JP2011042041A - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in so-called weatherability, for example, little deterioration in designability even if it is exposed to factors such as ultraviolet rays, wind and rain for a long period of time, and having after-processability such as bending. <P>SOLUTION: A surface protection layer includes, as a main component, an acrylic resin composition containing at least cyclohexyl (meta)acrylate as a copolymerization component. The layer contains one or more kinds of hydroxyphenyltriazine ultraviolet absorbers at least one of which has a structure shown in the following (formula 1). The weight of all the hydroxyphenyltriazine ultraviolet absorbers is 1-30 pts.wt. in total based on 100 pts.wt. of the acrylic resin composition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a decorative sheet used for building materials such as building interiors and exteriors, surfaces and frame materials of joinery, surface materials of household electrical appliances, flooring materials, etc., wood boards, inorganic boards, metal plates It is a decorative sheet that is used as a decorative material by being attached to the like.

  Conventionally, a decorative sheet used for the above application is generally provided with a surface protective layer on the outermost surface. The purpose includes improvement of weather resistance, scratch resistance and contamination resistance, adjustment of surface gloss, etc. Among them, improvement of weather resistance can be said to be the most important role of the surface protective layer. In recent years, with the long-term guarantee of housing becoming common sense, improving the weather resistance of decorative sheets has become a major issue.

  In order to improve the weather resistance of the decorative sheet, it is necessary that the surface protective layer itself is also excellent in weather resistance. Therefore, in general, an acrylic resin is often used as the surface protective layer to further improve the weather resistance. In general, a weathering agent, that is, an ultraviolet absorber or a radical scavenger is added to the surface protective layer (for example, Patent Documents 1 to 3). In order to further improve the weather resistance, it is necessary to increase the amount of weathering agent added, but depending on the type of weathering agent, there is a concern of bleed out, and it also leads to cost increase, so the amount of addition can not be increased so much It was a fact. In addition, even if those problems can be avoided, performance deactivation occurs due to decomposition of the weathering agent itself over time, the desired performance cannot be obtained, and long-term weather resistance cannot be obtained. There was a problem. There is no way to reduce the additive amount to a certain level as a measure against bleed-out without considering cost increase, and instead increase the thickness of the layer, but in that case, post-processing such as bending is necessary. There was a concern that the sex would decline.

JP 2008-238444 A JP 2007-118584 A Japanese Patent Laid-Open No. 2005-084881

  The present invention has been made in order to solve such problems, and the object of the present invention is so-called weather resistance, such as little deterioration in designability even when exposed to factors such as ultraviolet rays and wind and rain for a long time. Another object of the present invention is to provide a decorative sheet having excellent properties and having post-processing properties such as bending, and a decorative material using the decorative sheet.

  The present invention solves this problem, that is, the invention according to claim 1 is a decorative sheet having a surface protective layer on at least the outermost surface, and the surface protective layer contains at least cyclohexyl (meth) acrylate. The main component is an acrylic resin composition contained as a copolymerization component, and at least one type contains one or more hydroxyphenyltriazine-based ultraviolet absorbers having a structure represented by the following (formula 1): The decorative sheet is characterized in that the total amount of all hydroxyphenyltriazine-based ultraviolet absorbers is 1 to 30 parts by weight with respect to 100 parts by weight of the acrylic resin composition.

  Further, the invention according to claim 2 is characterized in that the hydroxyphenyl triazine-based ultraviolet absorber having the structure shown in the above (formula 1) is contained in the surface protective layer. The decorative sheet according to claim 1, comprising 30 to 95% by weight.

  The invention according to claim 3 is characterized in that the cyclohexyl (meth) acrylate accounts for 5 to 50% by weight of the acrylic resin composition as a main component of the surface protective layer. It is a decorative sheet in any one of Claims 1-2.

  The invention described in claim 4 is characterized in that at least one of the hydroxyphenyltriazine-based ultraviolet absorbers has a structure represented by the following (formula 2). The decorative sheet according to any one of the above.

  The invention according to claim 5 is characterized in that 1 to 30 parts by weight of a benzotriazole-based ultraviolet absorber is contained with respect to 100 parts by weight of the acrylic resin composition. A decorative sheet according to any one of the above.

  The invention according to claim 6 is characterized in that 1 to 30 parts by weight of a hindered amine radical scavenger is contained with respect to 100 parts by weight of the acrylic resin composition. A decorative sheet according to the above.

  The invention according to claim 7 is the decorative sheet according to any one of claims 1 to 6, wherein the surface protective layer is crosslinked by isocyanate curing.

