JP6863502B1 - Decorative member and manufacturing method of decorative member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative member having excellent weather resistance and reducing white turbidity which is a factor impairing design, and a method for manufacturing the decorative member. A decorative member (11) according to one aspect of the present invention includes a base material (7) and a decorative sheet (10) formed on the base material (7), and the decorative sheet (10) includes a transparent thermoplastic resin layer (4). The transparent thermoplastic resin layer 4 contains a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by a specific formula. [Selection diagram] Fig. 1

Description

The present invention relates to a decorative member and a method for manufacturing the decorative member, and in particular, a decorative member used for building materials such as building interiors and exteriors, surface and frame materials of fittings, surface materials of home appliances, and flooring materials. And a method for manufacturing a decorative member.

Some decorative sheets used as building materials for exteriors do not have high resistance to ultraviolet rays and water. For this reason, in applications that require resistance (weather resistance) to these, such as decorative sheets for exteriors and decorative members for exteriors, a transparent protective film (surface protective layer) is provided on the surface layer for the purpose of protecting printed matter. ..
As the material of the transparent protective film, fluororesin and acrylic resin having excellent weather resistance, as well as polyolefin, which is advantageous in terms of cost, are preferably used. However, since polyolefin often lacks weather resistance, UV absorbers and the like are used. Additives are commonly used. As an ultraviolet absorber having excellent performance of imparting weather resistance, for example, a hydroxyphenyltriazine compound has been proposed (Patent Documents 1 and 2). However, in the application of the hydroxyphenyltriazine-based ultraviolet absorber to polyolefin, not only the weather resistance of the transparent film differs depending on the structure of the ultraviolet absorber, but also the designability of the printed matter may be deteriorated due to white turbidity.

U.S. Patent Application Publication No. 2004/0241111 U.S. Pat. No. 6,191,199

An object of the present invention is to provide a decorative member having excellent weather resistance and reducing white turbidity, which is a factor impairing design, and a method for manufacturing the decorative member, in response to the above-mentioned problems.

In order to solve the above problems, the decorative member according to one aspect of the present invention is a decorative member including a base material and a decorative sheet formed on the base material, and the decorative sheet is transparent thermoplastic. The transparent thermoplastic resin layer including the resin layer is characterized by containing a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (1).

(In the general formula (1), R1 to R3 are independent of each other and represent a hydrogen atom or a methyl group or a phenyl group or an alkoxy group, and at least two are alkoxy groups having 8 to 18 carbon atoms, and R4 and R5 are respectively. Independently, they indicate a hydroxyl group or a methyl group or a hydrogen atom, and R6 to R8 are independent and indicate a methyl group or a hydrogen atom, respectively.)
The decorative member according to another aspect of the present invention is characterized in that the hydroxyphenyltriazine-based ultraviolet absorber has a structure represented by the following general formula (2).

(In the general formula (2), R1 and R2 represent an alkoxy group having 8 to 18 carbon atoms, R3 represents an alkoxy group having 1 to 4 carbon atoms, R4 represents a hydroxyl group, and R5 to R8 represent a hydrogen atom.)
The decorative member according to another aspect of the present invention is characterized in that the hydroxyphenyltriazine-based ultraviolet absorber has a structure represented by the following formula (3).

Further, the decorative sheet of the decorative member according to one aspect of the present invention further includes a surface protective layer formed on a surface of the transparent thermoplastic resin layer opposite to the base material side, and the transparent heat. An uneven pattern is formed on the surface of the plastic resin layer in contact with the surface protective layer, and the surface protective layer is embedded in the concave portion forming the uneven pattern.
Further, the method for manufacturing a decorative member according to one aspect of the present invention includes a step of forming a concavo-convex pattern on the surface of the transparent thermoplastic resin layer by embossing and a surface of the transparent thermoplastic resin layer having the concavo-convex pattern formed. The step of forming the surface protective layer is characterized by embedding the surface protective layer in the recesses constituting the uneven pattern of the transparent thermoplastic resin layer. To do.

According to one aspect of the present invention, it is possible to provide a decorative member having excellent weather resistance and reducing white turbidity, which is a factor impairing design, and a method for producing the decorative member.

It is sectional drawing which shows one structural example of the decorative sheet and the decorative member which concerns on embodiment of this invention.

(Composition of decorative sheet and decorative member)
Hereinafter, the decorative sheet and the decorative member according to the embodiment of the present invention will be described in detail with reference to the drawings, but if they are within the scope of the present invention, they do not necessarily have to be laminated in this order. Further, a layer not shown in this drawing may be added.
FIG. 1 shows a cross-sectional structure of an embodiment of a decorative sheet and a decorative member according to the present embodiment.
The decorative sheet 10 according to the present embodiment is obtained by laminating a colored thermoplastic resin layer 1, a pattern layer 2, an adhesive resin layer 3, a transparent thermoplastic resin layer 4, and a surface protective layer 5 in this order. A concavo-convex pattern is formed on the surface of the transparent thermoplastic resin layer 4, and the resin constituting the surface protective layer 5 is embedded in the recesses (recessed portions) 8 forming the concavo-convex pattern. Further, all the surfaces forming the recess 8 may be covered with the resin forming the surface protective layer 5.
The decorative member 11 according to the present embodiment is a stack of a base material 7, an adhesive layer 6, and a decorative sheet 10 in this order.
Hereinafter, the configuration of each layer described above will be described in detail.

[Surface protective layer]
The surface protective layer 5 according to the present embodiment is a layer provided for imparting functions such as weather resistance, scratch resistance, stain resistance, and design to the decorative sheet 10. The material constituting the surface protective layer 5 is not particularly limited, and for example, a resin material such as urethane-based, acrylic-based, acrylic silicon-based, fluorine-based, and epoxy-based can be appropriately selected and used.
The surface protective layer 5 contains various additives such as an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, if necessary. You may. Hereinafter, an example of the surface protective layer 5 according to the present embodiment will be described with reference to specific examples.

