JP2019030999A - Laminate and decorative sheet comprising the same - Google Patents

Abstract

To provide a decorative sheet having stable weather resistance.SOLUTION: A laminate contains, in a top coat layer 2 as a resin layer at the outermost surface side, a photo-stabilizer having a pKa of 4.0 to 7.0, and a gloss modifier composed of inorganic particles.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a resin laminate such as a resin film, and a decorative sheet used for a building interior material using the same, a building exterior member such as a front door, a surface of a fitting, a surface material of home appliances, and the like.

In recent years, many decorative sheets using olefinic resins have been proposed as decorative sheets that replace vinyl chloride decorative sheets. These decorative sheets are used for the protection of building interior materials for houses and public facilities, building exterior members such as entrance doors, surfaces of joinery, and surface materials of home appliances. Therefore, it is exposed to direct sunlight and wind and rain every day, and extremely high weather resistance is required. (See Patent Document 1)
All of the decorative sheets described in Patent Document 1 attempt to improve weather resistance by blending a light stabilizer, an ultraviolet absorber, or the like into a protective layer or a coat layer. However, after long-term use, bleed out from the surface of the olefin resin or coat causes the light stabilizer and UV absorber to disappear, and the chemical structure of each material is destroyed by oxygen and light, resulting in loss of function. It has been known.

Japanese Patent No. 4032829

However, if the target layer such as a protective layer or a coating layer contains an ultraviolet absorber or light stabilizer in an amount that provides sufficient weather resistance, the ultraviolet absorber or light in the resin composition constituting each layer. Aggregation of stabilizers may occur.
Furthermore, the chemical structure of the UV absorber and light stabilizer in the resin composition is broken and the molecular weight is lowered, so that the decomposed components of the UV absorber and the light stabilizer emerge from the surface of each layer, so-called bleed out occurs. It tends to occur. And the adhesiveness with another layer falls or it floats on the surface layer, and problems, such as stickiness, will arise.

  The present invention has been made paying attention to the above points, and an object thereof is to provide a decorative sheet having stable weather resistance.

The present inventors have studied various conditions that make it possible to prevent degradation of ultraviolet absorbers and light stabilizers over time and allow them to be used without deteriorating quality over a long period of time. I found it.
In order to solve the problem, the laminate of one embodiment of the present invention is a laminate including a plurality of resin layers, and the top coat layer located on the outermost surface side of the laminate has a pKa of 4.0 to 4.0. 7.0 light stabilizer was contained.

  According to one embodiment of the present invention, a decorative sheet having stable weather resistance over a long period of time can be provided by using the above laminate.

It is sectional drawing explaining the laminated body which concerns on embodiment based on this invention.

Embodiments of the present invention will be described with reference to the drawings.
Here, the configuration shown in FIG. 1 is schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiment described below exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the material, shape, structure, etc. of the component parts are as follows. It is not limited to things. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

  As shown in FIG. 1, the decorative sheet 1 of the present embodiment includes an ink layer 5, an adhesive layer 4, a transparent resin layer 3 as a surface protective layer, and a top coat on a raw fabric layer 6 constituting a base material layer. The layers 2 are arranged in this order. On the upper surface of the transparent resin layer 3, an embossed pattern 3a constituting an uneven pattern is formed. The uneven pattern may be formed by a method other than embossing. The transparent resin layer 3 is composed of an olefin resin layer. In the example of FIG. 1, an adhesive resin layer 7 is provided between the transparent resin layer 3 and the adhesive layer 4 in order to improve adhesiveness, but the adhesive resin layer 7 is not provided. Also good.

The decorative sheet 1 includes, for example, an adhesive layer 4 formed on a raw resin sheet in which an ink layer 5 is formed on one surface of the raw fabric layer 6 to form a first laminate, and a transparent resin layer. 3 and the adhesive resin layer 7 are co-pressed to form a top coat layer 2 containing a light stabilizer and a gloss adjusting agent to form a second laminate, and the first laminate and the second laminate Manufactured by bonding the laminate to each other by dry lamination or extrusion lamination.
Details of each layer will be described below.

<Topcoat layer>
On the outermost layer of the decorative sheet 1 is provided a top coat layer 2 that serves as surface protection and gloss adjustment. The top coat layer 2 contains at least a light stabilizer. In addition to the light stabilizer, the top coat layer 2 preferably contains an ultraviolet absorber.
Moreover, the top coat layer 2 of the present embodiment contains inorganic particles as a gloss adjusting agent.

  Here, FIG. 1 illustrates the case where the top coat layer 2 is formed along the surface of the transparent resin layer 3 with respect to the entire surface of the transparent resin layer 3, but is not limited thereto. The top coat layer 2 embeds the resin composition only in the recesses by applying a resin composition to the recesses of the embossed pattern 3a formed in the transparent resin layer 3 and scraping the coating liquid with a squeegee or the like. It may be embedded and provided by wiping. Further, the surface of the top coat layer 2 may be flat regardless of the concave portion of the embossed pattern 3a. The topcoat layer 2 only needs to be embedded in at least the recessed portion of the embossed pattern 3a. Even in the recessed portion where the layer thickness is reduced by forming the embossed pattern 3a, the topcoat layer 2 is formed by the embedded topcoat layer 2. High weather resistance can be maintained. In addition, by providing the topcoat layer 2 so as to cover the entire surface of the transparent resin layer 3, it is possible to provide the decorative sheet 1 having more excellent weather resistance.