  The invention according to claim 8 is characterized in that the thickness of the surface protective layer is in the range of 2 to 20 μm, and the total thickness of the decorative sheet is in the range of 40 to 300 μm. The decorative sheet according to any one of claims 1 to 7.

  The invention according to claim 9 is a decorative material obtained by bonding the decorative sheet according to any one of claims 1 to 8 on a metal base material such as a steel plate or aluminum.

  According to the first invention of the present invention, the hydrophobic performance of the surface protective layer is improved by using cyclohexyl (meth) acrylate, and cosmetics derived from moisture (humidity, rain, etc.) in weathering tests or long-term actual use. The embrittlement of the sheet can be suppressed. At the same time, the ability to suppress precipitation over time by copolymerizing cyclohexyl (meth) acrylate with the acrylic resin component is derived from moisture (humidity, rainfall, etc.) in weathering tests or long-term actual use. This contributes to suppression of embrittlement of the decorative sheet. In addition, by introducing a hydroxyphenyltriazine-based ultraviolet absorber having the structure shown in (Formula 1), a relatively low wavelength and high energy region having a wavelength of about 270 to 300 nm and falling on the earth's surface has a high level. In addition, it becomes possible to continue to absorb even over time, and the weather resistance of the decorative sheet is greatly improved. A combination of these, the weather resistance is improved by making the total content of the UV absorber 1-30 parts by weight with respect to 100 parts by weight of the acrylic resin composition, and the makeup has the performance to withstand long-term use A sheet is obtained.

  According to the second invention of the present invention, 30% by weight or more of all hydroxyphenyltriazine-based ultraviolet absorbers having the structure of (Formula 1), and hydroxyphenyltriazine-based ultraviolet rays other than (Formula 1) By using a plurality of kinds of hydroxyphenyltriazine-based ultraviolet absorbers so as to have 5 to 70% by weight of the absorber, the weather resistance of the decorative sheet can be further improved by these interactions.

  According to the third invention of the present invention, the cyclohexyl (meth) acrylate of all the acrylic resin compositions is 5% by weight or more, and the other acrylic resin composition is 50 to 95% by weight, thereby protecting the surface. Sufficient hydrophobic performance can be imparted to the decorative sheet surface protective layer without significantly impairing the performance as a layer.

  According to the fourth invention of the present invention, by using the hydroxyphenyltriazine-based ultraviolet absorbers of (Formula 1) and (Formula 2) in combination, the compound of (Formula 1) is the main component of the ultraviolet rays falling on the ground surface. Since the compound of (Formula 2) absorbs mainly the high wavelength region among the ultraviolet rays that fall on the ground surface, it can absorb the ultraviolet ray over a wide wavelength region. The weather resistance can be further improved.

  According to the fifth aspect of the present invention, by further using a benzotriazole-based ultraviolet absorber, the wavelength range that can be covered by the contained ultraviolet absorber can be further expanded, and the weather resistance of the decorative sheet is further improved.

  According to the sixth invention of the present invention, by further using a radical scavenger, radicals induced by light energy that could not be absorbed by the UV absorber, or thermal energy converted from light energy by the UV absorber It is possible to suppress the deterioration of the surface protective layer due to radicals induced by, and to further improve the long-term weather resistance of the decorative sheet.

  According to the seventh aspect of the present invention, by forming a surface protective layer by isocyanate curing, a certain degree of flexibility can be imparted to the surface protective layer. Post-processability such as bending, folding, and lapping can be improved. In addition to the effect of preventing the deterioration of the designability, this can also suppress the cracking of the surface protective layer during the bending process, thereby preventing the deterioration of weather resistance.

  According to the eighth aspect of the present invention, it is possible to obtain a decorative sheet that balances the thickness of the surface protective layer and the thickness of the decorative sheet layer and has an excellent balance between the post-processability and the weather resistance.

  According to the ninth aspect of the present invention, a decorative material using a decorative sheet that can be used not only indoors but also outdoors can be provided.

It is explanatory drawing which shows the structure of the cross section of one Example of the decorative sheet of this invention.

  Hereinafter, the decorative sheet of the present invention will be described in detail with reference to the drawings. However, the decorative sheet is not necessarily laminated in this order as long as it is within the scope of the present invention. Further, a layer not described in this drawing may be added. FIG. 1 shows a cross-sectional structure of one embodiment of the decorative sheet of the present invention. Here, the base material layer 1, the pattern layer 2, the adhesive layer 3, the transparent resin layer 4, and the surface protective layer 5 are laminated in this order.