The surface protective layer 5 according to the present embodiment may contain, for example, an acrylic resin composition containing cyclohexyl (meth) acrylate as a monomer component as a main component. In addition, in this embodiment, cyclohexyl (meth) acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By containing cyclohexyl (meth) acrylate as a monomer component, the affinity for water can be lowered, and deterioration due to hydrolysis or the like can be suppressed.

Regarding the content of cyclohexyl (meth) acrylate, among all the monomer components of the acrylic resin composition, that is, among the monomer components of the acrylic resin composition which is the main component of the surface protective layer 5, cyclohexyl (meth) acrylate Is preferably in the range of 5% by mass or more and 50% by mass or less. By setting the content of cyclohexyl (meth) acrylate to 5% by mass or more, a sufficient deterioration suppressing effect can be obtained. Further, by setting the content of cyclohexyl (meth) acrylate to 50% by mass or less, various performances of the surface protective layer 5 of the decorative sheet such as maintenance of surface hardness, improvement of stain resistance and adjustment of surface gloss are not significantly changed. , It becomes possible to impart high weather resistance over time. Here, the above-mentioned "main component" means that the content of the acrylic resin composition constituting the surface protective layer 5 is 50% by mass or more with respect to the mass of the entire surface protective layer 5. ..

As the monomer component of the acrylic resin composition that can be used for the surface protective layer 5 according to the present embodiment, in addition to cyclohexyl (meth) acrylate, for example, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, etc. Cyclohexylpropyl (meth) acrylate, cyclohexylbutyl (meth) acrylate, dimethylcyclohexanemono (meth) acrylate, dimethylcyclohexanedi (meth) acrylate, trimethylcyclohexanemono (meth) acrylate, trimethylcyclohexanedi (meth) acrylate, trimethylcyclohexanetri ( Meta) acrylate, tetramethylcyclohexane mono (meth) acrylate, tetramethylcyclohexanedi (meth) acrylate, tetramethylcyclohexanetri (meth) acrylate, tetramethylcyclohexanetetra (meth) acrylate, dicyclohexylmethyl (meth) acrylate, dicyclohexylmethyl (meth) Examples thereof include meta) acrylate, phenoxycyclohexylmethyl (meth) acrylate, and methoxycyclohexylmethyl (meth) acrylate. Among these, those containing isomers may be each isomer alone and / or a mixture of each isomer.

Further, in the present embodiment, the surface protective layer 5 is coated with a coating liquid containing the above-mentioned acrylic resin composition containing cyclohexyl (meth) acrylate as a monomer component and a weathering agent such as an ultraviolet absorber described later. It may be formed by coating on the outermost surface of the sheet. For example, a coating liquid containing the above-mentioned acrylic resin composition and a weather resistant agent is applied onto the transparent thermoplastic resin layer 4 provided with the recesses 8 and then wiped to enter the coating liquid in the recesses 8. May be embedded to form the surface protective layer 5.
Examples of the curing method of the coating liquid for forming the surface protective layer 5 include a one-component curing type, a two-component curing type using a curing agent, and an active energy ray-curing type that cures by irradiating ultraviolet rays, ionizing radiation, or the like. Any of these can be used, but in consideration of weather resistance, a two-component curing type or an active energy ray-curing type is preferable, and if consideration is given to post-workability after being bonded to various substrates to form a decorative member, A two-component curing type that is crosslinked by isocyanate curing is desirable.

The two-component curable type acrylic resin composition includes, for example, an acrylic resin having two or more functional groups of one or more selected from a hydroxyl group, an amino group and a carboxyl group in one molecule, and reacting with the functional groups. A composition containing a polyisocyanate compound having two or more possible isocyanate groups in one molecule is preferable. A composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound is particularly preferable.

Examples of the acrylic polyol having two or more hydroxyl groups in one molecule include a (meth) acrylic acid ester copolymer containing hydroxyethyl (meth) acrylate as a monomer component in addition to the above-mentioned cyclohexyl (meth) acrylate. Available. On the other hand, examples of the polyisocyanate compound having two or more isocyanate groups in one molecule include tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and hydrogenation thereof. Examples thereof include a compound, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), a trimester type obtained by synthesizing one or more kinds of compounds selected from these compounds by a known technique, a TMP adduct type, a bullet type and the like. In addition, a composition obtained by mixing one or more selected from these different types of polyisocyanates can be used. Among them, HDI or HDI trimer type, TMP adduct type, and burette type are preferable from the viewpoint of weather resistance. The content of the isocyanate compound with respect to the resin component described above can be arbitrarily set, but it is desirable to set the equivalent ratio of the hydroxyl group / isocyanate group to about 1/1 to 1/3. In particular, when the equivalent of the hydroxyl group is larger than the equivalent of the isocyanate group, the cross-linking does not proceed sufficiently and the desired performance is not added to the surface protective layer 5, which may not be preferable.

When the curing method of the coating liquid for forming the surface protective layer 5 is active energy ray curing, a monomer or oligomer having a (meth) acryloyl group known as an active energy ray curing type acrylic resin composition is used. Etc. can be used, and in addition to these monomers and oligomers, the above-mentioned cyclohexyl (meth) acrylate may be blended.

<UV absorber>
In order to further improve the weather resistance of the decorative sheet 10, a weather resistant agent such as an ultraviolet absorber or a radical scavenger may be added to the surface protective layer 5. As the ultraviolet absorber, known ones such as benzotriazole type, hydroxyphenyltriazine type and benzophenone type can be used. If a hydroxyphenyltriazine-based UV absorber is selected among them, the triazine skeleton suppresses bleeding, and the triazine skeleton is compared with the skeleton of benzotriazole-based UV absorbers and benzophenone-based UV absorbers. Due to its chemical stability and the like, it is possible to maintain the ultraviolet absorption performance for a long period of time.

Examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy]. Pphenol, 2- (2hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-) 1,3,5-Triazine-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2-ethyl-hexanoic acid, 2- [4- (4,6-diphenyl- [1,3,5] ] Triazine-2-yl) -3-hydroxy-phenoxy] -ethyl ester, octanoic acid, 2- [4- (4,6-diphenyl- [1,3,5] triazine-2-yl) -3 -Hydrazine-phenoxy] -ethyl ester, 2,4,6-tris {2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl)} -1,3,5-triazine, 2,4- Bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) -1,3,5-triazine, 2,4-bis (2,4-dimethylphenyl) -6 -(2-Hydroxy-4-iso-octyloxyphenyl) -s-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl)- Examples thereof include 1,3,5-triazine. In the present embodiment, the surface protective layer 5 has 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5- Triazine (hereinafter, referred to as "ultraviolet absorber A" for convenience) may be contained. In addition, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, which was used as the ultraviolet absorber A, was used. It is generally known as the main component of "Chinubin 479: manufactured by BASF Japan Ltd."

In the present embodiment, the amount of the above-mentioned hydroxyphenyltriazine-based ultraviolet absorber added is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition. By adding the above-mentioned ultraviolet absorber to 1 part by mass or more, the effect of improving weather resistance is exhibited, and by setting it to 30 parts by mass or less, the effect on physical properties other than the weather resistance of the surface protective layer 5 is practically used. It can be suppressed to a level that does not cause any problems.
In particular, when the above-mentioned ultraviolet absorber A is used as the ultraviolet absorber to be added to the surface protective layer 5, the amount added is 1 part by mass or more and 20 parts by mass with respect to 100 parts by mass of the acrylic resin composition. It is preferably within the following range, more preferably within the range of 5 parts by mass or more and 15 parts by mass or less, and further preferably within the range of 8 parts by mass or more and 12 parts by mass or less. When the amount of the ultraviolet absorber A added is 1 part by mass or more, the effect of improving the weather resistance is exhibited, and when it is 20 parts by mass or less, the influence on the physical properties other than the weather resistance of the surface protective layer 5 is practically problematic. It can be suppressed to a level that does not exist.

Further, in the present embodiment, as the hydroxyphenyltriazine-based ultraviolet absorber in the surface protective layer 5, the ultraviolet absorber A and 2- (4,6-diphenyl-1,3,5-triazine-2-yl) are used. ) -5- [2- (2-Ethylhexanoyloxy) ethoxy] phenol (hereinafter, referred to as "ultraviolet absorber B" for convenience) is used in combination to provide even better weather resistance. This is because the ultraviolet absorber B has a high ability to absorb ultraviolet rays in the short wavelength region, which has a relatively high energy among ultraviolet rays, and is chemically compared with other ultraviolet absorbers that absorb almost the same wavelength region. This is because it is stable and the wavelength range in which ultraviolet rays are absorbed becomes wider when used in combination. The 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol used as the ultraviolet absorber B is ". ADEKA STUB LA-46: Generally known as the main component of "Made by ADEKA Corporation".

In the present embodiment, the amount of the ultraviolet absorber A added is preferably in the range of 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the ultraviolet absorber B, and is 20 parts by mass or more and 100 parts by mass. It is more preferably within the range of 40 parts by mass or less, and further preferably within the range of 40 parts by mass or more and 80 parts by mass or less. By setting the addition amount of the ultraviolet absorber A within the above numerical range, further excellent weather resistance can be imparted.

(Modification example)
Although the hydroxyphenyltriazine-based ultraviolet absorbers that can be added to the surface protective layer 5 have been described above, the hydroxyphenyltriazine-based ultraviolet absorbers that can be used in the present embodiment are not limited thereto. The surface protective layer 5 according to the present embodiment may contain, for example, a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (1). Further, the surface protective layer 5 may contain an ultraviolet absorber having a structure represented by the following general formula (2). Specifically, it contains 2,4-bis [2-hydroxy-4- (2-ethylhexyloxy) phenyl)] -6- (4-methoxyphenyl) -s-triazine represented by the following formula (3). It may contain a hydroxyphenyltriazine-based ultraviolet absorber represented by the following formula (4).

In the general formula (1), R1 to R3 are independent, exhibiting a hydrogen atom or a methyl group, a phenyl group or an alkoxy group, and at least two are alkoxy groups having 8 to 18 carbon atoms which do not contain a carbonyl group. , R4 and R5 are independent and represent a hydroxyl group or a methyl group or a hydrogen atom, and R6 to R8 are independent and represent a methyl group or a hydrogen atom, respectively.

In the general formula (2), R1 and R2 represent an alkoxy group having 8 to 18 carbon atoms, R3 represents an alkoxy group having 1 to 4 carbon atoms, R4 represents a hydroxyl group, and R5 to R8 represent a hydrogen atom.

Further, by using a hydroxyphenyltriazine type and a benzotriazole type as the ultraviolet absorber in combination, further excellent weather resistance can be imparted by the interaction thereof. This is because the benzotriazole-based UV absorber has an absorption peak on the longer wavelength side than the hydroxyphenyltriazine-based UV absorber, so that the wavelength range in which UV rays are absorbed is further widened by the combined use. .. The amount of the benzotriazole-based ultraviolet absorber to be added is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition, and by adding 1 part by mass or more, The desired effect can be obtained, and the bleed-out of the weather resistant agent can be suppressed by setting the content to 30 parts by mass or less. However, the benzotriazole-based ultraviolet absorber may be yellowish because it has an absorption peak on the long wavelength side, and when it is necessary to pay attention to the hue, it is preferable to suppress the addition amount.

Examples of the benzotriazole-based ultraviolet absorber include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2- (2'-hydroxy-3', 5'-ditertiary butylphenyl)-. 5-Chlorobenzotriazol, 2- (2'-hydroxy-3'-tertiary butyl-5'-methylphenyl) -5-chlorobenzotriazol, 2- (2'-hydroxy-5' -Third octylphenyl) benzotriazol, 2- (2'-hydroxy-3', 5'-dicumylphenyl) benzotriazol, 2,2'-methylenebis (4-third octyl-6- (benzotria) Zoryl) phenol), 2- (2'-hydroxy-3'-third butyl-5'-carboxyphenyl) benzotriazole and the like, but are not limited thereto.

