Decorative sheets and decorative resin molded products

Abstract

To provide a decorative sheet including a barrier layer having excellent solid fragrance resistance and close adhesiveness.SOLUTION: The present disclosure provides a decorative sheet comprising at least a substrate sheet 1, a barrier layer 4, and a surface protecting layer 5 in this order, wherein the barrier layer includes a vinyl alcohol-based resin and a polyurethane resin. The vinyl alcohol-based resin is a modified polyvinyl alcohol resin with hydrophobic groups other than acetate groups.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present disclosure relates to a decorative sheet and a decorated resin molded product. [Background technology]

[0002] For example, decorative resin molded products in which a decorative sheet is laminated on the surface of a resin molded product are used as interior materials for vehicles.

[0003] Patent Document 1 discloses a three-dimensionally molded decorative sheet having at least a surface protective layer on a substrate, the surface protective layer being made of a cured product of a composition containing polycarbonate (meth)acrylate and a multifunctional (meth)acrylate in a predetermined ratio. The objective of this technology is to provide a decorative sheet having a surface protective layer that can achieve both scratch resistance and three-dimensional formability. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 6020642 specification Summary of the Invention [Problem to be solved by the invention]

[0005] When the aromatic components contained in the solid air freshener penetrate the surface protective layer of the decorative sheet and reach the base sheet, swelling of the base sheet may occur. On the other hand, in order to improve the resistance to the solid air freshener, it is expected that a barrier layer will be provided on the decorative sheet. A barrier layer containing a vinyl alcohol-based resin can easily improve the resistance to the solid air freshener, but tends to have low adhesion.

[0006] The present disclosure has been made in view of the above circumstances, and a main object of the present disclosure is to provide a decorative sheet having a barrier layer with good resistance to solid aromatic substances and good adhesion. [Means for solving the problem]

[0007] The present disclosure provides a decorative sheet having at least a substrate sheet, a barrier layer, and a surface protective layer in this order, wherein the barrier layer contains a vinyl alcohol-based resin and a polyurethane resin.

[0008] According to the present disclosure, by including a vinyl alcohol-based resin and a polyurethane resin in the barrier layer, it is possible to obtain a decorative sheet having a barrier layer that has good resistance to solid aromatic substances and good adhesion.

[0009] In the above disclosure, the barrier layer has an infrared absorption spectrum of 1130 cm -1 More than 1160cm -1 It may have a peak in the following range:

[0010] In the above disclosure, in the barrier layer, the proportion of the polyurethane resin with respect to the total of the vinyl alcohol resin and the polyurethane resin may be 5% by mass or more and 40% by mass or less.

[0011] In the above disclosure, the vinyl alcohol resin may be a modified polyvinyl alcohol resin having a hydrophobic group other than an acetate group.

[0012] In the above disclosure, the hydrophobic group may have a reactive group.

[0013] In the above disclosure, the reactive group may be a reactive carbonyl group.

[0014] In the above disclosure, the modified polyvinyl alcohol resin may have, as the hydrophobic group, an acetoacetyl group having the reactive carbonyl group.

[0015] In the above disclosure, the surface protective layer may contain a polyurethane resin.

[0016] In the above disclosure, the surface protective layer has a Martens hardness of 40 N / mm2 It may be the following:

[0017] In the above disclosure, the surface protection layer and the barrier layer may be in direct contact with each other.

[0018] The present disclosure also provides a decorated resin molded article having a resin molded article and a decorative sheet located on the surface of the resin molded article, wherein the decorative sheet has at least a base sheet, a barrier layer, and a surface protective layer in this order, and the barrier layer contains a vinyl alcohol-based resin and a polyurethane resin.

[0019] According to the present disclosure, by using the decorative sheet described above, a decorated resin molded product can be obtained that has a barrier layer that has good resistance to and adhesion to solid aromatic substances. [Effects of the Invention]

[0020] The present disclosure has the effect of providing a decorative sheet having a barrier layer that has good resistance to solid aromatic substances and good adhesion. [Brief explanation of the drawings]

[0021] [Figure 1] 1 is a schematic cross-sectional view showing an example of a decorative sheet according to the present disclosure. [Figure 2] 1 is an IR spectrum of the decorative sheet obtained in Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0022] The decorative sheet and the decorated resin molded product according to the present disclosure will be described in detail below.

[0023] A.Decorative sheet Fig. 1 is a schematic cross-sectional view showing an example of a decorative sheet according to the present disclosure. The decorative sheet 10 shown in Fig. 1 comprises, in this order, a base sheet 1, a design layer 2, a primer layer 3, a barrier layer 4, and a surface protective layer 5. The barrier layer 4 contains a vinyl alcohol resin and a polyurethane resin.

[0024] According to the present disclosure, by including a vinyl alcohol-based resin and a polyurethane resin in the barrier layer, a decorative sheet having a barrier layer with good solid air freshener resistance and adhesion can be obtained. As described above, when the aromatic components contained in the solid air freshener penetrate the decorative sheet from the surface protective layer side and reach the base sheet, swelling of the base sheet may occur. On the other hand, providing a barrier layer in the decorative sheet is expected to improve solid air freshener resistance. A barrier layer containing a vinyl alcohol-based resin is likely to improve solid air freshener resistance, but tends to have poor adhesion.