  As the surface protective layer 5 in the present invention, an acrylic resin composition containing cyclohexyl (meth) acrylate as a copolymerization component is a main component. In the present invention, cyclohexyl (meth) acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By including cyclohexyl (meth) acrylate as a copolymerization component, the affinity for water can be lowered over a long period of time, and degradation due to hydrolysis or the like can be suppressed. The amount of cyclohexyl (meth) acrylate is preferably 5 to 50% by weight of cyclohexyl (meth) acrylate among all acrylic resin compositions. By making it 5% by weight or more, it is possible to obtain a sufficient effect of suppressing deterioration, and by making it 50% by weight or less, the surface protection of the decorative sheet such as maintaining the surface hardness, improving the stain resistance and adjusting the gloss of the surface is possible. It is possible to provide high weather resistance over time without greatly changing the various performances of the layer 5.

  Examples of the copolymer component of the acrylic resin composition that can be used in the present invention include cyclohexyl (meth) acrylate, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, and cyclohexyl. Butyl (meth) acrylate, dimethylcyclohexane mono (meth) acrylate, dimethylcyclohexanedi (meth) acrylate, trimethylcyclohexanemono (meth) acrylate, trimethylcyclohexanedi (meth) acrylate, trimethylcyclohexanetri (meth) acrylate, tetramethylcyclohexanemono (Meth) acrylate, tetramethylcyclohexanedi (meth) acrylate, tetramethylcyclohexanetri (meth) acrylate Rate, tetramethylcyclohexane tetra (meth) acrylate, dicyclohexyl methyl (meth) acrylate, dicyclohexyl methyl (meth) acrylate, phenoxyethyl cyclohexylmethyl (meth) acrylate, methoxy cyclohexylmethyl (meth) acrylate. Among these, those containing isomers may be each isomer alone and / or each isomer mixture.

  In addition, as a method of providing the surface protective layer 5 in the present invention, the surface protective layer 5 may be formed by applying a coating liquid composed of an acrylic resin composition containing the cyclohexyl (meth) acrylate as a copolymerization component to the outermost surface of the decorative sheet. That's fine. As a curing method, any of a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type that cures by irradiating ultraviolet rays or ionizing radiation can be used. A two-component curing type or an active energy ray curing type is preferable, and a two-component curing type that is cross-linked by isocyanate curing is desirable in consideration of post-processing properties after being bonded to various base materials to form a cosmetic material.

  As the two-component curable acrylic resin composition, an acrylic resin having two or more functional groups selected from a hydroxyl group, an amino group and a carboxyl group in one molecule reacts with the functional group. A composition containing a polyisocyanate compound having two or more isocyanate groups in one molecule is preferred. Particularly preferred is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound.

As the acrylic polyol having two or more hydroxyl groups in one molecule, a (meth) acrylic acid ester copolymer containing hydroxyethyl (meth) acrylate as a copolymer component in addition to the cyclohexyl (meth) acrylate is used. it can. Giving a hydroxyl group to the side chain is accomplished by copolymerizing an unsaturated alcohol.
On the other hand, polyisocyanate compounds having two or more isocyanate groups in one molecule include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and hydrogenated compounds thereof. Examples thereof include isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and a trimer type obtained by synthesizing one or more compounds selected from these by known techniques, a TMP adduct type, a burette type, and the like. Moreover, the composition which mixed 1 or more types chosen from these different types of polyisocyanate can be used. Of these, HDI, or a trimer type of HDI, a TMP adduct type, and a burette type are preferable from the viewpoint of weather resistance.
Although the content of the isocyanate compound relative to the resin component described above can be set arbitrarily, it is desirable to set the hydroxyl group / isocyanate group equivalent ratio to be 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 crosslinking does not proceed sufficiently and the desired performance is not added to the surface protective layer 5, which is not preferable.

  In the case of active energy ray curing, as the active energy curing type acrylic resin composition, known monomers and oligomers having a (meth) acryloyl group can be used, and in addition to these monomers and oligomers, the cyclohexyl A (meth) acrylate may be copolymerized to form a prepolymer.

  In order to further improve the weather resistance of the decorative sheet, addition of a weathering agent such as an ultraviolet absorber or a radical scavenger is generally used for the surface protective layer 5. As UV absorbers, known ones such as benzotriazoles, hydroxyphenyl triazines, and benzophenones can be used. Among them, if a hydroxyphenyl triazine UV absorber is selected, the triazine skeleton suppresses bleeding. Since the triazine skeleton is chemically stable as compared with the benzotriazole-based and benzophenone-based skeletons, it is possible to maintain ultraviolet absorption performance over a long period of time.