<Radical scavenger>
Further, by using a hindered amine-based radical scavenger in combination, the weather resistance performance of the decorative sheet 10 can be further improved. Examples of the hindered amine-based radical trapping agent that can be used in the present embodiment include bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl. -4-piperidyl sebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2 6,6-Pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2) , 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2 , 3,4-Butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) ) -2-Butyl-2- (3,5-ditertiary butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / Diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1 , 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tertiary octylamino-s-triazine polycondensate, 1,5,8,12 -Tetrakiss [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5,8,12 -Tetraazaddecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine -6-yl] -1,5,8-12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-) 4-Piperidyl) amino) -s-triazine-6-yl] a Minoundecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine-6-yl ] Aminoundecane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butylmalonate cyclohexane Reaction product of N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro 1,3,5-triazine and 2-aminoethanol However, it is not limited to this.

The amount of the hindered amine-based radical scavenger added is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition, and it is desired to add 1 part by mass or more. The effect of the above can be obtained, and by setting the content to 30 parts by mass or less, the bleed-out of the weather resistant agent can be suppressed, and the influence on other physical properties of the surface protective layer 5 can be suppressed.

As for the thickness of the surface protective layer 5 in the present embodiment, if the amount of the ultraviolet absorber added is the same, a thicker film can obtain better weather resistance, but the flexibility of the decorative sheet 10 is impaired. , Problems such as easy cracking in the surface layer of the decorative sheet 10 during post-processing or the like are likely to occur. On the contrary, if the thin film is thinned, there is a problem that the weather resistance performance is impaired. Therefore, the thickness of the surface protective layer 5 is preferably in the range of 2 μm or more and 20 μm or less. For the same reason, if the total thickness of the decorative sheet 10 is within the range of 40 μm or more and 300 μm or less, both weather resistance and post-processability can be achieved.

As a method of providing the surface protective layer 5 in the present embodiment, various known coating methods such as a gravure coat, a reverse coat, a gravure reverse coat, a die coat, and a flow coat can be used. Further, various additives such as an anti-friction agent, an anti-blocking agent, and an anti-static agent may be added to the surface protective layer 5 in the present embodiment, if necessary.

[Transparent thermoplastic resin layer]
The transparent thermoplastic resin layer (olefin resin layer) 4 can be provided as needed to protect the pattern layer 2, and may be transparent or translucent as long as the pattern can be utilized. Alternatively, a matte pattern or an embossed surface may be provided as appropriate to provide surface irregularities (concave and convex patterns). Alternatively, the uneven pattern may be filled with a colorant.
In the present embodiment, the above-mentioned surface protective layer 5 is embedded in the recess 8 forming the uneven pattern. This point will be described below.
The shape of the concave-convex pattern provided on the surface of the transparent thermoplastic resin layer 4 is not particularly limited, but the shape of the concave portion 8 constituting the concave-convex pattern is the back surface side (adhesiveness) of the transparent thermoplastic resin layer 4. It is preferable that the shape is such that the opening diameter increases from the resin layer 3) toward the surface side (surface protection layer 5). With such a shape, when the surface protective layer composition (coating liquid) is embedded in the recess 8 by wiping, the embedding is facilitated.

Further, the side surface forming the recess 8 is preferably an inclined surface. If the side surface forming the recess 8 is an inclined surface, the surface protective layer composition (coating liquid) can be easily embedded in the recess 8 by wiping.
Further, all the side surfaces forming the recess 8 may be covered with the surface protective layer 5.
The depth of the recess 8 is preferably in the range of 1 μm or more and 100 μm or less, more preferably in the range of 10 μm or more and 50 μm or less, and more preferably in the range of 20 μm or more and 40 μm or less with respect to the thickness direction of the transparent thermoplastic resin layer 4. The inside is more preferable. When the depth of the recess 8 is within the above numerical range, when the surface protective layer composition (coating liquid) is embedded in the recess 8 by wiping, the embedding can be facilitated and the surface protective layer can be prevented from peeling off.

The width of the recess 8 is preferably in the range of 1 μm or more and 10 μm or less, more preferably in the range of 2 μm or more and 8 μm or less, and further preferably in the range of 4 μm or more and 6 μm or less. When the width of the concave portion 8 is within the above numerical range, when the surface protective layer composition (coating liquid) is embedded in the concave portion 8 by wiping, the embedding is facilitated, and the surface protective layer embedded in the concave portion 8 is peeled off. Can be prevented.

Further, it is preferable that the recess 8 is completely filled (filled) with the surface protective layer composition (coating liquid), but the filling ratio of the surface protective layer 5 with respect to the volume of the recess 8 is 10% or more. Is preferable. When the filling rate of the surface protective layer 5 with respect to the volume of the recess 8 is 10% or more, the weather resistance in the recess 8 can be improved. That is, when the filling rate of the surface protective layer 5 with respect to the volume of the recess 8 is 10% or more, it is possible to reduce the occurrence of whitening and breakage in the conduit portion. Further, as described above, the filling rate of the surface protective layer 5 with respect to the volume of the recess 8 is preferably 100%, but it is more preferable if the filling rate of the surface protective layer 5 with respect to the volume of the recess 8 is 80% or less. It is more preferable that the filling rate of the surface protective layer 5 with respect to the volume of the recess 8 is 60% or less. When the filling rate of the surface protective layer 5 with respect to the volume of the recess 8 is 80% or less, a sufficient tactile sensation can be obtained in the recess 8.
Further, by setting the filling rate of the surface protective layer 5 to 100% with respect to the volume of the recess 8, the surface of the surface protective layer 5 filled in the recess 8 and the transparent thermoplastic resin layer 4 in the region not provided with the recess 8 The surface may be so-called flush.

<Constituent resin>
The transparent thermoplastic resin layer 4 includes, for example, a synthetic resin such as polyolefin, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic, or a foam of these synthetic resins and ethylene-propylene. Examples thereof include polymerized rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and rubber such as polyurethane. Among them, a polyolefin resin is particularly preferably used. Specifically, a homopolymerization of ethylene, propylene, butene, a copolymer resin of two or more of these, or a mixed resin thereof is preferable. Further, various additives such as an ultraviolet absorber, a radical scavenger, an antioxidant, a processing stabilizer, and the like may be added to these resins, if necessary.