(Resin material)
The resin material as the main component of the topcoat layer 2 is appropriately selected from resin materials such as polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, and urea. Can be used. The form of the resin material is not particularly limited, such as aqueous, emulsion, solvent type. The curing method can be appropriately selected from a one-component type, a two-component type, an ultraviolet curing method, and the like.
Here, the main component in this specification refers to a resin material that is contained in an amount of 70% by mass or more, preferably 90% by mass or more of the material constituting the target layer.

  As the resin material used as the main component of the topcoat layer 2, urethane-based materials using isocyanate are suitable from the viewpoints of workability, cost, cohesion of the resin itself, and the like. Isocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis (isocyanate methyl) cyclohexane ( HXDI), trimethylhexamethylene diisocyanate (TMDI) and other derivatives such as adducts, burettes, and isocyanurates can be appropriately selected and used. However, in consideration of weather resistance, linear molecules Curing agents based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having a structure are preferred.

  In addition to this, in order to improve the surface hardness, it is preferable to use a resin curable with active energy rays such as ultraviolet rays and electron beams. Known materials such as various monomers and commercially available oligomers can be used as the main material, but pentaerythritol triacrylate (PET3A), pentaerythritol tetraacrylate (PET4A), trimethylolpropane triacrylate (TMPTA), It is preferable to use a polyfunctional monomer such as dipentaerythritol hexaacrylate (DPHA), a polyfunctional oligomer such as purple light UV-1700B (manufactured by Nippon Synthetic Chemical), or a mixture thereof.

These resins can be used in combination with each other. For example, by using a hybrid type of a thermosetting type and a photocurable type, it is possible to improve surface hardness, suppress curing shrinkage, and improve adhesion. Can be planned.
At this time, the topcoat layer 2 is composed of a plurality of layers, for example, a thermosetting layer mainly composed of a thermosetting resin and a photocuring layer mainly composed of a photocurable resin such as an ultraviolet curable resin. May be. Thus, by comprising from two hardened layers, the surface hardness of the decorative sheet 1 can be improved. At this time, it is preferable that the photocured layer is on the surface layer side.

(Light stabilizer)
In the present embodiment, the topcoat layer 2 contains a light stabilizer having a pKa of 4.0 or more and 7.0 or less. Here, when the topcoat layer 2 has a plurality of layers, it is preferable to contain a light stabilizer having a pKa of 4.0 or more and 7.0 or less for each layer. A light stabilizer having a pKa of 4.0 or more and 7.0 or less may be contained in one layer.
The light stabilizer is preferably a hindered amine light stabilizer. In particular, a hindered amine light stabilizer having an amino ether group and a molecular weight of 600 or more is more preferable. What is necessary is just to measure the molecular weight of a light stabilizer, for example by a number average molecular weight.

The method for measuring the number average molecular weight of the light stabilizer is not particularly limited, but it is preferable to use gel permeation chromatography. The GPC measuring device is not particularly limited, but the GPC column filler is preferably polystyrene gel, and tetrahydrofuran (THF) is preferably used as the eluent. A polystyrene polymer may be used as a GPC standard substance.
However, when the light stabilizer is composed of a single substance, the value calculated from the structural formula may be used as the molecular weight of the light stabilizer if the structure is known.
The light stabilizer is, for example, the following hindered amine compound (1), and the hindered amine compound can capture radicals by the reaction of the reaction formula (2).

  Examples of hindered amine light stabilizers include bis (2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis (2,2,6,6-tetramethylpiperidin-4-yl) succinate; bis ( 1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis (1,2 , 2,6,6-pentamethylpiperidin-4-yl) n-butyl 3,5-di-tert-butyl 4-hydroxybenzyl malonate; 1- (2-hydroxyethyl) -2,2,6,6 A condensate of tetramethyl-4-hydroxypiperidine and succinic acid; 2,2,6,6-tetramethylpiperidin-4-ylstearate; 2,2,6,6-tetramethylpiper 1,2,2,6,6-pentamethylpiperidin-4-yl stearate; 1,2,2,6,6-pentamethylpiperidin-4-yldodecanate; N, Condensate of N′-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine; (2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate; tetrakis (2,2,6,6-tetramethylpiperidin-4-yl) -1,2,3,4-butanetetracarboxyl 4-benzoyl-2,2,6,6-tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine; bis (1,2,2, , 6-Pentamethylpiperidyl) -2-n-butyl 2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonic acid; 3-n-octyl-7,7,9,9-tetramethyl -1,3,8-triazaspiro [4.5] decane-2,4-dione; bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate; bis (1-octyloxy-2) , 2,6,6-tetramethylpiperidyl) succinate; N, N′-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4-morpholino 2,6-dichloro-1 , 3,5-triazine condensates; 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1, 2- Condensate of bis (3-aminopropylamino) ethane; 2-chloro-4,6-bis (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5 A condensate of triazine and 1,2-bis- (3-aminopropylamino) ethane; 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4. 5] Decane-2,4-dione; 3-dodecyl-1- (2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione; 3-dodecyl-1- (1- Ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl) pyrrolidine-2,5-dione; 3-dodecyl-1- (1,2,2,6,6-pentamethylpiperidin-4-yl) ) Pyrrolidine-2,5-dione; 4-he A mixture of sadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine; N, N′-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylenediamine and 4 -Condensate of cyclohexylamino-2,6-dichloro-1,3,5-triazine; 1,2-bis (3-aminopropylamino) ethane, 2,4,6-trichloro-1,3,5-triazine And 4-butylamino-2,2,6,6-tetramethylpiperidine condensate; 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro [ 4.5] decane; oxo-piperandinyl-triazine; 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxos B [4.5] decane and the reaction product of epichlorohydrin, and the like.

