more and 300 kV or less. Is 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 kGy or more and 300 kGy or less (0.5 Mrad or more and 30 Mrad or less), preferably 10 kGy or more and 50 kGy or less (1 Mrad or more and 5 Mrad or less). To.
The electron beam source is not particularly limited, and for example, a cockloft Walton type, a van de Graaff 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 nm or more and 380 nm or less 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.

When a thermosetting resin composition is used for forming the surface side resin layer, it may be subjected to heat treatment according to the resin composition to be used and cured to form the surface side resin layer.

When forming a recess in the surface-side resin layer, for example, in consideration of ease of work, it is preferable to adopt embossing. The embossing may be performed by a usual method using a known single-wafer or rotary embossing machine.
When embossing, for example, the decorative sheet is heated to preferably 80 ° C. or higher and 260 ° C. or lower, more preferably 85 ° C. or higher and 160 ° C. or lower, and further preferably 100 ° C. or higher and 140 ° C. or lower, and the embossed plate is pressed against the decorative sheet. Then, embossing can be performed.

[Cosmetic material]
The decorative material of the present invention has an adherend and the above-mentioned decorative sheet of the present invention. Specifically, the surface of the adherend that requires decoration, the side surface of the resin layer on the back surface side of the decorative sheet, or It is laminated so that the surface on the base resin layer side faces each other. That is, the decorative material of the present invention has at least an adherend, a back surface side resin layer, and a front surface side resin layer in this order. FIG. 3 shows a schematic view showing a cross section of an example of a preferred embodiment of the decorative material of the present invention. The decorative material 20 of the present invention shown in FIG. 3 has an adherend 11 and a decorative sheet 10 of the present invention (base resin layer 3, back surface side resin layer 2, front surface side resin layer 1) in this order.

(Applied material)
Examples of the adherend include flat plates of various materials, plate materials such as curved plates, three-dimensional shaped articles, sheets (or films), and the like. For example, wood single boards made of various kinds of wood such as cedar, cypress, pine, and lauan, wood plywood, particle boards, wood fiber boards such as MDF (medium density fiber board), and wood members used as three-dimensional shaped articles. ; Plate materials such as iron and aluminum, steel plates, three-dimensional shaped articles, or metal members used as sheets; ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, and non-ceramic materials such as ALC (lightweight bubble concrete) plates. Ceramic members used as plate materials such as ceramic materials and three-dimensional shaped articles; polyolefin resins such as acrylic resin, polyester resin, polystyrene resin, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol resin, vinyl chloride Examples thereof include 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 a plurality of types.

The adherend may be appropriately selected from the above depending on the application, and is used for interior or exterior materials of buildings such as walls, ceilings, and floors, window frames, doors, handrails, skirting boards, surrounding edges, and moldings. When fittings or building members such as, etc. are used, those made of at least one member selected from wood members, metal members, and resin members are preferable, and exterior members such as entrance doors, window frames, and fittings such as doors are used. In this case, it is preferable that the member is composed of at least one member selected from a metal member and a resin member.

The thickness of the adherend may be appropriately selected depending on the intended use and material, preferably 0.1 mm or more and 10 mm or less, more preferably 0.3 mm or more and 5 mm, and further preferably 0.5 mm or more and 3 mm or less.

(Manufacturing method of decorative material)
The decorative material can be manufactured through a process of laminating a decorative sheet and an adherend.
This step is a step of laminating the adherend and the decorative sheet of the present invention, in which the surface of the adherend that requires decoration and the surface of the decorative sheet on the back surface side of the resin layer are opposed to each other and laminated. As a method of laminating the adherend and the decorative sheet, for example, a laminating method in which the decorative sheet is pressed against the plate-shaped adherend with a pressure roller and laminated with an adhesive in between, and an adhesive is sandwiched between them. While supplying the decorative sheet through, the decorative sheet is sequentially pressure-bonded and laminated on a plurality of side surfaces constituting the adherend by a plurality of rollers having different orientations, and is fixed to a fixed frame. The decorative sheet is heated with a heater through a silicone rubber sheet until it reaches a predetermined temperature at which the decorative sheet softens, the vacuum forming mold is pressed against the heated and softened decorative sheet, and at the same time, air is sucked from the vacuum forming mold with a vacuum pump or the like. A vacuum forming process for firmly adhering the decorative sheet to the vacuum forming mold is preferably mentioned.