[0025] Here, vinyl alcohol-based resins exhibit good resistance to solid air fresheners by crystallizing through hydrogen bonding. Meanwhile, the barrier layer of the present disclosure contains not only a vinyl alcohol-based resin but also a polyurethane resin. It is expected that adding a different type of resin, such as a polyurethane resin, to a vinyl alcohol-based resin may inhibit the crystallization of the vinyl alcohol-based resin. Surprisingly, however, it has been found that even when a polyurethane resin is used, the vinyl alcohol-based resin crystallizes or a structure similar to a crystal is formed, thereby maintaining good resistance to solid air fresheners. Furthermore, since the barrier layer of the present disclosure contains a polyurethane resin, it is possible to improve adhesion. In this way, by including a vinyl alcohol-based resin and a polyurethane resin in the barrier layer, it is possible to achieve both resistance to solid aromatic substances and adhesion.

[0026] 1. Barrier layer The barrier layer in the present disclosure contains a vinyl alcohol-based resin and a polyurethane resin.

[0027] (1) Vinyl alcohol resin The vinyl alcohol resin is a resin having a [—CH2—CH(OH)—] unit. Examples of vinyl alcohol resins include copolymer resins using vinyl alcohol and polyvinyl alcohol resins (PVA).

[0028] Polyvinyl alcohol resins are generally resins obtained by saponifying polyvinyl acetate. The degree of saponification of polyvinyl alcohol resins is not particularly limited, but a higher degree is preferable from the viewpoint of resistance to solid fragrances. The degree of saponification is, for example, 70 mol% or more, or may be 80 mol% or more, 90 mol% or more, 95 mol% or more, or 99 mol% or more.

[0029] The average degree of polymerization of the polyvinyl alcohol resin is not particularly limited, but is, for example, 200 or more and 6000 or less, or may be 300 or more and 4000 or less, or may be 400 or more and 2000 or less.

[0030] The polyvinyl alcohol resin may be a modified polyvinyl alcohol resin having a hydrophobic group other than an acetate group (-OCOCH3). By using such a modified polyvinyl alcohol resin, the hydrophobicity (water resistance) of the barrier layer is improved, and a barrier layer with good sunscreen resistance (sunscreen cream resistance) can be obtained.

[0031] The modified polyvinyl alcohol resin preferably has a hydrophobic group other than an acetate group as a side chain. The hydrophobic group refers to a functional group having at least carbon and no OH group. The hydrophobic group may be linear, branched, or cyclic. From the viewpoint of crystallization of the vinyl alcohol resin, the hydrophobic group is preferably linear or branched. The number of carbon atoms in the hydrophobic group is, for example, 2 or more, or may be 3 or more, or 5 or more. An example of the hydrophobic group is a functional group represented by -OR. R has at least carbon. Examples of R include hydrocarbon groups such as alkyl groups having 3 or more carbon atoms, alkenyl groups having 3 or more carbon atoms, and alkynyl groups having 3 or more carbon atoms.

[0032] Examples of alkyl groups having 3 or more carbon atoms include n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 1-methylpentyl, cyclopentylmethyl, n-heptyl, 1-ethylpentyl, cyclohexylmethyl, and n-octyl. Examples of alkenyl groups having 3 or more carbon atoms include allyl, isopropenyl, and butynyl. Examples of alkynyl groups having 3 or more carbon atoms include propynyl, propargyl, and butynyl.

[0033] The hydrophobic group may have a reactive group. Specifically, in a functional group represented by -OR, R has at least carbon and may further have a reactive group. An example of the reactive group is a reactive carbonyl group. The hydrophobic group may have only one reactive group, or may have two or more reactive groups. An example of a hydrophobic group having two reactive carbonyl groups is an acetoacetyl group (-OCOCH2COCH3).

[0034] The modified polyvinyl alcohol resin may have only one kind of the above hydrophobic group, or may have two or more kinds of the above hydrophobic group, and may or may not have an acetate group.

[0035] On the other hand, examples of copolymer resins using vinyl alcohol include copolymers of acrylic acid or acrylates with vinyl alcohol, copolymers of maleic anhydride or maleic acid or fumaric acid with vinyl alcohol, and copolymers of ethylene and vinyl alcohol (EVOH). Commercially available EVOH products include EVAL (manufactured by Kuraray Co., Ltd.) and Soarnol (manufactured by Mitsubishi Chemical Corporation).

[0036] The barrier layer may contain only one type of vinyl alcohol resin, or may contain two or more types of vinyl alcohol resins.

[0037] (2) Polyurethane resin The polyurethane resin is a resin obtained by reacting a polyol with a polyisocyanate. If necessary, the polyurethane resin may be obtained by further reacting a compound having a hydrophilic functional group in the molecule or a compound such as a chain extender in addition to the polyol and the polyisocyanate.

[0038] Examples of the polyol include polyester polyol, polyether polyol, polycarbonate polyol, and polyolefin polyol.

[0039] Examples of polyester polyols include condensates of low-molecular-weight diol components such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, cyclohexanedimethanol, bisphenol A, and hydrogenated bisphenol A with polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalic acid, and biphenyldicarboxylic acid.

[0040] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide copolymers (random and / or block copolymers), and polytetramethylene glycol.