  Further, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate; 1,2,3,4 as an N-alkoxyhindered amine light stabilizer -Butanetetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester; 1,2,3,4-butanetetracarboxylic acid 1,2,2,6,6-pentamethyl-4 -Piperidinyl tridecyl ester; 1,2,3,4-butanetetracarboxylic acid 2,2,6,6-tetramethyl-4-piperidinyl tridecyl ester; 1,2,3,4-butanetetracarboxylic acid And 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] -undecane 3,9-diethanol polymer 1,2,2,6,6-pen Methyl-4-piperidinyl ester; 1,2,3,4-butanetetracarboxylic acid and 2,2,6,6-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] -undecane 2,2,6,6-tetramethyl-4-piperidinyl ester of a polymer of 3,9-diethanol; bis (1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate Etc.

  Further, as hydroxyl-substituted N-alkoxy HALS, 1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethyl-4-piperidinol; 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine; 1- (4-octadecanoyloxy-2,2,6,6-tetramethylpiperidin-1-yloxy) -2-octa Decanoyloxy-2-methylpropane; 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol; 1- (2-hydroxyethyl) -2,2,6,6- Examples include reaction products of tetramethyl-4-piperidinol and dimethyl succinate.

Among these hindered amine light stabilizers, typical commercially available ones are, for example, Tinuvin 123, Tinuvin 152, Tinuvin NOR 371 FF, Tinuvin XT850 FF, Tinuvin XT855 FF, TINUVIN 5100 manufactured by BASF Japan Ltd. TINUVIN 622SF, Flamestab NOR 116 FF, ADEKA ADEKA STAB LA-81, and the like. These may be used alone or in combination of two or more.
When mix | blending a light stabilizer with the topcoat layer 2, it is preferable to mix | blend 0.1 to 5.0 mass parts with respect to 100 mass parts of resin of the layer to mix | blend. More preferably, it is 0.3 to 3.0 parts by mass. If the blending amount of the light stabilizer is less than 0.1 parts by mass, the effect of the stability of the resin against the generated radicals may be low. On the other hand, if the amount is more than 5.0 parts by mass, the possibility of bleeding out increases.

(UV absorber)
When blending an ultraviolet absorber in the topcoat layer 2, it is preferable to blend an ultraviolet absorber having a pKa of -4.5 to -5.5 when irradiated with light. Here, when the topcoat layer 2 has a plurality of layers, it is preferable to blend an ultraviolet absorber having a pKa of −4.5 to −5.5 when irradiated with light.
When mix | blending a ultraviolet absorber with the topcoat layer 2, it is preferable to mix | blend 1.0 mass part or more and 15.0 mass parts or less with respect to 100 mass parts of resin of the layer to mix | blend. More preferably, it is 2.5 parts by mass or more and 8.0 parts by mass or less. If the blending amount of the UV absorber is less than 1.0 part by mass, the effect of the stability of the resin against UV rays may be low. On the other hand, if the amount is more than 15.0 parts by mass, the possibility of bleeding out increases.

In addition, when it has a thermosetting layer and a photocuring layer as mentioned above as the topcoat layer 2, it is preferable to mix | blend many said ultraviolet absorbers relatively on the thermosetting layer side.
As the ultraviolet absorber, at least one selected from benzotriazole, triazine, benzophenone, benzoate, and cyanoacrylate can be used.
In particular, a benzotriazole-based or triazine-based organic ultraviolet absorber has a high ultraviolet-absorbing ability and is excellent in heat resistance, volatilization resistance, and resin compatibility. Furthermore, the ultraviolet absorber is preferably an ultraviolet absorber having a triazine skeleton or a benzotriazole skeleton and having a molecular weight of 400 or more. The molecular weight of the ultraviolet absorber may be calculated from the structural formula thereof, or may be a number average molecular weight measured by a known method.

  The ultraviolet absorber is the following compound (3) having a hydroxyphenyltriazine skeleton or compound (4) having a benzotriazole skeleton, and these are preferably compounds having a maximum absorption at 270 nm to 400 nm. Said ultraviolet absorber is excited by absorbing light, and a hydrogen atom moves within a molecule according to the skeleton. It can return to the ground state by releasing heat. These can be shown by reaction formula (5) and reaction formula (6), respectively.

  Examples of the compound having a hydroxyphenyltriazine skeleton include 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2- Hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) -4,6-bis (2,4-dimethylphenyl)- s-triazine, 2- [2-hydroxy-4- (3-dodecyloxy-2-hydroxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- [2 -Hydroxy-4- (3-tridecyloxy-2-hydroxypropyloxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -s-tri 2- [2-hydroxy-4- [3- (2-ethylhexyloxy) -2-hydroxypropyloxy] phenyl] -4,6-bis (2,4-dimethylphenyl) -s-triazine, 2- (2-hydroxy-4-hexyloxyphenyl) -4,6-dibiphenyl-s-triazine, 2- [2-hydroxy-4- [1- (i-octyloxycarbonyl) ethyloxy] phenyl] -4,6 -Dibiphenyl-s-triazine, 2,4-bis (2-hydroxy-4-octoxyphenyl) -6- (2,4-dimethylphenyl) -s-triazine, 2,4-bis (4-butoxy- 2-hydroxyphenyl) -6- (2,4-dibutoxyphenyl) -s-triazine, 2,4,6-tris (2-hydroxy-4-octoxyphenyl) -s- Liazine, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine (trade name CYASORB (registered trademark) UV-1164 ), 2,4,6-tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine (trade name LA-F70).