<UV absorber>
Among the above, examples of the ultraviolet absorber, particularly the hydroxyphenyltriazine-based ultraviolet absorber, include 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- ( 2-Ethylhexanoyloxy) ethoxy] phenol, 2- (2hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-[(hexyl) oxy] -phenol, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) ) Oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2-ethyl-hexanoic acid, 2- [4- (4,6) -Diphenyl- [1,3,5] triazine-2-yl) -3-hydroxy-phenoxy] -ethyl ester, octanoic acid, 2- [4- (4,6-diphenyl- [1,3,5] ] Triazine-2-yl) -3-hydroxy-phenoxy] -ethyl ester, 2,4,6-tris {2-(2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl)} -1,3 , 5-Triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bis-butyloxyphenyl) -1,3,5-triazine, 2,4-bis ( 2,4-dimethylphenyl) -6- (2-hydroxy-4-iso-octyloxyphenyl) -s-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2, 4-Bis-butyloxyphenyl) -1,3,5-triazine and the like can be mentioned.

In the present embodiment, among the above-mentioned ultraviolet absorbers, a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (1) may be contained, and the following general formula (2) may be used. It is more preferable to contain an ultraviolet absorber having a structure represented by the above, and in particular, 2,4-bis [2-hydroxy-4- (2-ethylhexyloxy) phenyl)] -6 represented by the following formula (3). -(4-Methenylphenyl) -s-triazine is preferred.

In the general formula (1), R1 to R3 are independent of each other, exhibit a hydrogen atom or a methyl group, a phenyl group or an alkoxy group, and at least two are alkoxy groups having 8 to 18 carbon atoms, and R4 and R5 are They are independent and represent a hydroxyl group or a methyl group or a hydrogen atom, and R6 to R8 are independent and represent a methyl group or a hydrogen atom, respectively.

In the general formula (2), R1 and R2 represent an alkoxy group having 8 to 18 carbon atoms, R3 represents an alkoxy group having 1 to 4 carbon atoms, R4 represents a hydroxyl group, and R5 to R8 represent a hydrogen atom.

The content of the above-mentioned ultraviolet absorber is preferably in the range of 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component constituting the transparent thermoplastic resin layer 4, and more preferably. It is in the range of 0.05 parts by mass or more and 5 parts by mass or less.

<Radical scavenger>
Of the above, as the radical scavenger, a hindered amine compound is preferably used. In this embodiment, for example, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2 6,6-Pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2) , 2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2 , 3,4-Butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) di (tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,4,4-pentamethyl-4-piperidyl) ) -2-Butyl-2- (3,5-ditertiary butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / Diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1 , 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tertiary octylamino-s-triazine polycondensate, 1,5,8,12 -Tetrakiss [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazine-6-yl] -1,5,8,12 -Tetraazaddecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine -6-yl] -1,5,8-12-tetraazadodecane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-) 4-piperidyl) amino) -s-triazine-6-yl] aminoundecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl) -4-piperidyl) amino) -s-triazine-6-yl] Amino undecane and other hinders Doamine compounds can be mentioned. The content of the above-mentioned radical scavenger is preferably in the range of 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component constituting the transparent thermoplastic resin layer 4, and more preferably. It is in the range of 0.05 parts by mass or more and 5 parts by mass or less.

<Antioxidant>
Of the above, phenolic agents are preferably used as the antioxidant. In this embodiment, for example, 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditritiary butyl-4-hydroxybenzyl). Phosphonate, 1,6-hexamethylenebis [(3,5-ditertiary butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tertiary butyl-m-cresol), 2, 2'-Methylenebis (4-methyl-6-tertiary butylphenol), 2,2'-methylenebis (4-ethyl-6-third butylphenol), 4,4'-butylidenebis (6-third butyl-m-cresol) ), 2,2'-Etilidenebis (4,6-di-tertiary butylphenol), 2,2'-Etilidenebis (4-second butyl-6-third butylphenol), 1,1,3-Tris (2) -Methyl-4-hydroxy-5-third butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-thirdbutylbenzyl) isocyanurate, 1,3,5- Tris (3,5-ditertiary butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditriary butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene , 2-3rd Butyl-4-Methyl-6- (2-Acryloyloxy-3-3rd Butyl-5-Methylbenzyl) Phenol, Stearyl (3,5-Di3rd Butyl-4-Hydroxyphenyl) Propionate, Tetraquis [3- (3,5-ditertiary butyl-4-hydroxyphenyl) methyl propionate] methane, thiodiethylene glycol bis [(3,5-ditertiary butyl-4-hydroxyphenyl) propionate], 1,6 -Hexamethylenebis [(3,5-dithiary butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-third butylphenyl) butyl acid] glycol ester, bis [2-3rd Butyl-4-methyl-6- (2-Hydroxy-3-3rd Butyl-5-Methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-di3rd butyl) -4-Hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl]- 2,4,8,10-Tetraoxaspiro [5,5] Undecane, Trietile Nglycolbis [(3-tertiary butyl-4-hydroxy-5-methylphenyl) propionate] and the like can be mentioned. Further, the content of the above-mentioned antioxidant is preferably in the range of 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component constituting the transparent thermoplastic resin layer 4, and more preferably. It is in the range of 0.05 parts by mass or more and 5 parts by mass or less.