[0041] Polycarbonate polyols are compounds obtained by reacting a diol with a compound that serves as a carbonyl component. Examples of the diol include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methylpentanediol, neopentyl glycol, dipropylene glycol, bisphenol A, hydrogenated bisphenol A, trimethylolpropane, and cyclohexanedimethanol. The compound that serves as the carbonyl component is, for example, a carbonic acid diester, phosgene, or any compound selected from the group consisting of these equivalents. Specific examples thereof include carbonate diesters such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate, phosgene, and halogenated formates such as methyl chloroformate, ethyl chloroformate, and phenyl chloroformate. Polycarbonate polyols are produced by common production methods such as the phosgene method or the transesterification method of a diol and a carbonate ester.

[0042] Examples of polyolefin polyols include polybutadiene polyols, polyisoprene polyols, and hydrogenated polyols thereof.

[0043] Examples of the polyisocyanate include aromatic polyisocyanates, araliphatic polyisocyanates, alicyclic polyisocyanates, and aliphatic polyisocyanates.

[0044] Examples of aromatic polyisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 4,4'-dibenzyl diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, 1,3-phenylene diisocyanate, and 1,4-phenylene diisocyanate.

[0045] Examples of the aromatic aliphatic polyisocyanate include tetraalkyldiphenylmethane diisocyanate, dialkyldiphenylmethane diisocyanate, and α,α,α,α-tetramethylxylylene diisocyanate.

[0046] Examples of alicyclic polyisocyanates include isophorone diisocyanate, hydrogenated xylylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and 1,3-bis(isocyanatemethyl)cyclohexane.

[0047] Examples of aliphatic polyisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2-methylpentane-1,5-diisocyanate, and 3-methylpentane-1,5-diisocyanate.

[0048] The weight-average molecular weight of the polyurethane resin is not particularly limited, but is preferably increased as much as possible by introducing at least one of a branched structure and an internal crosslinked structure. The weight-average molecular weight of the polyurethane resin is, for example, 10,000 or more, and may be 50,000 or more. On the other hand, the weight average molecular weight of the polyurethane resin is, for example, 15,000,000 or less, and may be 5,000,000 or less.

[0049] The polyurethane resin may also have a hydrophilic functional group to impart dispersibility in water. Examples of hydrophilic functional groups include carboxyl groups and sulfonyl groups. The hydrophilic functional group can be introduced using the following compounds. Examples include carboxyl group-containing compounds such as dimethylolpropionic acid, dimethylolbutanoic acid, lactic acid, and glycine, sulfonic acid group-containing compounds such as taurine, and polyester polyols made from compounds containing at least one of a carboxyl group and a sulfonic acid group. A chain extender may also be used to increase the molecular weight of the polyurethane resin. Preferred chain extenders include diamines and polyamines that also function to introduce internal crosslinking structures. Examples of diamines include ethylenediamine, trimethylenediamine, piperazine, and isophoronediamine. Examples of polyamines include diethylenetriamine, dipropylenetriamine, and triethylenetetramine.

[0050] Furthermore, the polyurethane resin is preferably an aqueous polyurethane resin. The aqueous polyurethane resin is an emulsion of a urethane resin. The aqueous polyurethane resin may be a non-reactive type or a reactive type. In the reactive type aqueous polyurethane resin, the terminal isocyanate groups are protected with a blocking agent. The aqueous polyurethane resin may be a water-soluble type or a self-emulsifying type. Both the water-soluble type and the self-emulsifying type have the above-mentioned hydrophilic functional groups. The aqueous polyurethane resin preferably has an internal crosslinked structure in which the polyurethane resin is crosslinked in a network form. Furthermore, the aqueous polyurethane resin preferably has a urea bond. A urea bond is formed by the reaction of an isocyanate group with an amine.

[0051] The barrier layer may contain only one type of polyurethane resin, or may contain two or more types of polyurethane resins.

[0052] (3) Barrier layer The barrier layer in the present disclosure contains a vinyl alcohol-based resin and a polyurethane resin.

[0053] The barrier layer has an infrared absorption spectrum (IR spectrum) of 1130 cm -1 More than 1160cm -1 It is preferable that the peak is in the following range: The peak associated with the crystallization of vinyl alcohol-based resin is 1130 cm -1 More than 1160cm -1 The barrier layer is observed in the range of 1130 cm -1 More than 1160cm -1 A decorative sheet having a peak in the following range can be obtained that has excellent resistance to solid aromatic substances. The infrared absorption spectrum of the barrier layer can be obtained, for example, by cutting a cross section of the barrier layer and measuring the exposed layer using an attenuated total reflection method (ATR method). The cross section can be obtained, for example, by gradually scraping the surface layer from the decorative sheet to expose the underlying layers one by one, or by exposing the entire cross section using a device such as a microtome or a cutter knife. The former method is effective when the layer structure, such as the number of layers and film thickness, is known from cross-sectional observation. In the latter method, it is preferable to cut the decorative sheet at an angle to expose the cross section in order to ensure a measurement area.

[0054] In the barrier layer, the proportion of polyurethane resin relative to the total of polyvinyl alcohol resin and polyurethane resin is, for example, 5% by mass or more, or alternatively 10% by mass or more, or 15% by mass or more, or even 20% by mass or more. If the proportion of polyurethane resin is too low, good adhesion may not be obtained. On the other hand, the proportion of polyurethane resin is, for example, 40% by mass or less, or alternatively 35% by mass or less, or alternatively 30% by mass or less, or even 25% by mass or less. If the proportion of polyurethane resin is too high, good solid fragrance resistance may not be obtained.

[0055] The barrier layer may or may not contain a crosslinking agent that improves the crosslink density of the vinyl alcohol resin. Examples of the crosslinking agent include dihydrazide compounds such as adipic acid dihydrazide (ADH), metal salts, boric acid, and polymeric acids such as polyacrylic acid.