  Examples of the compound having the benzotriazole skeleton include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl)- 5-chlorobenzotriazole, 2- (2′-hydroxy-3′-t-butyl-5 ′-(2- (octyloxycarbonyl) ethyl) phenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy) -3'-dodecyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amylpheny ) Benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di- (dimethylbenzyl) phenyl) benzotriazole, 2- (2′-hydroxy-4′-octyloxyphenyl) benzotriazole, 2,2′-methylene-bis (2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2- (2′- Hydroxy-3 '-(3,4,5,6-tetrahydrophthalimidylmethyl) -5'-methylbenzyl) phenyl) benzotriazole, 2- (5-chloro-2H-benzotriazol-2-yl) -6 -Tert-butyl-4-methylphenol (trade name LA-36), 2- (5-chloro-2-benzotriazolyl) -6-te t- butyl -p- cresol (trade name tinuvin (registered trademark) 326), and the like.

  And as a benzotriazole type ultraviolet absorber, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzo Triazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) benzotriazole, 2,2 Examples include '-methylenebis (4-tert-octyl-6-benzotriazolyl) phenol.

  Examples of triazine-based ultraviolet absorbers include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2 -[4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4 -Bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) ) Oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) ) Hexy And l) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.

Examples of the benzophenone-based UV absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone). ) And the like.
Examples of the benzoate-based ultraviolet absorber include phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3 ′, 5′-ditertiarybutyl-4′-hydroxybenzoate, 2,4-ditertiary Examples include amylphenyl-3 ′, 5′-ditert-butyl-4′-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate, and the like.
Examples of cyanoacrylate-based ultraviolet absorbers include ethyl-α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate, and the like.

(Gloss adjuster)
The top coat layer 2 includes inorganic particles as a gloss adjusting agent. Examples of inorganic particles include silica, clay, calcium carbonate, barium sulfate, alumina white, aluminum hydroxide, talc, bentonite, titanium oxide, and the like, anhydrous silicic acid, hydrous silicic acid, hydrous calcium silicate known as colloidal silica. And white carbon such as hydrous aluminum silicate, alumina sol and the like. In addition, surface modification with polydimethylsiloxane, polyethylene wax, surfactant, or the like is preferable because dispersibility and stain resistance are improved.

The particle diameter of the inorganic particles is preferably 1 μm or more and 20 μm or less. More preferably, they are 3 micrometers or more and 10 micrometers or less. If the particle size is smaller than 1 μm, the gloss adjustment effect may be low. On the other hand, if it is larger than 20 μm, the possibility that the filler is missing from the coat surface increases.
The pH of the inorganic particles to be blended is desirably in the vicinity of neutrality greater than 5.0 and 8.5 or less. If inorganic particles having a pH of 5.0 or less or greater than 8.5 are used, there is a possibility that a by-product may be generated due to the pKa of the light stabilizer.
Since the said inorganic particle contributes to the design (glossiness) of a decorative sheet, the quantity according to it is mix | blended (added). The blending amount of the inorganic particles may be 1 to 20 parts by mass with respect to 100 parts by mass of the resin as the main component of the top coat layer 2.

<Transparent resin layer>
The transparent resin layer 3 constitutes the base material of the topcoat layer 2 and serves as a protective layer for protecting the ink layer 5 when the ink layer 5 is provided. The transparency of the transparent resin layer 3 may be as long as the ink layer 5 is visible. In addition, as a laminated body, the transparent resin layer 3 and the topcoat layer 2 should just be provided at the minimum. When the ink layer 5 is not provided, the transparent resin layer 3 does not need to be transparent.
The transparent resin layer 3 is preferably a resin layer in which the main component of the resin is an olefin resin and a compound having a pKa of 7.0 or less is contained by 0.3 part by mass or more with respect to 100 parts by mass of the resin material. The compound having a pKa of 7.0 or less is preferably 15.0 parts by mass or less.
The compound having a pKa of 7.0 or less is, for example, the same light stabilizer and ultraviolet absorber as those compounded in the topcoat layer 2 as described above.

In the transparent resin layer 3 of the present embodiment, an embossed pattern is formed as shown in FIG.
The embossed pattern 3a is formed in order to improve design properties. The embossed pattern 3a is formed by a method of forming the embossed pattern 3a by applying heat and pressure using an embossed plate having a concavo-convex pattern before forming the topcoat layer 2, or when forming a film using an extruder. The embossed pattern 3a can be formed simultaneously with the cooling of the sheet using a cooling roll having an uneven pattern.

  The resin material used as the main component of the transparent resin layer 3 is preferably made of an olefin-based resin. -Hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1 -Nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4, 4 -Dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, -Methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) homopolymerized or copolymerized of two or more, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl Ethylene such as methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, etc. Or the thing which copolymerized alpha olefin and the monomer other than that is mentioned. Moreover, when improving the surface strength of the decorative sheet 1, it is preferable to use highly crystalline polypropylene.

The resin composition constituting the transparent resin layer 3 has various functionalities such as a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjusting agent as necessary. An additive may be contained. These various functional additives can be appropriately selected from known ones and used.
When nonpolar polypropylene is used for the transparent resin layer 3, the adhesive resin layer 7 is preferably provided when the adhesiveness between the transparent resin layer 3 and the resin layer disposed on the lower surface is low. The adhesive resin layer 7 is preferably a resin made of polypropylene, polyethylene, acrylic, or the like that is acid-modified, and the layer thickness is preferably 2 μm or more and 20 μm or less from the viewpoint of adhesion and heat resistance. The adhesive resin layer 7 is preferably formed by coextrusion laminating with the transparent resin layer 3 from the viewpoint of improving the adhesive strength.