<Processing stabilizer>
Of the above, a phosphorus-based agent is preferably used as the processing stabilizer. In this embodiment, for example, trisnonylphenyl phosphite, tris [2-third butyl-4- (3-third butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tri. Decylphosphite, octyldiphenylphosphite, di (decyl) monophenylphosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditertiary butylphenyl) ) Pentaerythritol diphosphite, bis (2,6-ditertiary butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritrith butylphenyl) pentaerythritol diphosphite, bis (2,4-Dicumylphenyl) pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenol diphosphite, tetra (tridecyl) -4,4'-n-butylidenebis (2-tertiary butyl-5-methyl) Phenol) diphosphite, hexa (tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-3 butylphenyl) butanetriphosphite, tetrakis (2,4-ditertiary butylphenyl) biphenylenedi Phosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tertiary butylphenyl) -2-ethylhexyl phosphite, 2, 2'-Methylenebis (4,6-3rd Butylphenyl) -Octadecylphosphite, 2,2'-Echilidenebis (4,6-di3rd Butylphenyl) Fluorophosphite, Tris (2-[(2,4) , 8,10-Tetraxyl butyldibenzo [d, f] [1,3,2] dioxaphosfepin-6-yl) oxy] ethyl) amine, 2-ethyl-2-butylpropylene glycol and 2, Examples thereof include phosphite of 4,6-tritertiary butylphenol. The content of the above-mentioned processing stabilizer is preferably in the range of 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin component constituting the transparent thermoplastic resin layer 4, and more preferably. It is in the range of 0.05 parts by mass or more and 5 parts by mass or less.

The film thickness of the transparent thermoplastic resin layer 4 is preferably in the range of 15 μm or more and 150 μm or less. As a method of laminating the colored thermoplastic resin layer 1 and the transparent thermoplastic resin layer 4, a dry laminating method of laminating the colored thermoplastic resin layer 1 and the transparent thermoplastic resin layer 4 via the adhesive resin layer 3 or a colored thermoplastic resin layer 1 provided with the adhesive resin layer 3 An extrusion laminating method in which a transparent resin is melt-extruded from a T-die and bonded while forming a film can be used.

[Adhesive resin layer]
The adhesive resin layer 3 is provided as needed in order to bond the colored thermoplastic resin layer 1 provided with the pattern layer 2 and the transparent thermoplastic resin layer 4. It may not be necessary to exist when the target adhesive strength can be obtained without the adhesive resin layer 3 or when the transparent thermoplastic resin layer 4 is not provided.
The constituent material of the adhesive resin layer 3 is not particularly limited as long as it contributes to the improvement of the adhesive strength between any resin-based materials, and is, for example, various acrylic-based, polyester-based, polyurethane-based, epoxy-based, and the like. The material can be used. As the constituent material of the adhesive resin layer 3, a two-component curable polyurethane adhesive having a high coating film cohesive force is generally used. Further, the coating method can be appropriately selected depending on the viscosity of the coating liquid and the like. The layer thickness of the adhesive resin layer 3 is preferably about 0.5 μm to 6 μm.

[Colored thermoplastic resin layer]
As the colored thermoplastic resin layer 1, it is preferable that the pattern layer 2 can be provided by gravure printing or the like. Examples of the colored thermoplastic resin layer 1 include thin leaf paper, titanium paper, resin-impregnated paper and the like, polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and the like. Synthetic resin, or foam of these synthetic resins, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene It can be arbitrarily selected from block copolymer rubber, rubber such as polyurethane, organic or inorganic non-woven fabric, synthetic paper, metal foil such as aluminum, iron, gold and silver.

[Pattern layer]
The pattern layer 2 is a layer for imparting concealment or design, and can be provided by printing a solid or partially pattern ink on the colored thermoplastic resin layer 1.
As the binder for the pattern ink, for example, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, or the like alone or each modified product may be appropriately selected. There is no problem whether these are aqueous, solvent-based, or emulsion-based, and the curing method can be arbitrarily selected as a one-component type or a two-component type using a curing agent. Furthermore, it is also possible to cure the ink by irradiating with active energy rays such as ultraviolet rays and electron beams.

As the pigment of the pattern ink, various known pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthracinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, pearl pigment such as mica are used. can do. These ink materials need to be selected in consideration of the adhesiveness with the colored thermoplastic resin layer 1 under the pattern layer 2 and the resin laminated on the pattern layer 2.

If necessary, various additives such as an ultraviolet absorber, a radical scavenger, and a dispersant may be added to the pattern layer 2. As a method of providing the pattern layer 2, for example, it is applied directly to the colored thermoplastic resin layer 1 by a known printing technique such as gravure printing, offset printing, screen printing, flexo printing, silk printing, electrostatic printing, and inkjet printing. Can be done. In addition to the application of ink, it is also possible to apply a metallic design by vapor deposition or sputtering of various metals.

[Base material]
In the present embodiment, the above-mentioned decorative sheet 10 may be attached to the base material 7 to form the decorative member 11. Specifically, by laminating the decorative sheet 10 on a metal-based base material such as a steel plate or an aluminum plate, a wood-based base material such as MDF, or a resin-based base material such as PET, a makeup having high weather resistance performance is obtained. The member 11 can be obtained, and even when it is used for outdoor purposes, there is almost no deterioration in designability over time.

[Adhesive layer]
The adhesive layer 6 is a layer made of an adhesive, and is a layer for bonding the base material 7 and the colored thermoplastic resin layer 1.
As the adhesive constituting the adhesive layer 6, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer-based, polyester-based, or the like can be adopted. In particular, in the present embodiment, a two-component curable urethane-based adhesive obtained by blending a polyester polyol and a polyisocyanate is preferable. Further, when the adhesive layer 6 is formed by adding inorganic powders such as silica, barium sulfate, and calcium carbonate to these materials, it is effective in preventing blocking during winding storage and improving the adhesive force due to the anchoring effect. ..
The layer thickness of the adhesive layer 6 is preferably about 0.5 μm to 6 μm.
As the constituent material of the adhesive layer 6, the same material as the constituent material of the adhesive resin layer 3 described above may be used.

(Manufacturing method of decorative sheet and decorative member)
Hereinafter, an example of a method for manufacturing the decorative sheet 10 according to the present embodiment will be briefly described.
The colored thermoplastic resin layer 1, the pattern layer 2, and the adhesive resin layer 3 described above are laminated in this order.
Next, the transparent thermoplastic resin layer 4 is formed on the adhesive resin layer 3, and at the same time, an uneven pattern is formed on the surface of the transparent thermoplastic resin layer 4 by embossing.
Next, a coating liquid for forming the surface protective layer 5 is applied to the surface of the transparent thermoplastic resin layer 4 on which the uneven pattern is formed.
Finally, the coating liquid is wiped so as to be embedded in the recesses 8 forming the uneven pattern, and the coating liquid is cured to form the surface protective layer 5 on the transparent thermoplastic resin layer 4.
In this way, the decorative sheet 10 according to the present embodiment is formed.
Hereinafter, an example of a method for manufacturing the decorative member 11 according to the present embodiment will be briefly described.
The above-mentioned decorative sheet 10 and the base material 7 are bonded to each other via the above-mentioned adhesive layer 6.
Finally, the adhesive layer 6 is cured to form the decorative member 11.