  Examples of the hydroxyphenyl triazine-based UV absorber include: 2- (4,6-diphenyl-1,3,5-triazin-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-triazin-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, ] Triazin-2-yl) -3-hydroxy-phenoxy] -ethyl ester, octanoic acid 2- [4- (4,6-diphenyl- [1,3,5] triazin-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-butyloxy) Phenyl) -1,3,5-triazine and the like. In the present invention, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2 -Ethylhexanoyloxy) ethoxy] phenol (corresponding to (formula 1)) is contained. This is because the hydroxyphenyltriazine-based UV absorber of the chemical formula (1) has a high UV-absorbing ability in the low-wavelength region, which is relatively high energy among UV rays, and absorbs almost the same wavelength region. This is because it is chemically stable as compared with the ultraviolet absorbers of No. 1, and the ultraviolet absorbing performance over a long period of time is sustained.

  In the present invention, the addition amount of all hydroxyphenyltriazine ultraviolet absorbers including those having the structure of (Formula 1) is 1 to 30 parts by weight with respect to 100 parts by weight of the acrylic resin composition. And When the amount is 1 part by weight or more, the effect of improving the weather resistance is exhibited, and when the amount is 30 parts by weight or less, the influence on the physical properties other than the weather resistance of the surface protective layer 5 can be suppressed to a level with no practical problem.

  In the present invention, as the hydroxyphenyltriazine-based ultraviolet absorber in the surface protective layer 5, those having the structure of (Formula 1) and 2- (2hydroxy-4- [1-octyloxycarbonylethoxy] Phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine and a compound having a structure of (corresponding to (Formula 2)) are used in combination to provide further excellent weather resistance performance. The This is because the ultraviolet absorber having the structure of (Equation 2) is chemically stable, and the ultraviolet absorption performance for a long period of time is sustained, and longer than that having the structure of (Equation 1). This is because the light absorption peak is present on the wavelength side, so that the wavelength region for absorbing ultraviolet light becomes wider when used in combination.

  Further, by using a combination of hydroxyphenyl triazine and benzotriazole as the ultraviolet absorber, it is possible to impart further excellent weather resistance performance by the interaction. 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 combined wavelength range for absorbing UV is further increased. . As the addition amount, 1 to 30 parts by weight is preferable with respect to 100 parts by weight of the acrylic resin composition, and by adding 1 part by weight or more, a desired effect can be obtained, and 30 parts by weight or less. By doing so, the bleed-out of the weathering agent can be suppressed. However, the benzotriazole-based ultraviolet absorber has an absorption peak on the long wavelength side, so that it may have a yellowish color, and when the hue needs attention, the addition amount may be suppressed.

  Examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5- Chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-5'- Trioctylphenyl) benzotriazol, 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) benzotriazole, 2,2′-methylenebis (4-tert-octyl-6- (benzotriazolyl) ) Phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole and the like, but are not limited thereto.

  Furthermore, the weather resistance performance of the decorative sheet can be further improved by using a hindered amine radical scavenger in combination. For example, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 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-ditert-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-pi Lysylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (2,2 , 6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis [2,4- Bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-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-triazin-6-yl] aminoundecane, , 6,11-tris [2,4-bis (N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-yl] aminoundecane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-Bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate cyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2 , 4,6-trichloro 1,3,5-triazine reaction product and 2-aminoethanol reaction product, but are not limited thereto.

  As the addition amount, 1 to 30 parts by weight is preferable with respect to 100 parts by weight of the acrylic resin composition, and by adding 1 part by weight or more, a desired effect can be obtained, and 30 parts by weight or less. By doing so, the bleed-out of the weathering agent can be suppressed, and the influence on the other physical properties of the surface protective layer 5 can be suppressed.

  If the thickness of the surface protective layer 5 in the present invention is the same as the addition amount of the ultraviolet absorber, it is possible to obtain better weatherability when the film is thickened, but the flexibility of the sheet is impaired and post-processing is performed. Problems such as cracking on the surface of the decorative sheet are likely to occur at times. On the other hand, when the film is thinned, there is a problem that the weather resistance is impaired. Therefore, the thickness of the surface protective layer 5 is preferably 2 to 20 μm. For the same reason, if the total thickness of the decorative sheet is in the range of 40 to 300 μm, both weather resistance and post-workability can be achieved.

  As a method of providing the surface protective layer 5 in the present invention, various known coating methods such as gravure coating, reverse coating, gravure reverse coating, die coating, and flow coating can be used. Furthermore, you may add various additives, such as a lubricant, an antiblocking agent, and an antistatic agent, to the surface protective layer 5 in this invention as needed.