<Ink layer and adhesive layer>
On the lower surface side of the transparent resin layer 3, as shown in FIG. 1, an adhesive layer 4 for further improving the adhesion between the ink layer 5 on the lower surface side and the transparent resin layer 3 is provided.
The material of the adhesive layer 4 is not particularly limited, but can be appropriately selected from acrylic, polyester, polyurethane, epoxy, and the like. The coating method can be appropriately selected according to the viscosity of the adhesive and the like, but generally, a gravure coat is used and applied to the raw fabric layer 6 side on which the ink layer 5 has been applied. Thereafter, the transparent resin layer 3 and the adhesive resin layer 7 are laminated. The adhesive layer 4 can be omitted when the adhesive strength between the transparent resin layer 3 and the ink layer 5 is sufficiently obtained.

An ink layer 5 is provided on the lower surface side of the adhesive layer 4. The ink layer 5 preferably contains at least a light stabilizer. It is preferable to use a hindered amine material as the light stabilizer. By including a light stabilizer in the ink layer 5, the binder resin itself forming the ink layer 5 and radicals generated by deterioration of the resin in the other layer reduce the chemical components of the pigment in the ink, thereby fading the pigment. And a colorful pattern can be maintained over a long period of time.
The ink layer 5 of the present embodiment includes a pattern pattern layer 5a and a solid ink layer 5b. And at least with respect to the pattern layer 5a, the light stabilizer is contained for the above-mentioned purpose. Further, by providing the solid ink layer 5b on the lower surface side of the picture pattern layer 5a, it is possible to provide concealment.

  The ink for the pattern layer 5a may be selected from nitrified cotton as a binder, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, etc. it can. The binder is not particularly limited such as aqueous, solvent-based, or emulsion-based, and the curing method may be a one-component type or a two-component type using a curing agent. Furthermore, you may use the method of hardening ink by active energy ray irradiation, such as an ultraviolet-ray and an electron beam. In particular, a general method is a method in which urethane-based ink is used and is cured by isocyanate. In addition to these binders, coloring agents such as pigments and dyes, extender pigments, solvents, various additives, and the like that are included in ordinary inks are included. Examples of highly versatile pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, mica and other pearls.

In the solid ink layer 5b, basically, the same material as the ink used for the pattern layer 5a can be used. However, when the ink is a transparent material, an opaque pigment, iron oxide, titanium oxide, or the like is used. be able to. In addition to this, it is possible to provide concealment properties by blending metals such as silver, copper, and aluminum. Generally, flaky aluminum is used. The solid ink layer 5b may be omitted.
These ink layers 5 can be directly formed on the original fabric layer 6 by gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, inkjet printing, or the like. Moreover, when concealing property is imparted by a metal, it is preferable to use a comma coater, knife coater, lip coater, metal vapor deposition or sputtering method.
For the interface where the resin material or ink is laminated, the surface to be laminated is subjected to corona treatment, ozone treatment, plasma treatment, electron beam in consideration of its adhesiveness before applying the resin material or ink. Adhesion between layers can be improved by performing a lamination process after activating the surface by performing surface treatment such as treatment, ultraviolet treatment, or dichromic acid treatment.

<Original fabric layer>
On the lower surface side of the ink layer 5, an original fabric layer 6 serving as a base material layer is provided. The raw fabric layer 6 is made of paper such as thin paper, titanium paper, resin-impregnated paper, polyethylene, polypropylene, polystyrene, polybutylene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic or other synthetic resin, or These synthetic resin foams, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, rubber such as polyurethane, organic or inorganic nonwoven fabric, synthetic paper, aluminum, It can be arbitrarily selected from metal foils such as iron, gold and silver.

Further, when an olefin resin is used as the raw fabric layer 6, the surface is often in an inactive state, and therefore a base material (not shown) to which the original fabric layer 6 and the decorative sheet 1 are attached is provided. It is preferable to provide a primer layer (not shown) between them. In addition to this, in order to improve the adhesion between the raw fabric layer 6 made of an olefin resin and the substrate, the back surface of the raw fabric layer 6 is subjected to corona treatment, plasma treatment, ozone treatment, electron beam treatment. It is preferable that ultraviolet treatment or dichromic acid treatment is performed.
In addition, as a primer layer, although the same material as the ink layer 5 can be applied, in consideration of winding up the decorative sheet 1 in a web shape, in order to avoid blocking and to improve the adhesion to the adhesive. Inorganic fillers such as silica, alumina, magnesia, titanium oxide or barium sulfate are preferably contained.
In the decorative sheet 1 of the present embodiment, the raw fabric layer 6 is 20 μm to 150 μm in consideration of printing workability, cost, etc., the adhesive layer 4 is 1 μm to 20 μm, the transparent resin layer 3 is 20 μm to 200 μm, and the topcoat layer. 2 is preferably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 45 μm to 400 μm.

<About other functions>
Since the ultraviolet absorber and the light stabilizer require intermolecular interaction, it is preferable that they are present close to each other. Here, let us look at the interaction when using a triazine skeleton or benzotriazole skeleton UV absorber and a hindered amine skeleton light stabilizer. In general, the intermolecular interaction between the UV absorber and the light stabilizer occurs between the conjugated system of the UV absorber and the hindered amine skeleton of the light stabilizer. Ultraviolet absorbers have a high probability of existence of intramolecular hydrogen bonds on the nitrogen of the triazine skeleton or benzotriazole skeleton upon light absorption. In other words, the hydrogen on the hydroxyl group is easily dissociated.