[Example]
(Example 1)
A wood grain pattern was gravure-printed on a concealing polyethylene raw fabric (thickness 70 μm) using a two-component urethane ink (V180: manufactured by Toyo Ink Co., Ltd.) to provide a pattern layer (thickness 3 μm).
Next, the following transparent thermoplastic resin layer composition having a thickness of 80 μm was applied to a polyethylene raw fabric provided with a pattern layer via a dry laminating adhesive (Takelac A540: manufactured by Mitsui Chemicals, Inc.) (thickness 2 μm). It was extruded and laminated to form a transparent thermoplastic resin layer, and at the same time, the surface was embossed with a wood grain pattern (conduit portion).
Next, the following surface protective layer composition was applied and dried on the outermost surface of the transparent thermoplastic resin layer with a gravure coat. At this time, the surface protective layer composition was wiped and embedded in the recesses of the transparent thermoplastic resin layer.
Finally, the decorative sheet prepared by the above step and the alumite-treated aluminum base material (thickness 1 mm) are bonded to each other via the following adhesive (thickness 20 μm) and cured at 25 ° C. for 3 days. As a result, the decorative member of Example 1 was obtained.

(Transparent thermoplastic resin layer composition)
-Transparent homopolypropylene resin (Prime PP; manufactured by Prime Polymer Co., Ltd.)
・ ・ ・ 99 parts by mass ・ Ultraviolet absorber (Chinosorb S; manufactured by BASF Japan Ltd.) ・ ・ ・ 0.5 parts by mass ・ Light stabilizer (Chinubin XT55; manufactured by BASF Japan Ltd.) ・ ・ ・ 0.5 Mass part The molecular structure of the main component of "Chinosorb S" is shown in the following formula (3).

(Surface protective layer composition)
・ Main agent (methyl methacrylate / 2 hydroxyethyl methacrylate = 95/5 copolymer) ・ ・ ・ 90 parts by mass ・ Ultraviolet absorber (Tinubin 479); manufactured by BASF Japan Ltd.) ・ ・ ・ 9 parts by mass ・ Light stabilizer (Chinubin 123; manufactured by BASF Japan Ltd.) ・ ・ ・ 1 part by mass ・ Hardener (Takenate D170; Mitsui Chemicals Co., Ltd.) ・ ・ ・ 10 parts by mass ・ Solvent (ethyl acetate) ・ ・ ・ 240 parts by mass (adhesive) Agent)
・ Main agent (No. 5211; manufactured by No Tape Industry Co., Ltd.) ・ ・ ・ 95 parts by mass ・ Curing agent (U-5; manufactured by No Tape Industry Co., Ltd.) ・ ・ ・ 5 parts by mass

(Comparative Example 1)
A decorative member of Comparative Example 1 was obtained in the same manner as in Example 1 except that the ultraviolet absorber added to the transparent thermoplastic resin layer of Example 1 was ADEKA STUB LA-F70 manufactured by ADEKA Corporation.
The molecular structure of the main component of "Adecaster LA-F70" is shown in the following formula (5).

(Comparative Example 2)
A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that the ultraviolet absorber added to the transparent thermoplastic resin layer of Example 1 was Tinubin 1600 (manufactured by BASF Japan Ltd.).
The molecular structure of the main component of "Chinubin 1600" is shown in the following formula (6).

(Comparative Example 3)
A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1 except that the ultraviolet absorber added to the transparent thermoplastic resin layer of Example 1 was Siasorb UV1164 (manufactured by Sun Chemical Co., Ltd.).
The molecular structure of the main component of "Siresorb UV1164" is shown in the following formula (7).

<Evaluation>
The decorative members obtained in the above Examples and Comparative Examples were evaluated for design and weather resistance by the following methods. The evaluation results are shown in Table 1 below.

a) Weather resistance The appearance of the decorative member after the weather resistance promotion test was visually evaluated according to the following criteria. The weather resistance acceleration test was performed using a metal weather tester (KU-R5DCI-A) manufactured by Daipla Wintes Co., Ltd. at a black panel temperature of 63 ° C. and an illuminance of 65 mW / cm ² (UV irradiation 20 hours + condensation 4 hours). Was set as one cycle, and 30 cycles were carried out. This evaluation standard is shown below.
〔Evaluation criteria〕
◯: No discoloration of the decorative sheet or white turbidity of the transparent thermoplastic resin and the surface protective layer is observed (or extremely small).
X: Discoloration of the pattern on the decorative sheet or white turbidity of the transparent thermoplastic resin and the surface protective layer is noticeably observed. If the evaluation of weather resistance is "○", there is no problem in use, so the result was accepted.

b) Design The appearance of the decorative member was visually evaluated according to the following criteria. However, the reference sheet is obtained by separately producing a sheet containing no ultraviolet absorber in the transparent thermoplastic resin layer in Example 1. This evaluation standard is shown below.
〔Evaluation criteria〕
◯: No difference in appearance is observed with respect to the reference sheet by visual observation.
X: A feeling of cloudiness is observed with respect to the reference sheet by visual observation.
If the evaluation of the design is "○", there is no problem in use, so it was accepted.

As shown in Table 1, the decorative sheet (decorative member) according to the present embodiment illustrated in Example 1 is obtained by adding a hydroxyphenyltriazine-based ultraviolet absorber having a specific structure to the transparent thermoplastic resin layer. It has less cloudiness, excellent design, and excellent weather resistance.

The decorative sheet (decorative member) of the present invention relates to a decorative sheet used for building materials such as building interior and exterior, surface and frame materials of fittings, surface materials of home appliances, flooring, etc. It can be used as a decorative member by sticking it to inorganic boards, metal plates, etc.