[0056] The barrier layer may be a cured product of a resin composition containing a vinyl alcohol resin and a polyurethane resin. The resin composition may contain a curing agent. Examples of the curing agent include carbodiimide curing agents and isocyanate curing agents. The carbodiimide curing agent is not particularly limited as long as it is a compound having a carbodiimide structure (-N=C=N-) in the molecule. Examples of compounds having a carbodiimide group include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. Commercially available products include Carbodilite V-02, Carbodilite V-02-L2, Carbodilite SV-02, Carbodilite V-04, Carbodilite V-10, Carbodilite SW-12G, Carbodilite E-02, Carbodilite E-03A, and Carbodilite E-05 (all manufactured by Nisshinbo Chemical).

[0057] Examples of isocyanate curing agents include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenylether diisocyanate, polymethylene polyphenylene polyisocyanate, 2-nitrodiphenyl-4 Examples of aromatic isocyanates include 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate. Examples of the isocyanate compound include aliphatic isocyanates such as 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (1,6-hexamethylene diisocyanate, HDI), 1,6-diisocyanato-2,2,4-trimethylhexane, and methyl 2,6-diisocyanatohexanoate (lysine diisocyanate). Examples of the isocyanate compound include alicyclic diisocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate.

[0058] The proportion of the curing agent contained in the resin composition is not particularly limited, but may be, for example, 0.5 parts by mass or more, 1 part by mass or more, or 3 parts by mass or more relative to 100 parts by mass of the resin, while the proportion of the curing agent may be, for example, 50 parts by mass or less, or 35 parts by mass or less relative to 100 parts by mass of the resin.

[0059] In the present disclosure, it is preferable that a layer in direct contact with the barrier layer contains a polyurethane resin. This is because the layer in direct contact with the barrier layer contains a polyurethane resin, thereby improving the adhesion between the layer and the barrier layer. The layer in direct contact with the barrier layer is not particularly limited, and examples thereof include a surface protection layer, a primer layer, and a pattern layer. In particular, it is preferable that the layer in direct contact with one surface of the barrier layer and the layer in direct contact with the other surface of the barrier layer each contain a polyurethane resin.

[0060] The barrier layer is disposed between the surface protective layer and the substrate sheet in the decorative sheet. At least one of a design layer and a primer layer, which will be described later, may also be disposed between the barrier layer and the substrate sheet.

[0061] An example of a method for forming a barrier layer is a method of coating a resin composition containing a vinyl alcohol resin and a polyurethane resin. Examples of coating methods include common methods such as gravure coating, bar coating, roll coating, reverse roll coating, and comma coating. Furthermore, when the resin composition contains a curing agent, the uncured resin layer (uncured barrier layer) after coating is usually subjected to a curing treatment. Examples of curing treatments include heat treatment.

[0062] The heat treatment temperature is not particularly limited as long as it is a temperature at which the desired curing reaction occurs, but it is, for example, 90°C or higher, or may be 120°C or higher, or may be 150°C or higher. On the other hand, the upper limit of the heat treatment temperature can be selected appropriately. The heat treatment method is not particularly limited, and a general heat treatment method can be used.

[0063] The thickness of the barrier layer is, for example, 1 μm or more, or may be 3 μm or more, or may be 5 μm or more. If the thickness is too small, the function as a barrier layer may be reduced. On the other hand, the thickness of the barrier layer is, for example, 50 μm or less, may be 30 μm or less, or may be 10 μm or less. If the thickness is too large, three-dimensional formability may be reduced.

[0064] 2.Surface protection layer The surface protection layer in the present disclosure is preferably a cured product of a resin composition containing at least a resin. The resin composition may contain a curing agent. The resin may be a thermosetting resin or an ionizing radiation curable resin such as an electron beam curable resin. Examples of the resin include polyurethane resin and fluororesin, and among these, polyurethane resin is preferred because it allows for the production of a decorative sheet with good scratch resistance. The curing agent is the same as that described above in "1. Barrier layer."

[0065] The polyurethane resin is preferably a resin that can react with a curing agent. The polyurethane resin is obtained by reacting a polyol with a polyisocyanate. If necessary, the polyurethane resin may be obtained by further reacting a compound having a hydrophilic functional group in the molecule or a compound such as a chain extender with the polyol and the polyisocyanate.

[0066] The polyurethane resin (second polyurethane resin) in the surface protective layer and the polyurethane resin (first polyurethane resin) in the barrier layer may be the same resin or different resins. Details of the second polyurethane resin are the same as those of the first polyurethane resin described above. The second polyurethane resin is preferably an aqueous polyurethane resin. Furthermore, it is particularly preferable that the second polyurethane resin is a thermosetting polyurethane resin that can promote a curing reaction simultaneously with the curing treatment of the barrier layer.

[0067] The surface protective layer preferably has a low Martens hardness, because this allows a decorative sheet with good scratch resistance to be obtained. The Martens hardness of the surface protective layer is, for example, 40 N / mm 2 less than 35N / mm 2 It may be less than 30N / mm 2 It may be the following: On the other hand, the Martens hardness of the surface protection layer is, for example, 0.01 N / mm 2Above 0.8N / mm 2 It may be more than 3N / mm 2 It may be more than that.