The adherend and the decorative sheet are preferably bonded together via an adhesive in order to obtain excellent adhesiveness. The adhesive is not particularly limited, and a known adhesive can be used. For example, an adhesive such as a heat-sensitive adhesive or a pressure-sensitive adhesive is preferable. Examples of the resin used for the adhesive constituting this adhesive layer include acrylic resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, and polyester resin. , Polyamide resin and the like, 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 as the adhesive. 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.

The adhesive shall be a solution or emulsion of the above resin in a form that can be applied, and then applied and dried by means such as a gravure printing method, a screen printing method, or a reverse coating method using a gravure plate. Can be done.
The thickness of the adhesive 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.

When a hot melt adhesive (heat-sensitive adhesive) is used in the laminating process or wrapping process, the heating temperature is preferably 160 ° C or higher and 200 ° C or lower, although it depends on the type of resin constituting the adhesive, and the reactive hot melt. The adhesive is preferably 100 ° C. or higher and 130 ° C. or lower. Further, in the case of vacuum forming, it is generally performed while heating, and it is preferably 80 ° C. or higher and 130 ° C. or lower, and more preferably 90 ° C. or higher and 120 ° C. or lower.

The decorative material obtained as described above 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 materials or exterior materials of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, surrounding edges, fittings and building materials such as moldings, kitchens, furniture Alternatively, it can be used for a decorative plate on the surface of a cabinet such as a light electric product or an OA device, an interior or an exterior of a vehicle, and the like.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.
(Evaluation and measurement method)
(1) Evaluation of weather resistance For the decorative sheets obtained in each Example and Comparative Example, a UV lamp (trade name "ME10-L31WX / SUV", manufactured by Iwasaki Electric Co., Ltd.), a lamp jacket (trade name "WJ80-SUV"). , Iwasaki Electric Co., Ltd.) and a super-accelerated weather resistance test device (trade name "I Super UV Tester SUV-W261") equipped with an illuminance meter (trade name "UVP-365-03", manufactured by Iwasaki Electric Co., Ltd.), Iwasaki Electric Co., Ltd.) was used. The decorative sheet was repeatedly irradiated with a black panel temperature of 63 ° C., an illuminance of 100 mW / cm ² , 20 hours and dew condensation for 4 hours, and the appearance of the decorative sheet after 800 hours was visually observed and evaluated according to the following criteria.
A: No change in appearance was confirmed.
B: Slight whitening of the resin layer on the surface side was confirmed, but no change in color tone of the decorative layer was confirmed.
C: A slight whitening of the resin layer on the surface side and a slight change in color tone of the decorative layer were confirmed.
D: Remarkable whitening of the surface-side resin layer and the decorative layer was confirmed, and a large color change was confirmed.
(2) Evaluation of designability The decorativeness of the decorative sheets obtained in each Example and Comparative Example was evaluated according to the following criteria.
A: There was no change in the appearance of the resin layer on the surface side, and high designability was confirmed.
B: The resin layer on the surface side was slightly colored, but there was no significant effect on the design.
C: The resin layer on the surface side was colored and the design was low.