  By coexisting with a light stabilizer having a pKa greater than 7.0, the ultraviolet absorber that absorbs light and is in an excited state is liable to cause a side reaction through an acid-base reaction with the light stabilizer. That is, the reaction of the reaction formula (2), the reaction formula (5), and the reaction formula (6) in which the ultraviolet absorber and the light stabilizer are originally generated cannot be performed and the side reaction increases. In other words, it is easily decomposed by light, leading to a decrease in weather resistance. On the other hand, when a light stabilizer having a pKa of 7.0 or less is used, an acid-base reaction with hydrogen on the hydroxyl group of the ultraviolet absorber that is in an excited state is absorbed. The agent is likely to undergo the reactions of Reaction Formula (2), Reaction Formula (5), and Reaction Formula (6). Therefore, the weather resistance with respect to light can be improved.

In view of such a situation, in the present embodiment, by adding a light stabilizer having a pKa of 4.0 to 7.0 in the resin composition constituting the topcoat layer 2, the topcoat layer 2 is stable over a long period of time. A laminate and a decorative sheet 1 having weather resistance can be provided.
Further, as in this embodiment, by containing a light stabilizer having a pKa of 4.0 to 7.0 in the resin composition of the topcoat layer 2, the topcoat layer 2 contains an inorganic as a gloss adjusting agent. A decrease in weather resistance due to the blending of the particles can be prevented. This is because when the light stabilizer has a pKa greater than 7.0, the vicinity of the top coat layer 2 in contact with the surface of the inorganic particles is liable to cause a side reaction due to an acid-base reaction, and the light stabilizer in the top coat layer 2 This is because the ratio of the value is likely to decrease. Therefore, it is preferable to use a light stabilizer having a pKa of 7.0 or less as the light stabilizer to be blended in the top coat layer 2.

  Moreover, the residual monomer derived from material raw materials in the topcoat layer 2 by containing the light stabilizer of pKa 4.0-7.0 in the resin composition of the topcoat layer 2 like this embodiment. Etc., it is possible to prevent a decrease in weather resistance. This is because when the pKa of the light stabilizer is larger than 7.0, a side reaction is likely to occur due to an acid-base reaction in the vicinity of the residual monomer, and the ratio of the light stabilizer in the topcoat layer 2 is likely to decrease. It is to become. Therefore, it is preferable to use a light stabilizer having a pKa of 7.0 or less.

(Measurement method of pKa of light stabilizer)
A 0.1N perchloric acid / dioxane acetonitrile: chloroform = 1: 1 solution was dropped into an organic reference substance having a known pKa value in an aqueous system, and the semi-neutralization potential (HNP) in the non-aqueous system was titrated. At that time, a plot of an HNP calibration curve against pKa was created. Subsequently, the light stabilizer was titrated in the same manner, and the corresponding pKa was determined from the calibration curve plot.

(Measurement method of pKa during light absorption of UV absorber)
Here, the ultraviolet absorber was dissolved in acetonitrile so that the absorbance at the maximum absorption wavelength was 1, and bubbled with nitrogen for 15 minutes. Thereafter, 70% perchloric acid was added dropwise to the solution to change the pH of the solution. At that time, the absorption spectrum of the solution was measured, and the UV absorber at each pH and the benzotriazole skeleton of the UV absorber or the nitrogen added to the nitrogen of the triazine skeleton were calculated from the absorbance at λmax. From the point where the values become equal, the pKa at the time of light absorption of the ultraviolet absorber was determined. A U-4000 spectrophotometer manufactured by Hitachi High-Tech was used for the measurement of the absorption spectrum.

(Method for measuring pH of silica particles)
Measurement was performed in accordance with JIS. First, 200 g of purified water is added to 10 g of silica particles dried at 170 ° C. for 2 hours under the atmosphere, and covered with a watch glass. Then, after heating and stirring at 80 ± 3 ° C. for 1 hour, the solution is cooled to room temperature and the supernatant is recovered. The supernatant was cooled to 25 ° C. and then measured using an analog pH meter HM-7J (manufactured by Toa DKK Corporation) in accordance with JISZ8802.

Below, the specific example of the laminated body and decorative sheet based on this invention is demonstrated.
<Example 1>
0.5 parts by mass of a hindered phenolic antioxidant (Irganox 1010; manufactured by BASF) and triazine ultraviolet absorber (CYASORB UV-1164; manufactured by SUNCHEM) with respect to 100 parts by mass of the highly crystalline homopolypropylene resin And 0.5 parts by mass of a NOR type light stabilizer (Tinvin XT850 FF; manufactured by BASF) were melt-extruded using an extruder to obtain a transparent high 100 μm thickness. A sheet-like transparent resin layer 3 as a crystalline polypropylene sheet was formed. And the corona treatment was given to both surfaces of the obtained transparent resin layer 3, and the wet tension of the sheet | seat surface was 40 dyn / cm or more.

On the other hand, pattern printing was performed on one side of a concealing 80 μm polyethylene sheet (raw fabric layer 6) using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.) by a gravure printing method. A pattern layer 5a was provided, and a primer coat was applied to the other surface of the original fabric layer 6.
Thereafter, the transparent resin layer 3 is dried on the surface of the pattern layer 5a of the original fabric layer 6 through an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc .; coating amount 2 g / m ² ). Bonding was performed by a laminating method. The embossed pattern 3a was applied to the surface of the transparent resin layer 3 of the bonded sheet.
The top coat layer 2 is formed on the transparent resin layer 3 having the embossed pattern 3a by applying and drying the following composition for forming the top coat layer at a coating thickness of 3 g / m ² , and the total thickness is 185 μm. A decorative sheet 1 of Example 1 was obtained.