  The transparent 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, surface irregularities may be provided by appropriately applying a matte pattern or embossing. Alternatively, the unevenness may be filled with a colorant. As the transparent resin layer 4, polyolefin, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic, or other synthetic resins, or foams of these synthetic resins, ethylene-propylene copolymer rubber, ethylene- Examples include propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and polyurethane rubbers. Resins are preferably used. Specifically, a homopolymer of ethylene, propylene, butene, or a copolymer resin of two or more of these or a mixed resin thereof is preferable. Moreover, you may add various additives, such as a ultraviolet absorber, a radical scavenger, antioxidant, a process stabilizer, in these resins as needed.

  Among these, examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis (2-hydroxy-4- 2-hydroxybenzophenones such as methoxybenzophenone); 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 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 such as 2,2′-methylenebis (4-tert-octyl-6- (benzotriazolyl) phenol), 2- (2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl) benzotriazole -(2'-hydroxyphenyl) benzotriazoles; phenyl salicylate, resorcinol monobenzoate, 2,4-ditertiarybutylphenyl-3,5-ditertiarybutyl-4-hydroxybenzoate, 2,4-ditertiary Benzoates such as amylphenyl-3,5-ditert-butyl-4-hydroxybenzoate, hexadecyl-3,5-ditert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2 Substituted oxanilides such as -ethoxy-4'-dodecyloxanilide; ethyl-α-cyano-β, β-diphenyla Cyanoacrylates such as relate, methyl-2-cyano-3-methyl-3- (p-methoxyphenyl) acrylate; 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4 -Di-tert-butylphenyl) -s-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-s-triazine, 2- (2-hydroxy-4-propoxy-5-methylphenyl) ) -4,6-bis (2,4-ditertiarybutylphenyl) -s-triazine and the like, and triaryltriazines are mentioned, and 0.001 to 10 parts by weight with respect to 100 parts by weight of acrylic resin, More preferably, 0.05 to 5 parts by weight are used.

  As the radical scavenger, hindered amine compounds are preferably used. 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, , 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-ditert-butyl-4-hydroxybenzyl) malonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / succinic acid Diethyl 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-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis [ 2,4-bis N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12-tetraazadodecane, 1,5, 8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-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- Triazin-6-yl] aminoundecane, 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s -Triazin-6-yl] hindered amine compounds such as aminoundecane For example, 0.001 to 10 parts by weight, and more preferably 0.05 to 5 parts by weight is used with respect to 100 parts by weight of the acrylic resin.

  Of the above, phenolic compounds are preferably used as the antioxidant. For example, 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, 1,6 -Hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionic acid amide], 4,4'-thiobis (6-tert-butyl-m-cresol), 2,2'-methylenebis ( 4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-butylidenebis (6-tert-butyl-m-cresol), 2,2 '-Ethylidenebis (4,6-ditert-butylphenol), 2,2'-ethylidenebis (4-secondarybutyl-6-tert-butylphenol), 1,1,3-tris (2- Til-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-ditert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-ditert-butyl-4-hydroxyphenyl) propionate, tetrakis [Methyl 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis [(3,5-ditert-butyl-4- Droxyphenyl) propionate], 1,6-hexamethylenebis [(3,5-ditert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-tert-butyl) Phenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris [(3,5-ditert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, 3,9-bis [1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5 -Methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like, and 0.001 to 10 parts by weight, more preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the acrylic resin. 5 parts by weight are used.

  Among the above, phosphorus processing agents are preferably used as the processing stabilizer. For example, trisnonylphenyl phosphite, tris [2-tert-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) -5-methylphenyl] phosphite, tridecyl phosphite, octyl Diphenyl phosphite, di (decyl) monophenyl phosphite, di (tridecyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, bis (2,4-ditert-butylphenyl) pentaerythritol diphos Phyto, bis (2,6-ditert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tritert-butylphenyl) pentaerythritol diphosphite, bis (2,4- Dicumylphenyl) pentaerythritol diphosphite Tetra (tridecyl) isopropylidenediphenol diphosphite, tetra (tridecyl) -4,4′-n-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) -1,1,3- Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis (2,4-ditert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10- Phosphaphenanthrene-10-oxide, 2,2'-methylenebis (4,6-tert-butylphenyl) -2-ethylhexyl phosphite, 2,2'-methylenebis (4,6-tert-butylphenyl)- Octadecyl phosphite, 2,2'-ethylidenebis (4,6-ditert-butylphenyl) phenyl Olophosphite, tris (2-[(2,4,8,10-tetrakis tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl) oxy] ethyl) amine Phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritert-butylphenol, etc., and 0.001 to 10 parts by weight, more preferably 100 parts by weight of acrylic resin 0.05 to 5 parts by weight are used.