[0068] The Martens hardness can be adjusted by, for example, the crosslink density of the cured resin and the average molecular weight of the uncured resin. As the crosslink density of the cured resin increases, the Martens hardness tends to increase. In addition, the Martens hardness can be adjusted by changing the amount of curing agent used.

[0069] The Martens hardness is measured by pressing an indenter into the surface protective layer. For example, a Vickers indenter can be used as the indenter. Furthermore, for example, a "PICODENTOR HM-500" (manufactured by Fisher Instruments) can be used as the measuring instrument. Note that, if the depth to which the indenter penetrates the surface protective layer is sufficiently small compared to the thickness of the surface protective layer, the influence of other layers of the decorative sheet (e.g., the substrate sheet) can be ignored. Specifically, if the depth to which the indenter penetrates the surface protective layer is approximately 1 / 10 of the thickness of the surface protective layer, the influence of other layers of the decorative sheet (e.g., the substrate sheet) can be ignored. Therefore, even if the decorative sheet itself is measured as the measurement object, the Martens hardness of the surface protective layer can be measured. On the other hand, if the influence of other layers of the decorative sheet (e.g., the substrate sheet) cannot be ignored, it is preferable to measure the Martens hardness by measuring only the surface protective layer.

[0070] An example of a method for forming the surface protective layer is a method of applying a resin composition containing a polyurethane resin. Examples of the application method include the same application method as for the barrier layer described above. Furthermore, the uncured resin layer (uncured surface protective layer) after application may be subjected to a curing treatment. Examples of the curing treatment include heat treatment and ionizing radiation irradiation treatment.

[0071] The heat treatment temperature is not particularly limited as long as it is a temperature at which the desired curing reaction occurs, but it is, for example, 50°C or higher, or may be 70°C or higher, or may be 80°C or higher. On the other hand, the upper limit of the heat treatment temperature can be appropriately selected depending on the types of resin composition and curing agent. The heat treatment method is not particularly limited, and a general heat treatment method can be used.

[0072] The ionizing radiation irradiation treatment is a treatment in which a coated uncured resin layer is irradiated with ionizing radiation such as electron beams or ultraviolet rays to cure it. When electron beams are used as the ionizing radiation, the acceleration voltage is not particularly limited, but is, for example, 70 kV or more and 300 kV or less. The exposure dose is also not particularly limited, but is, for example, 5 kGy or more and 300 kGy or less. On the other hand, when ultraviolet rays are used as the ionizing radiation, it is preferable to use ultraviolet rays with a wavelength of, for example, 190 nm or more and 380 nm or less.

[0073] The surface protective layer may contain various additives as needed. Examples of additives include weather resistance improvers, abrasion resistance improvers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropy-imparting agents, coupling agents, plasticizers, antifoaming agents, fillers, solvents, and colorants. The content of the additives can be appropriately set depending on the purpose.

[0074] Examples of weather resistance improvers include ultraviolet absorbers and light stabilizers. The ultraviolet absorbers may be either inorganic or organic. Examples of inorganic ultraviolet absorbers include titanium dioxide, cerium oxide, and zinc oxide. On the other hand, examples of organic ultraviolet absorbers include benzotriazole-based ultraviolet absorbers. Examples of light stabilizers include hindered amine-based light stabilizers.

[0075] The wear resistance improver preferably has a particulate shape. The wear resistance improver may be either inorganic or organic. Examples of inorganic wear resistance improvers include α-alumina, silica, kaolinite, iron oxide, diamond, and silicon carbide. On the other hand, examples of organic wear resistance improvers include crosslinked acrylic resins and polycarbonate resins.

[0076] The thickness of the surface protective layer is, for example, 2 μm or more, or may be 4 μm or more, or may be 6 μm or more. If the thickness is too small, the function as a protective layer may be reduced. On the other hand, the thickness of the surface protection layer is, for example, 100 μm or less, or may be 60 μm or less, or may be 30 μm or less. If the thickness is too large, three-dimensional formability may decrease.

[0077] Furthermore, it is preferable that the surface protective layer has a large breaking elongation, as this improves three-dimensional formability. The breaking elongation of the surface protective layer in a tensile test at 150°C is, for example, 120% or more, or may be 150% or more, or may be 200% or more. On the other hand, the breaking elongation of the surface protective layer in a tensile test at 150°C is not particularly limited, but is, for example, 500% or less. The breaking elongation of the surface protective layer can be measured, for example, as follows, for the decorative sheet or as a single surface protective layer.

[0078] The breaking elongation of the surface protective layer of a decorative sheet can be measured under the following conditions in accordance with JIS K 7127. First, a decorative sheet is cut into a 25 mm wide, 120 mm long test piece. Next, the tensile elongation of this test piece is measured until cracks appear in the surface protective layer under the following measurement conditions: a pulling speed of 1000 mm / min, a chuck distance of 80 mm, a gauge length of 50 mm, and a temperature of 160°C. For example, if a thermosetting resin is used for the surface protective layer and a thermoplastic resin is used for the other layers, the layer using the thermoplastic resin generally has a higher breaking elongation than the layer using the thermosetting resin, so it is easy to determine that any cracks that appear during the breaking elongation measurement of the decorative sheet originate from the surface protective layer.

[0079] The breaking elongation of a single surface protective layer can be measured under the following conditions in accordance with JIS K 7127. First, a transfer sheet with a surface protective layer formed on its surface is cut into a piece 25 mm wide and 120 mm long, and the transfer sheet is peeled off to obtain a test piece. Next, the tensile elongation of this test piece is measured under the following conditions: a pulling speed of 1000 mm / min, a chuck distance of 80 mm, a gauge length of 50 mm, and a temperature of 160°C, until the surface protective layer cracks.