(Composition for forming top coat layer A)
The composition for forming the topcoat layer A was constituted by blending the following polymer solution A with the following curing agent, gloss adjuster, ultraviolet absorber, and light stabilizer.
・ Polymer solution A
Into a four-necked flask equipped with a stirrer, a nitrogen introducing tube and a reflux condenser, 80 g of methyl methacrylate and 20 g of 2-hydroxyethyl methacrylate are introduced and dissolved by adding 70 g of ethyl acetate, and a nitrogen atmosphere on an oil bath Stirred under. Polymerization is started by adding 0.2 g of α, α'-azobisisobutyronitrile to this, and the mixture is heated and stirred on an oil bath at 60 ° C. for 5 hours to obtain a colorless and viscous polymer solution A. Got.
・ Curing agent Product name: Duranate 24A-100
Formulation: 5 parts by mass / gloss modifier (inorganic particles)
Product name: P-801 (Mizusawa Chemical Co., Ltd.)
Properties: irregular shape, average particle size 6.0 μm, pH 6.8
Formulation: 10 parts by mass UV absorber Product name: Tinuvin 329 (BASF)
Formulation: 2.5 parts by mass / light stabilizer
Product name: Tinuvin 123 (BASF)
Formulation: 1.5 parts by mass

<Example 2>
A decorative sheet 1 of Example 2 was obtained in the same manner as in Example 1 except that the gloss modifier of Example 1 was replaced with C-402 (Mizusawa Chemical Co., Ltd.).
<Example 3>
A decorative sheet 1 of Example 3 was obtained in the same manner as in Example 1 except that the gloss modifier of Example 1 was replaced with NP-8 (Mizusawa Chemical Co., Ltd.).

<Example 4>
A decorative sheet 1 of Example 4 was obtained in the same manner as in Example 1 except that the type of light stabilizer of Example 1 was Tinuvin 152 (manufactured by BASF).
<Example 5>
A decorative sheet 1 of Example 5 was obtained in the same manner as in Example 2 except that the type of light stabilizer of Example 2 was Tinuvin 152 (manufactured by BASF).

<Example 6>
A decorative sheet 1 of Example 6 was obtained in the same manner as Example 3 except that the type of light stabilizer of Example 3 was Tinuvin 152 (manufactured by BASF).
<Example 7>
A decorative sheet 1 of Example 7 was obtained in the same manner as in Example 1 except that the blending amount of the light stabilizer of Example 1 was changed to 0.5 parts by mass.

<Example 8>
A decorative sheet 1 of Example 8 was obtained in the same manner as Example 1 except that the blending amount of the light stabilizer of Example 1 was changed to 3.0 parts by mass.
<Example 9>
A decorative sheet 1 of Example 9 was obtained in the same manner as Example 1 except that the blending amount of the light stabilizer of Example 1 was 15.0 parts by mass.

<Comparative Examples 1-3>
The decorative sheets 1 of Comparative Examples 1 to 3 were obtained in the same manner as in Example 1 except that the light stabilizers of Examples 1 to 3 were replaced with Tinuvin 292 (manufactured by BASF).
<Comparative example 4>
A decorative sheet 1 of Comparative Example 4 was obtained in the same manner as Example 1 except that the light stabilizer of Example 1 was not blended.

  Table 1 shows the light stabilizers and gloss modifiers used. In addition, Table 1 also describes the evaluation results.

Moreover, based on Example 1, the topcoat layer was changed and the decorative sheets of the following Examples 10 to 18 were produced.
<Example 10>
The decorative sheet of Example 10 which consists of the topcoat layer B which changed the composition for topcoat layer formation of Example 1 into the following was obtained.
(Composition for forming the topcoat layer B)
The composition for forming the topcoat layer B was constituted by blending the following resin liquid A with the following initiator, gloss modifier, ultraviolet absorber, and light stabilizer.
・ Resin liquid A
Product name: M405 (Toagosei)
・ Initiator Product name: Irgcure 184 (manufactured by BASF)
Formulation: 5 parts by mass-Gloss modifier (inorganic particles) Same as Example 1-Ultraviolet absorber Same as Example 1-Light stabilizer Same as Example 1

<Example 11>
The top coat layer A of Example 1 is coated with a top coat layer C which is the same as that of Example 1 except that the polymer solution A of Example 1 is replaced with the polymer solution B. Eleven decorative sheets were obtained. The method for preparing the polymer solution B was described below.
・ Polymer solution B
Into a four-necked flask equipped with a stirrer, a nitrogen introduction tube and a reflux condenser, 50 g of methyl methacrylate and 50 g of 2-hydroxyethyl methacrylate are introduced and dissolved by adding 70 g of ethyl acetate. Stirred under. Polymerization was started by adding 0.2 g of α, α'-azobisisobutyronitrile to this, and the mixture was heated and stirred for 5 hours in an oil bath at 60 ° C. to obtain a colorless and viscous polymer solution B Got.

<Example 12>
The topcoat layer B used in Example 10 was coated on the topcoat layer A of Example 1 to obtain a decorative sheet of Example 12 consisting of two layers.