及び光安定剤ａとして、ヒンダードアミン光安定剤（ビス（１−オクチルオシキ−２，２，６，６−テトラメチル−４−ピペリジニル)セバケート、「ＴＩＮＵＶＩＮ１２３」、ＢＡＳＦ社製）３質量部を含む樹脂組成物を調製した。この樹脂組成物と硬化剤としてヘキサメチレンジイソシアネート（ＨＤＩ）とを１００対５の質量割合で混合し、該混合物を透明樹脂層上に塗布して裏面側樹脂層となるプライマー層を形成した。なお、プライマー層の厚みは４μｍとした。
次に、電離放射線硬化性樹脂組成物として、ウレタンアクリレートオリゴマー（重量平均分子量：４，０００、官能基数：３）に、金属酸化物系紫外線遮蔽剤として、酸化チタン（平均一次粒子径２０ｎｍ、ルチル型）をウレタンアクリレートオリゴマー１００質量部に対して１５質量部含有させ、該電離放射線硬化性樹脂組成物を用いてグラビアコート法にてプライマー層上に塗膜を形成した。その後、１７５ｋｅＶ及び５Ｍｒａｄ（５０ｋＧｙ）の条件で電子線を照射して、塗膜を架橋硬化させることにより、表面側樹脂層（５ｇ／ｍ^２）を形成させて化粧シートを得た。なお、表面側樹脂層の厚みは、５μｍであった。得られた化粧シートの表面側樹脂層の上からエンボス加工により、深さ５０μｍの木目導管状の凹凸模様を形成し、エンボス加工を施した化粧シートを得た。得られた化粧シートについて、上記の評価を行い、その評価結果を第１表に示す。 Example 1
Polypropylene resin sheet treated with double-sided corona discharge (thickness: 60 μm, white colored resin sheet (white pigment: rutile-type titanium oxide (average particle size: 0.25 μm), content: 100 parts by mass of polypropylene resin) 10 parts by mass)) as the base resin layer, and a printing ink (rutyl-type titanium oxide as a white pigment (average particle size: 0)) using a two-component curable acrylic-urethane resin as a binder on one surface of the base resin layer. .25 μm) (containing 20% by mass) is applied by the gravure printing method to provide a decorative layer with a wood grain pattern (thickness: 3 μm), and a two-component curable urethane-nitrated cotton mixed resin composition is applied to the other surface. A back surface primer layer (thickness: 2 μm) was formed.
A transparent polyurethane resin-based adhesive is applied onto the decorative layer to form an adhesive layer (thickness after drying: 3 μm), and the transparent polypropylene resin is heated, melted and extruded by a T-die extruder.
A transparent resin layer (thickness: 80 μm) was formed.
Next, after corona discharge treatment is applied to the surface of the transparent resin layer, the hydroxyphenyltriazine-based ultraviolet absorber α (“TINUVIN479”” is used as an organic ultraviolet absorber in the resin component composed of the polycarbonate-based urethane acrylic copolymer and the acrylic polyol. , BASF), 3 parts by mass with respect to 100 parts by mass of the resin component, and as other organic ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorber β (“TINUVIN400”, BASF) represented by the following formula (3). (Manufactured by) 12 parts by mass

And as the light stabilizer a, a resin composition containing 3 parts by mass of a hindered amine light stabilizer (bis (1-octyl osiki-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, "TINUVIN123", manufactured by BASF). The thing was prepared. This resin composition and hexamethylene diisocyanate (HDI) as a curing agent were mixed at a mass ratio of 100: 5, and the mixture was applied onto the transparent resin layer to form a primer layer to be a back surface resin layer. The thickness of the primer layer was 4 μm.
Next, as an ionizing radiation curable resin composition, a urethane acrylate oligomer (weight average molecular weight: 4,000, number of functional groups: 3) was used, and as a metal oxide-based ultraviolet shielding agent, titanium oxide (average primary particle diameter 20 nm, rutyl) was used. The mold) was contained in an amount of 15 parts by mass with respect to 100 parts by mass of the urethane acrylate oligomer, and a coating film was formed on the primer layer by a gravure coating method using the ionizing radiation curable resin composition. Then, the coating film was cross-linked and cured by irradiating with an electron beam under the conditions of 175 keV and 5 Mrad (50 kGy ^{) to form a surface-side resin layer (5 g / m 2} ) to obtain a decorative sheet. The thickness of the surface-side resin layer was 5 μm. An embossed decorative sheet was obtained by embossing the surface-side resin layer of the obtained decorative sheet to form an uneven pattern in the shape of a wood grain conduit having a depth of 50 μm. The obtained decorative sheet was evaluated as described above, and the evaluation results are shown in Table 1.

Examples 2-9
In Example 1, a decorative sheet was produced in the same manner as in Example 1 except that the metal oxide-based ultraviolet shielding agent of the surface-side resin layer was changed to the metal oxide-based ultraviolet shielding agent shown in Table 1. The obtained decorative sheet was evaluated as described above, and the evaluation results are shown in Table 1.

Example 10
In Example 1, the metal oxide-based ultraviolet shielding agent used for the surface-side resin layer was changed to 15 parts by mass of zinc oxide having an average primary particle diameter of 35 nm, and the hydroxyphenyltriazine-based ultraviolet absorber α (“TINUVIN479”, BASF, Inc.) was changed. (Manufactured by) Add 0.5 parts by mass, and use 12 parts by mass to 0 parts of hydroxyphenyltriazine-based ultraviolet absorber β (“TINUVIN400”, manufactured by BASF) used for the primer layer to be the resin layer on the back surface side. A decorative sheet was produced in the same manner as in Example 1 except that the amount was changed to 5.5 parts by mass. The obtained decorative sheet was evaluated as described above, and the evaluation results are shown in Table 1.