[0080] 3. Base sheet The substrate sheet in the present disclosure contains a resin. The resin used in the substrate sheet is preferably a thermoplastic resin. Examples of thermoplastic resins include acrylonitrile-butadiene-styrene resin (ABS resin); acrylic resin; polyolefin resin such as polypropylene or polyethylene; polycarbonate resin; and vinyl chloride resin. These resins may be used alone or in combination of two or more. The substrate sheet may be a single-layer sheet or a multi-layer sheet.

[0081] The thickness of the base sheet varies depending on the application, but may be, for example, 0.05 mm or more, or 0.1 mm or more, while the thickness of the base sheet may be, for example, 1.0 mm or less, or 0.7 mm or less.

[0082] At least one surface of the substrate sheet may be surface-treated. Surface treatment can improve adhesion between the substrate sheet and other layers, for example. Examples of surface treatment methods include oxidation and roughening. Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone / ultraviolet treatment. Examples of roughening methods include sandblasting and solvent treatment. The substrate sheet may also be provided with decorative features such as paint or a pattern. Not only the substrate sheet, but also at least one surface of each layer constituting the decorative sheet may be surface-treated. This is because it can improve adhesion between layers.

[0083] 4.Picture layer The decorative sheet of the present disclosure may have a pattern layer. By providing the pattern layer, decorativeness can be easily imparted to the decorative sheet. The pattern layer is preferably located between the base sheet and the barrier layer.

[0084] Examples of patterns for the design layer include wood grain patterns, stone patterns that imitate the surface of rock, such as marble patterns (e.g., travertine marble patterns), fabric patterns that imitate fabric or cloth-like patterns, tile patterns, and brickwork patterns. Furthermore, marquetry and patchwork that combine these patterns may also be used. Furthermore, the design layer pattern may be a solid color.

[0085] The design layer preferably contains a colorant and a binder. Examples of the colorant include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; metal pigments such as aluminum and brass; and pearlescent pigments such as titanium dioxide-coated mica and basic lead carbonate.

[0086] Examples of binders include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, and cellulose acetate resins.

[0087] The design layer may also contain additives such as extender pigments, solvents, stabilizers, plasticizers, catalysts, and hardeners. The design layer has a thickness of, for example, 1 μm or more and 20 μm or less. The design layer can be formed by a common printing method such as gravure printing.

[0088] The decorative sheet of the present disclosure may have a concealing layer between the substrate sheet and the pattern layer. By providing the concealing layer, for example, it is possible to prevent the color of the substrate sheet from affecting the pattern layer. The color of the concealing layer is preferably an opaque color. Furthermore, the concealing layer is preferably a so-called solid layer.

[0089] 5. Primer layer The decorative sheet of the present disclosure may have a primer layer. By providing the primer layer, for example, even when the surface protective layer is stretched, the occurrence of fine cracks or whitening in the surface protective layer can be suppressed. The primer layer is preferably located between the substrate sheet and the barrier layer. Furthermore, when the decorative sheet has a pattern layer, the primer layer is preferably located between the pattern layer and the barrier layer.

[0090] The primer layer preferably contains a resin. Examples of such resins include (meth)acrylic resins, urethane resins, (meth)acrylic-urethane copolymer resins, vinyl chloride-vinyl acetate copolymer resins, polyester resins, butyral resins, chlorinated polypropylene, and chlorinated polyethylene. These resins may be used alone or in combination of two or more. In this specification, (meth)acrylic means acrylic or methacrylic.

[0091] Examples of (meth)acrylic resins include homopolymers of (meth)acrylic acid esters, copolymers of two or more different (meth)acrylic acid ester monomers, and copolymers of (meth)acrylic acid esters with other monomers. Specific examples of (meth)acrylic resins include polymethyl(meth)acrylate, polyethyl(meth)acrylate, polypropyl(meth)acrylate, polybutyl(meth)acrylate, methyl(meth)acrylate-butyl(meth)acrylate copolymer, ethyl(meth)acrylate-butyl(meth)acrylate copolymer, ethylene-methyl(meth)acrylate copolymer, and styrene-methyl(meth)acrylate copolymer.

[0092] Examples of urethane resins include polyurethanes that use polyols (polyhydric alcohols) as the main component and isocyanates as the crosslinking agents (curing agents). Polyols have two or more hydroxyl groups in their molecules. Examples of polyols include polyester polyols, polyethylene glycols, polypropylene glycols, acrylic polyols, and polyether polyols. On the other hand, examples of isocyanates include polyhydric isocyanates having two or more isocyanate groups in their molecules; aromatic isocyanates such as 4,4-diphenylmethane diisocyanate; and aliphatic (or alicyclic) isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. The primer layer may contain a butyral resin in addition to the urethane resin.

[0093] Examples of (meth)acrylic-urethane copolymer resins include acrylic / urethane (polyester urethane) block copolymer resins. The various isocyanates mentioned above can be used as curing agents. The acrylic / urethane ratio (mass ratio) in the acrylic / urethane (polyester urethane) block copolymer resin is, for example, from (9 / 1) to (1 / 9) or from (8 / 2) to (2 / 8).