1 ・ ・ ・ Colored thermoplastic resin layer 2 ・ ・ ・ Pattern layer 3 ・ ・ ・ Adhesive resin layer 4 ・ ・ ・ Transparent thermoplastic resin layer 5 ・ ・ ・ Surface protection layer 6 ・ ・ ・ Adhesive layer 7 ・ ・ ・Base material 8 ・ ・ ・ Recessed part 10 ・ ・ ・ Decorative sheet 11 ・ ・ ・ Decorative member

Claims (16)

A decorative member including a base material and a decorative sheet formed on the base material.
The decorative sheet includes a transparent thermoplastic resin layer formed on the base material side and a surface protective layer formed on a surface of the transparent thermoplastic resin layer opposite to the base material side.
The transparent thermoplastic resin layer contains a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (1), and contains.
An uneven pattern is formed on the surface of the transparent thermoplastic resin layer in contact with the surface protective layer.
The surface protective layer is embedded in the recesses forming the uneven pattern.
Filling factor of the surface protective layer in the recess state, and are within the scope of 10% to 80% or less,
The transparent thermoplastic resin layer contains a homopolypropylene resin as a thermoplastic resin and contains a homopolypropylene resin.
The surface protective layer is composed of a hydroxyphenyltriazine-based ultraviolet absorber having a structure different from that of the hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (1), and an acrylic resin composition. cosmetic member characterized by Tei Rukoto.

(In the general formula (2), R1 and R2 represent an alkoxy group having 8 to 18 carbon atoms, R3 represents an alkoxy group having 1 to 4 carbon atoms, R4 represents a hydroxyl group, and R5 to R8 represent a hydrogen atom.) A decorative member including a base material and a decorative sheet formed on the base material.
The decorative sheet includes a transparent thermoplastic resin layer formed on the base material side and a surface protective layer formed on a surface of the transparent thermoplastic resin layer opposite to the base material side.
The transparent thermoplastic resin layer contains a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (2) and contains.
An uneven pattern is formed on the surface of the transparent thermoplastic resin layer in contact with the surface protective layer.
The surface protective layer is embedded in the recesses forming the uneven pattern.
The filling rate of the surface protective layer in the recess is 100%.
The surface of the surface protective layer filled in the recess and the surface of the transparent thermoplastic resin layer in the region not provided with the recess are flush with each other.
The transparent thermoplastic resin layer contains a homopolypropylene resin as a thermoplastic resin and contains a homopolypropylene resin.
The surface protective layer is composed of a hydroxyphenyltriazine-based ultraviolet absorber having a structure different from that of the hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (2), and an acrylic resin composition. cosmetic member characterized by Tei Rukoto.

(In the general formula (2), R1 and R2 represent an alkoxy group having 8 to 18 carbon atoms, R3 represents an alkoxy group having 1 to 4 carbon atoms, R4 represents a hydroxyl group, and R5 to R8 represent a hydrogen atom.) The decorative member according to claim 1 or 2 , wherein the hydroxyphenyltriazine-based ultraviolet absorber contained in the transparent thermoplastic resin layer has a structure represented by the following formula (3).

The transparent thermoplastic resin layer contains the hydroxyphenyltriazine-based ultraviolet absorber in a range of 0.001 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the resin composition constituting the transparent thermoplastic resin layer. The decorative member according to any one of claims 1 to 3, wherein the decorative member is contained in. The decorative member according to any one of claims 1 to 4, wherein all the surfaces constituting the recess are covered with a resin constituting the surface protective layer. The decorative member according to any one of claims 1 to 5, wherein the base material is a metal-based base material, a wood-based base material, or a resin-based base material. The recess according to any one of claims 1 to 6, wherein the depth thereof is within the range of 10 μm or more and 50 μm or less, and the width thereof is within the range of 1 μm or more and 10 μm or less. Cosmetic material. The content of the hydroxyphenyl triazine UV absorber contained in the prior Symbol surface protective layer, characterized in that with respect to the acrylic resin composition 100 parts by weight, in the range of 1 part by weight or more than 30 parts by weight The decorative member according to any one of claims 1 to 7. The hydroxyphenyltriazine-based ultraviolet absorber contained in the surface protective layer is 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1. , 3,5-The decorative member according to claim 8, which is triazine. The content of the hydroxyphenyltriazine-based ultraviolet absorber contained in the surface protective layer is in the range of 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition. The decorative member according to claim 9. The surface protective layer is 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) as a hydroxyphenyltriazine-based ultraviolet absorber. Ethoxy] The decorative member according to claim 9, which further contains phenol. The content of 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine is 2- (4,6). -Diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] Phenol is 10 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass. The decorative member according to claim 11, wherein the decorative member is within the range. The surface protective layer, and the hydroxyphenyl triazine-based UV absorber, is configured to include a benzotriazole based ultraviolet absorber, and the acrylic resin composition,
Claims 1 to 12 are characterized in that the content of the benzotriazole-based ultraviolet absorber is in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition. The decorative member according to any one of the above items. The base material and the decorative sheet are adhered to each other via an adhesive layer.
The decorative sheet includes a colored thermoplastic resin layer, a pattern layer, an adhesive resin layer, a transparent thermoplastic resin layer, and a surface protective layer in this order from the adhesive layer side.
The decorative member according to any one of claims 1 to 13, wherein the base material is a metal-based base material. The method for manufacturing a decorative member according to any one of claims 1 to 14.
A step of forming an uneven pattern on the surface of the transparent thermoplastic resin layer by embossing,
It has a step of forming a surface protective layer on the surface of the transparent thermoplastic resin layer on which the uneven pattern is formed.
A method for producing a decorative member, which comprises embedding the surface protective layer in the recesses constituting the uneven pattern of the transparent thermoplastic resin layer in the step of forming the surface protective layer. The production of the decorative member according to claim 15, wherein in the step of forming the surface protective layer, the surface protective layer is embedded in the concave portion forming the uneven pattern of the transparent thermoplastic resin layer by wiping. Method.

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