  The film thickness of the transparent resin layer 4 is preferably 15 to 150 μm. As a method of laminating the base material layer 1 and the transparent resin layer 4, a dry laminating method in which the base material layer 1 is bonded via the adhesive layer 3, or a transparent resin is formed on the base material layer 1 provided with the adhesive layer 3 from a T die. An extrusion laminating method or the like that is bonded while melt extrusion is performed can be used.

  The adhesive layer 3 is provided as necessary in order to bond the base material layer 1 provided with the pattern layer 2 and the transparent resin layer 4 together. When the target adhesive strength can be obtained without the adhesive layer 3 or when the transparent resin layer 4 is not provided, the presence may not be necessary. The constituent material is not particularly limited as long as it contributes to improving the adhesive strength between arbitrary resin systems, and various materials such as acrylic, polyester, polyurethane, and epoxy can be used. In general, a two-component curable polyurethane adhesive having a high coating cohesive force is often used. The coating method can also be appropriately selected depending on the viscosity of the coating solution. The layer thickness is preferably about 0.5 to 6 μm.

  It is preferable that the base material layer 1 can provide the pattern layer 2 by gravure printing. Paper such as thin paper, titanium paper, resin-impregnated paper, polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and other synthetic resins, or foams 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 block copolymer rubber, rubber such as polyurethane, organic It can be arbitrarily selected from metallic or inorganic nonwoven fabrics, synthetic paper, aluminum, iron, gold, silver or other metal foils.

  The design pattern layer 2 is a layer for imparting concealability or design properties, and can be provided by printing the design ink on the entire surface of the base material layer 1 in a solid or partial manner. The binder of the pattern ink may be appropriately selected from nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester and the like alone or each modified product. There is no problem even if these are water-based, solvent-based, or emulsion-based, and the curing method can be arbitrarily selected from a one-component type and a two-component type using a curing agent. Further, the ink can be cured by irradiation with active energy rays such as ultraviolet rays and electron beams. As pigments for pattern inks, various known pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, mica and other pearl pigments should be used. Can do. These ink materials need to be selected in consideration of the adhesiveness with the base material layer 1 under the design pattern layer 2 and the resin laminated on the design pattern layer 2.

  You may add various additives, such as a ultraviolet absorber, a radical scavenger, a dispersing agent, to the pattern layer 2 as needed. As a method for providing the pattern layer 2, it can be directly applied to the base material layer 1 by a known printing technique such as gravure printing, offset printing, screen printing, flexographic printing, silk printing, electrostatic printing, and ink jet printing. In addition to the application of ink, it is also possible to give a metallic design by vapor deposition or sputtering of various metals.

  By attaching the decorative sheet obtained in this way onto a metal-based substrate such as a steel plate / aluminum plate, a decorative material having high weather resistance can be obtained, even when used for outdoor use, etc. Almost no deterioration in design properties over time.

<Formation of base material layer 1, pattern layer 2, adhesive layer 3, and transparent resin layer 4>
As the substrate layer 1, a 70 μm thick polypropylene film (made by Riken Technos Co., Ltd .; OW) to which titanium oxide and calcium carbonate are added is subjected to corona treatment, and gravure ink (manufactured by Toyo Ink Co., Ltd.) is applied to the surface side thereof. The grain pattern was gravure-printed using Lamister, and the pattern pattern layer 2 was applied. At this time, when the thickness of the ink applied was measured using a thickness meter, the average value was 2 μm. A two-component curable polyurethane adhesive (manufactured by Mitsui Chemicals, Inc .; Takelac, Takenate) was applied as an adhesive layer 3 on the pattern layer 2 so that the thickness after drying was 1 μm. Subsequently, 0.5 parts by weight of a benzotriazole ultraviolet absorber (Ciba Japan Co., Ltd .; Tinuvin 326) and 0.5 hindered amine radical scavenger (Ciba Japan Co., Ltd .; Kimasorb 2020) Transparent homopolypropylene resin added by parts by weight (manufactured by Prime Polymer; Prime TPO F3900) and adhesive resin imparted with a functional group by modification with maleic anhydride (manufactured by Mitsui Chemicals, Inc .; Admer SE800), The transparent resin layer 4 was obtained by lamination at a transparent homopolypropylene resin thickness of 80 μm, an adhesive resin thickness of 10 μm, and an extrusion temperature of 230 ° C. so that the adhesive resin side was in contact with the adhesive layer 3 by a coextrusion laminating method.