Example 11
In Example 1, the metal oxide-based ultraviolet shielding agent used for the surface-side resin layer was changed to 15 parts by mass of zinc oxide having an average primary particle diameter of 35 nm, and the resin component 100 was added to the resin of the base resin layer and the decorative layer. Except for adding 1 part by mass of hindered amine light stabilizer a (bis (1-octyl oshiki-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, "TINUVIN123", manufactured by BASF) to each part by mass. Made a decorative sheet in the same manner as in Example 1. The obtained decorative sheet was evaluated as described above, and the evaluation results are shown in Table 1.

Comparative Example 1
In Example 1, instead of titanium oxide, which is a metal oxide-based ultraviolet shielding agent used in the ionizing radiation-curable resin composition used for forming the surface-side resin layer, benzotriazole-based as an organic ultraviolet absorber. A decorative sheet was prepared in the same manner as in Example 1 except that 0.5 part by mass of the ultraviolet absorber γ (“TINUVIN326”, manufactured by BASF) was used with respect to 100 parts by mass of the urethane acrylate oligomer. The obtained decorative sheet was evaluated as described above, and the evaluation results are shown in Table 1.

From the results in Table 1, in the decorative sheet of the present invention, the surface-side resin layer is made of a cured product of a curable resin composition containing a metal oxide-based ultraviolet shielding agent, and the intermediate resin layer contains an organic-based ultraviolet absorber. Thereby, it is shown that a decorative sheet having excellent weather resistance and designability can be obtained. On the other hand, it has been shown that the decorative sheet of Comparative Example 1 has reduced weather resistance when the surface resin layer contains an organic ultraviolet absorber instead of the metal oxide-based ultraviolet shielding agent.

The decorative sheet of the present invention has excellent weather resistance and design, and the decorative material using the decorative sheet is an interior material or exterior member of a building such as a wall, a ceiling, a floor, a window frame, a door, and the like. It is suitably used for fittings and building members such as handrails, skirting boards, peripheral edges, and moldings, as well as surface decorative boards for kitchens, furniture or light electrical products, cabinets for OA equipment, vehicle interior materials, and exterior members. In particular, due to its excellent weather resistance, it is suitably used for exterior members such as entrance doors, window frames, fittings such as doors, and other members used in an environment exposed to direct sunlight.

10. Cosmetic sheet 1. Surface side resin layer 2. Back side resin layer 3. Base resin layer 4. Adhesive material 20. Cosmetic material

Claims (14)

A decorative sheet having a back surface side resin layer and a front surface side resin layer, wherein the front surface side resin layer is a cured product of a curable resin composition containing a metal oxide-based ultraviolet ray shielding agent (provided that it contains an organic ultraviolet ray absorber. A decorative sheet comprising (excluding those) , the back surface side resin layer containing an organic ultraviolet absorber (however, excluding those containing a metal oxide-based ultraviolet shielding agent). The decorative sheet according to claim 1, further comprising a base resin layer, and having a base resin layer, a back surface side resin layer, and a front surface side resin layer in this order. The decorative sheet according to claim 1 or 2 , wherein the back surface side resin layer has at least one of a primer layer and a transparent resin layer. The decorative sheet according to claim 3 , wherein at least one of the primer layer and the transparent resin layer contains an organic ultraviolet absorber. The decorative sheet according to any one of claims 2 to 4 , which has a decorative layer between the back surface side resin layer and the base material resin layer. The decorative sheet according to claim 5 , wherein at least one of the base resin layer and the decorative layer contains a white pigment. The decorative sheet according to any one of claims 1 to 6 , wherein the curable resin composition is an ionizing radiation curable resin composition. The decorative sheet according to any one of claims 1 to 7 , wherein the metal oxide-based ultraviolet shielding agent has an average primary particle size of 8 nm or more and less than 100 nm. The decorative sheet according to any one of claims 1 to 8 , wherein the metal oxide-based ultraviolet shielding agent is at least one selected from titanium oxide, zinc oxide, iron oxide, cerium oxide, zirconium oxide and bismuth oxide. .. The decorative sheet according to any one of claims 1 to 9 , wherein the organic ultraviolet absorber is a triazine ultraviolet absorber. One of claims 1 to 10 , wherein the content of the metal oxide-based ultraviolet shielding agent is 0.2 parts by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the resin constituting the surface-side resin layer. Cosmetic sheet described in. The item according to any one of claims 1 to 11 , wherein the content of the organic ultraviolet absorber is 0.4 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin constituting the resin layer on the back surface side. Cosmetic sheet. The decorative sheet according to any one of claims 1 to 12 , which has a recess on the surface of the front surface side resin layer opposite to the surface of the back surface side resin layer side. A decorative material having an adherend and a decorative sheet according to any one of claims 1 to 13.

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