[0094] The thickness of the primer layer is, for example, 0.1 μm or more, and may be 1 μm or more. On the other hand, the thickness of the primer layer is, for example, 10 μm or less. Examples of methods for forming the primer layer include general coating methods such as gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, and reverse roll coating.

[0095] 6.Adhesive layer The decorative sheet according to the present disclosure may also have an adhesive layer on the opposite side of the substrate sheet from the surface protective layer, which improves adhesion between the decorative sheet and the resin molded article.

[0096] The adhesive layer preferably contains a resin. Examples of resins used in the adhesive layer include thermoplastic resins and thermosetting resins. Examples of thermoplastic resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, and rubber-based resins. Examples of thermosetting resins include urethane resins and epoxy resins. These resins may be used alone or in combination of two or more.

[0097] The thickness of the adhesive layer is, for example, 0.1 μm or more, and may be 1 μm or more. On the other hand, the thickness of the adhesive layer is, for example, 10 μm or less. The method for forming the adhesive layer is not particularly limited, and includes a general coating method.

[0098] 7.Decorative sheet The decorative sheet of the present disclosure has at least a base sheet, a barrier layer, and a surface protective layer in this order, and may further have at least one of a design layer, a primer layer, and an adhesive layer.

[0099] The present disclosure can also provide a method for manufacturing the above-described decorative sheet, that is, the method for manufacturing the above-described decorative sheet includes a barrier layer forming step of forming the barrier layer and a surface protective layer forming step of forming the surface protective layer.

[0100] The decorative sheet of the present disclosure is preferably used for producing a decorated resin molded product (particularly a three-dimensional molded product), the details of which will be described later.

[0101] B. Decorative resin molding The decorated resin molded article of the present disclosure includes a resin molded article and a decorative sheet located on the surface of the resin molded article.

[0102] According to the present disclosure, by using the decorative sheet described above, a decorated resin molded product can be obtained that has a barrier layer that has good resistance to and adhesion to solid aromatic substances.

[0103] The decorative sheet in this disclosure is similar to that described above in "A. Decorative Sheet," and therefore will not be described here. The decorative sheet in a decorated resin molded product is usually formed to follow the shape of at least a portion of the outer surface of the resin molded product. Furthermore, the decorative sheet in a decorated resin molded product is usually integrated with the resin molded product. Furthermore, the decorative sheet in a decorated resin molded product usually has a surface protection layer located on the outside and a base sheet located on the inside.

[0104] The resin molded article in the present disclosure preferably has, for example, at least one of a curved portion, a bent portion, and a flat portion. The resin used for the resin molded article may be a thermoplastic resin or a thermosetting resin.

[0105] Examples of thermoplastic resins include polyolefin resins such as polyethylene and polypropylene, acrylonitrile-butadiene-styrene resin (ABS resin), styrene resin, polycarbonate resin, acrylic resin, and vinyl chloride resin. On the other hand, examples of thermosetting resins include urethane resin and epoxy resin. These resins may be used alone or in combination of two or more.

[0106] Examples of methods for producing the decorated resin molded article of the present disclosure include injection molding methods such as insert molding, simultaneous injection molding and decoration, blow molding, and gas injection molding.

[0107] For example, in the insert molding method, a decorative sheet is vacuum-formed into the surface shape of the molded product in advance (offline preforming) using a vacuum forming mold during the vacuum forming process, and then excess parts are trimmed as needed to obtain a molded sheet. This molded sheet is then inserted into an injection mold, which is then clamped, and a fluid resin is injected into the mold and solidified, integrating the decorative sheet with the outer surface of the resin molded product at the same time as injection molding. This results in a decorated resin molded product.

[0108] In addition, for example, in the simultaneous injection molding and decoration method, the decorative sheet is placed in a female mold that also serves as a vacuum forming mold and is provided with suction holes for injection molding, and preforming (in-line preforming) is performed in this female mold. The injection mold is then clamped, and the fluid resin is injected into the mold and solidified, thereby integrating the decorative sheet with the outer surface of the resin molded product at the same time as injection molding, thereby obtaining a decorated resin molded product.

[0109] The decorated resin molded product of the present disclosure can also be produced by a decoration method, such as vacuum bonding, in which a decorative sheet is attached to a pre-prepared three-dimensional resin molded product. In the vacuum bonding method, the decorative sheet and the resin molded product are first placed in a vacuum bonding machine having a first vacuum chamber located above and a second vacuum chamber located below, with the decorative sheet facing the first vacuum chamber and the resin molded product facing the second vacuum chamber, with the base sheet of the decorative sheet facing the resin molded product. The two vacuum chambers are then evacuated. The resin molded product is placed on a lifting platform provided in the second vacuum chamber, which can be raised and lowered. Next, the first vacuum chamber is pressurized, and the lifting platform is used to press the resin molded product against the decorative sheet. The pressure difference between the two vacuum chambers is used to stretch and attach the decorative sheet to the surface of the resin molded product. Finally, the two vacuum chambers are opened to the atmosphere, and excess portions of the decorative sheet are trimmed as necessary to obtain the decorated resin molded product. In the vacuum pressure bonding method, it is preferable to include a step of heating the decorative sheet before the step of pressing the resin molded product against the decorative sheet in order to soften the decorative sheet and improve its formability. A vacuum pressure bonding method including such a step is sometimes called a vacuum heat-press bonding method.