<Formation of surface protective layer 5>
After the corona treatment on the surface side of the transparent resin layer 4, 80 parts by weight of methyl methacrylate monomer and 20 parts by weight of cyclohexyl methacrylate monomer are used as the surface protective layer 5, and an unsaturated alcohol is added to impart a hydroxyl group to the side chain. The main component is a polymerized acrylic resin composition prepolymer, and the composition shown in the column of Example 1 in Table 1 and Table 2 below is used for adjusting the ultraviolet absorber, radical scavenger, and solid content. A main agent solution having a solid content of 33 parts by weight to which an ethyl acetate solvent has been added, and a hexamethylene diisocyanate type curing agent solution having a solid content of 75 parts by weight to which an ethyl acetate solvent has been added for adjusting the solid content, Mix so that the ratio is 10: 1 (the ratio of the number of hydroxyl groups in the main agent solution to the number of isocyanate groups in the curing agent solution is about 1: 2). Agent coating solution having an adjusted solid content to 20 parts by weight of ethyl acetate was added as component was applied so as to 9μm in thickness after solvent volatilization, to obtain a decorative sheet of Example 1.

  A decorative sheet of Example 2 was obtained in the same manner as Example 1 except that a polypropylene backer sheet (manufactured by Riken Technos Co., Ltd.) having a thickness of 220 μm was used for the base material layer 1.

  A decorative sheet of Example 3 was obtained in the same manner as in Example 1 except that the thickness of the surface protective layer 5 was changed to 22 μm.

  Instead of hexamethylene diisocyanate type curing agent, 3 parts by weight of Irgacure 184 was added as a photopolymerization initiator, and high molecular weight was increased by irradiating 1000 mJ / cm 2 of ultraviolet light at 10 cm under the light source with a high pressure mercury lamp. Obtained a decorative sheet of Example 4 in the same manner as Example 1.

  A decorative sheet of Example 5 was obtained in the same manner as Example 1 except that no radical scavenger was added to the surface protective layer.

  A decorative sheet of Example 6 was obtained in the same manner as in Example 5 except that no benzotriazole-based UV absorber was added to the surface protective layer 5.

  As a hydroxyphenyltriazine-based UV absorber in the surface protective layer 5, manufactured by Ciba Japan Co., Ltd .; instead of Tinuvin 479 (corresponding to Formula 2); A decorative sheet of Example 7 was obtained in the same manner as Example 6.

  A decorative sheet of Example 8 was obtained in the same manner as in Example 7 except that the content of cyclohexyl methacrylate in the surface protective layer 5 was 3 parts by weight.

  Addition amount of hydroxyphenyl triazine UV absorber (manufactured by ADEKA; LA-46 (corresponding to (Formula 1)) is 12 parts by weight, hydroxyphenyl triazine UV absorber (manufactured by Ciba Japan Co., Ltd.) A decorative sheet of Example 9 was obtained in the same manner as in Example 7 except that Tinuvin 400) was not added.

<Comparative Example 1>
A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that cyclohexyl methacrylate in the surface protective layer 5 was not used.

<Comparative Example 2>
As hydroxyphenyltriazine-based ultraviolet absorbers in the surface protective layer 5, manufactured by ADEKA; LA-46 (corresponding to (Formula 1)) and manufactured by Ciba Japan Co., Ltd .; equivalent to Tinuvin 479 ((Formula 2)) The decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1 except that 12 parts by weight of Tinuvin 400 was added.

<Comparative Example 3>
A decorative sheet of Comparative Example 3 was obtained by the same production method as in Comparative Example 2, except that Tinuvin 479 was added instead of Tinuvin 400 as a hydroxyphenyltriazine-based ultraviolet absorber in the surface protective layer 5.

<Comparative example 4>
A decorative sheet of Comparative Example 4 was obtained in the same manner as in Example 1 except that the cyclohexyl methacrylate monomer was added alone without copolymerization.

<Lamination to steel plate substrate>
In order to compare the performance of the decorative sheets of Examples 1 to 9 and Comparative Examples 1 to 4, an adhesive for olefin / steel sheet bonding (Hitachi After applying Chemical Polymer Co., Ltd. (Hybon) with a coating thickness of 20 μm, the adhesive was activated by heating at 180 ° C. for 3 minutes, and then described in Examples 1 to 9 and Comparative Examples 1 to 4 The decorative sheet was laminated while being nipped by a silicon roll, and cooled with cooling water immediately after the lamination, and then the surface moisture was removed to prepare a steel sheet decorative material.