<Example 13>
The decorative sheet of Example 13 which consists of the topcoat layer D which changed the composition for topcoat layer formation of Example 1 into the following was obtained.
(Composition for forming the topcoat layer D)
The composition for forming the top coat layer D was constituted by blending the following resin liquid B with the following curing agent, initiator, gloss adjusting agent, ultraviolet absorber, and light stabilizer.
・ Resin liquid B
50 parts by mass of polymer liquid A and resin liquid A were blended to obtain resin liquid B.
・ Initiator Product name: Irgcure 184 (manufactured by BASF)
Formulation: 5 parts by mass / curing agent Product name: Duranate 24A-100
Formulation: 5 parts by mass-Gloss modifier (inorganic particles) Same as Example 1-Ultraviolet absorber Same as Example 1-Light stabilizer Same as Example 1

<Example 14>
The topcoat layer D used in Example 13 was coated on the topcoat layer A of Example 1 to obtain a decorative sheet of Example 14 consisting of two layers.

<Example 15>
The topcoat layer D of Example 13 was coated on topcoat layer D of Example 13 with the topcoat layer E changed as follows to obtain a decorative sheet of Example 15 consisting of two layers.
(Composition for forming topcoat layer E)
The composition for forming the top coat layer E was constituted by blending the following resin liquid C with the following curing agent, initiator, gloss adjusting agent, ultraviolet absorber, and light stabilizer.
・ Resin liquid C
A resin liquid C was obtained by blending 20 parts by mass of the polymer liquid B and 80 parts by mass of the resin liquid A.
Initiator Same as Example 10 Curing agent Same as Example 10 Gloss modifier (inorganic particles) Same as Example 1 Ultraviolet absorber Same as Example 1 Light stabilizer Same as Example 1

<Example 16>
The topcoat layer B used in Example 10 was coated on the topcoat layer D of Example 13 to obtain a decorative sheet of Example 16 consisting of two layers.
<Example 17>
On the topcoat layer of Example 1, the coats used in Example 13 and Example 10 were sequentially laminated to obtain a decorative sheet of Example 17 consisting of three layers.
<Example 18>
The top coat layer of Example 11 was coated with that used in Example 10 to obtain a decorative sheet of Example 18 consisting of three layers.

In Table 2, it shows about the layer structure of the topcoat layer of Example 1, Examples 10-18, the used light stabilizer, and the glossiness regulator. In addition, Table 2 also describes the evaluation results.
Here, in the layer structure, “heat” represents a thermosetting layer, “UV” represents a photocuring layer, and “UV / heat” represents a mixed layer of a photocuring resin and a thermosetting resin.

<Evaluation>
(Weather resistance (appearance))
The decorative sheets obtained in Examples and Comparative Examples were set in a metal weather manufactured by Daipura Wintes Co., Ltd., and the light conditions (illuminance: 60 mW / cm ² , black panel temperature 63 ° C., inner layer humidity 50% RH) were 20 Weather resistance for 500 hours or 1000 hours under conditions of time, condensation conditions (illuminance: 0 mW / cm ² , black panel temperature 30 ° C., in-layer humidity 98% RH) for 4 hours, water spray conditions (10 seconds before and after the condensation conditions) A sex test was performed. After the above test, after maintaining for 2 days under conditions of 25 ° C. and 50% RH, appearances such as cracks and yellowing on the plate surface were visually evaluated according to the following criteria.

(Appearance of coating film)
○: No change in appearance.
Δ: There were fine cracks on the surface.
X: There were innumerable cracks on the surface.
(Substrate yellowing)
○: No change in appearance.
Δ: Some yellowing was observed.
X: Yellowish remarkably.

In the decorative sheet of each example, as shown in Table 1, the gloss after the weather resistance test is generated without causing haze by combining a light stabilizer having a pKa of 4.0 to 7.0 and blending it with the resin. As a result, it was possible to produce a decorative sheet that could suppress the change in the degree and that hardly caused the appearance change.
As can be seen from Tables 1 and 2, when a light stabilizer having a pKa value greater than 7.0 is blended in the surface protective layer, the pKa value is from 4.0 for both the coating film appearance and the base material yellowing. It was worse than the case where 7.0 light stabilizer was used. In addition, when 15.0 parts by mass of the light stabilizer was blended, the coating film had haze at the time of production, but no change in appearance or yellowing of the resin was observed before and after the weather resistance test. This is because ultraviolet absorbers and light stabilizers bleed out on the surface protective layer and the haze value increased, but it is considered that the performance was exhibited because sufficient weathering agents were included.

From the above results, it can be seen that the decorative sheet 1 of the example based on the present invention is excellent in weather resistance.
The decorative sheet 1 of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the characteristics of the invention.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Top coat layer 3 Transparent resin layer 3a Embossed pattern 4 Adhesive layer 5 Ink layer 5a Picture pattern layer 5b Solid ink layer 6 Original fabric layer (base material layer)
7 Adhesive resin layer

Claims (7)

A laminate composed of a plurality of resin layers,
A laminate comprising a light stabilizer having a pKa of 4.0 to 7.0 in a topcoat layer located on the outermost surface side of the laminate.   The laminate according to claim 1, wherein the light stabilizer is a hindered amine light stabilizer.   The laminate according to claim 1 or 2, wherein the top coat layer contains a gloss modifier made of inorganic particles.   The laminate according to claim 3, wherein the inorganic particles are inorganic particles having a pH of greater than 5.0 and not greater than 8.5 when dispersed.   The said topcoat layer is equipped with the thermosetting layer and the photocuring layer formed on the said thermosetting layer, The laminated body of any one of Claims 1-4 characterized by the above-mentioned. An olefin resin layer that is a resin layer in which the main component of the resin is an olefin resin and a pKa of 7.0 or less is contained in an amount of 0.3 parts by mass or more with respect to 100 parts by mass of the resin material;
The laminate according to any one of claims 1 to 5, wherein the topcoat layer is formed on the olefin resin layer.   A decorative sheet comprising the laminate according to any one of claims 1 to 6.

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