<Weather resistance evaluation>
The steel sheet decorative material thus obtained was subjected to a weather resistance test using a die plastic / metal weather tester. The test conditions for the weather resistance test are shown below.
Testing machine: Daipla Metal Weather (Model: KU-R5DCI-A manufactured by Daipura Wintes Co., Ltd.)
Test conditions: 1 cycle = Light (illuminance 70 mW / cm 2, temperature 53 ° C., humidity 50% RH) 20 hours + Dew (temperature 30 ° C., humidity 95% RH) 4 hours (front and back shower 30 seconds) + Rest (temperature 30 ° C. , Humidity 95% RH) A 0.01 hour cycle test was conducted with a maximum of 70 cycles.
Evaluation method: Evaluation is based on the number of repetitions of occurrence of fading, white turbidity, or significant embrittlement that can be clearly seen visually (the higher the number, the higher the weather resistance).

<Post-processability evaluation>
The post-processability of the steel sheet decorative material thus obtained was evaluated by a bending test. The bending process conditions are shown below.
Atmospheric temperature: 5 ° C
Bending direction: TD direction bending (bending in a direction perpendicular to the flow direction during lamination)
Bending angle: 90 ° L-shaped bending (however, the decorative sheet side should be the outer surface)
Test conditions: Each steel sheet decorative material is cut into a size of 50 mm × 50 mm, a sample is set between an L-shaped acute angle jig and an obtuse angle jig, and post-processing is performed by air pressing with a press machine.
Evaluation method: Performed by comparing the degree of whitening and cracking of the bent portion.
Table 4 shows the results of the above performance comparison.

  As shown above, the decorative sheet of the present invention has excellent weather resistance. However, since the decorative sheets of Examples 2 to 4 tend to be somewhat inferior in post-processability as compared with the decorative sheets of other examples, it is necessary to consider the intended use.

  The decorative sheet of the present invention relates to a decorative sheet used for building materials such as building interiors and exteriors, surfaces and frame materials of joinery, surface materials of household electrical appliances, flooring materials, etc., wood boards, inorganic boards It can be used as a decorative material by being bonded to a metal plate or the like.

DESCRIPTION OF SYMBOLS 1 ... Base material layer 2 ... Pattern pattern layer 3 ... Adhesive layer 4 ... Transparent resin layer 5 ... Surface protective layer

Claims (9)

A decorative sheet having a surface protective layer on at least the outermost surface, wherein the surface protective layer is mainly composed of an acrylic resin composition containing at least cyclohexyl (meth) acrylate as a copolymerization component, and at least one kind is as follows: 1 or more types of hydroxyphenyl triazine type | system | group ultraviolet absorbers which have the structure shown in (Formula 1) are contained, and with respect to 100 weight part of said acrylic resin compositions, all hydroxyphenyl triazine type ultraviolet absorbers are contained. A total of 1 to 30 parts by weight of a decorative sheet.
  The hydroxyphenyl triazine-based ultraviolet absorber having the structure shown in (Formula 1) accounts for 30 to 95% by weight of all the hydroxyphenyltriazine-based ultraviolet absorbers contained in the surface protective layer. The decorative sheet according to claim 1, wherein the decorative sheet is provided.   The said cyclohexyl (meth) acrylate occupies 5 to 50 weight% of the acrylic resin composition used as the main component of the said surface protective layer, The any one of Claims 1-2 characterized by the above-mentioned. Cosmetic sheet The decorative sheet according to any one of claims 1 to 3, wherein at least one of the hydroxyphenyltriazine-based ultraviolet absorbers has a structure represented by the following (formula 2).
  The decorative sheet according to any one of claims 1 to 4, comprising 1 to 30 parts by weight of a benzotriazole-based ultraviolet absorber with respect to 100 parts by weight of the acrylic resin composition.   The decorative sheet according to any one of claims 1 to 5, comprising 1 to 30 parts by weight of a hindered amine radical scavenger with respect to 100 parts by weight of the acrylic resin composition.   The decorative sheet according to any one of claims 1 to 6, wherein the surface protective layer is crosslinked by isocyanate curing.   The thickness of the surface protective layer is in the range of 2 to 20 μm, and the total thickness of the decorative sheet is in the range of 40 to 300 μm. The decorative sheet as described.   A decorative sheet obtained by bonding the decorative sheet according to any one of claims 1 to 8 on a metal-based substrate such as a steel plate or aluminum.