[0110] Applications of the decorated resin molded products of the present disclosure include, for example, interior or exterior materials for vehicles such as automobiles; fittings such as window frames and door frames; interior materials for building materials such as walls, floors, and ceilings; housings for home appliances such as television sets and air conditioners; and containers.

[0111] The present disclosure is not limited to the above-described embodiments. The above-described embodiments are merely examples, and any configuration that is substantially identical to the technical idea described in the claims of the present disclosure and that exhibits similar effects is included within the technical scope of the present disclosure in any case. [Example]

[0112] [Example 1] An ABS resin film (flexural modulus: 2000 MPa, thickness: 400 μm) was prepared as a substrate sheet. Next, a wood grain pattern layer was formed on the surface of the substrate sheet by gravure printing using an ink containing an acrylic resin as a binder. In this way, a first member having a substrate sheet and a pattern layer was obtained.

[0113] Next, aqueous polyurethane resin dispersion 1 was prepared as a polyurethane resin for forming a surface protective layer as follows: First, 65.00 parts by mass of polycarbonate polyol (manufactured by Asahi Kasei Corporation, product name "Duranol T-4671", containing 1,4-butanediol and 1,6-hexanediol as raw materials, repeating units: 1,4-butanediol / 1,6-hexanediol = 7 / 3 (molar ratio), hydroxyl value = 112.2 mg KOH / g, number average molecular weight = 1000), 5.00 parts by mass of dimethylolpropionic acid, and 100 parts by mass of methyl ethyl ketone were added to a four-neck flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, and the mixture was thoroughly stirred and dissolved. Next, 30.00 parts by mass of dicyclohexylmethane diisocyanate was added and the mixture was reacted at 75°C until the NCO content reached 1.00%. The prepolymer solution was then cooled to 45°C, and 3.77 parts by mass of triethylamine was added as a neutralizer. 400.00 parts by mass of water was gradually added using a homomixer to emulsify and disperse the mixture. 0.65 parts by mass of diethylenetriamine was then added, and a chain extension reaction was carried out at 30°C for 30 minutes. The resin solution was heated under reduced pressure to distill off the methyl ethyl ketone, yielding an aqueous polyurethane resin dispersion 1 with a solids content of 25%.

[0114] A resin composition containing 100 parts by mass of aqueous polyurethane resin dispersion 1 and 5 parts by mass of a carbodiimide curing agent (V-02-L2 manufactured by Nisshinbo Chemical, solids content 40% by mass) was prepared. Next, the prepared resin composition was applied to one side of a polyethylene terephthalate sheet used as a transfer substrate to form an uncured surface protective layer. The uncured surface protective layer was heated at 100°C for 5 minutes to form a surface protective layer (thickness after curing: 10 μm).

[0115] Next, polyvinyl alcohol-polyurethane mixed resin 1 was prepared as a mixed resin of polyvinyl alcohol-based resin and polyurethane resin for forming the barrier layer as follows. First, water was placed in a beaker equipped with a stirrer, and polyvinyl alcohol (PVA1: Mitsubishi Chemical Corporation's Gohsenex Z Series (Z-200), an acetoacetyl-modified polyvinyl alcohol) was added while stirring at room temperature. After confirming that the PVA was uniformly dispersed in the water, the solution was gradually heated to 95°C until the PVA was completely dissolved. The solution was then slowly cooled to room temperature, yielding polyvinyl alcohol aqueous solution 1. Next, polyvinyl alcohol aqueous solution 1 and aqueous urethane resin dispersion 1 were added to a beaker equipped with a stirrer so that the solids ratio was polyvinyl alcohol:aqueous urethane resin dispersion 1 = 7:3. The solution was stirred until uniform, yielding polyvinyl alcohol-polyurethane mixed resin 1.

[0116] Next, the prepared polyvinyl alcohol-polyurethane mixed resin 1 was applied to the surface of the surface protective layer to form an uncured barrier layer. The uncured barrier layer was heated at 120°C for 5 minutes to form a barrier layer (thickness after curing: 5 μm). In this way, a second member having, in this order, a transfer substrate, a surface protective layer, and a barrier layer was obtained.

[0117] A composition containing acrylic polyol and hexamethylene diisocyanate was applied to the surface of the obtained second member to form a primer layer. The first member and the second member were arranged so that the design layer of the first member and the barrier layer of the second member faced each other with the primer layer interposed between them. The transfer substrate was then peeled off from the second member to obtain a decorative sheet.

[0118] [Examples 2 to 8] A decorative sheet was obtained in the same manner as in Example 1, except that the coating amount and composition of the barrier layer-forming composition were changed as shown in Table 1. In Table 1, PVA2 is polyvinyl alcohol, N-type / A-type Gohsenol (N-300) manufactured by Mitsubishi Chemical Corporation; PVA3 is polyvinyl alcohol having 1,2-glycol bonds, Nichigo G-Polymer (OKS-1109) manufactured by Mitsubishi Chemical Corporation; PVA4 is diacetone-modified polyvinyl alcohol, D-Polymer (DF-17) manufactured by Nippon Vinyl Acetate & Poval Co., Ltd.; and EVOH is Eversolve #10 manufactured by Nippon Cima Co., Ltd.

[0119] [Example 9] The prepared polyvinyl alcohol-polyurethane mixed resin 1 was applied to one side of the transfer substrate of Example 1 to form an uncured barrier layer. The uncured barrier layer was heated at 120°C for 5 minutes to form a barrier layer (thickness after curing: 5 μm). In this way, a third member having the transfer substrate and the barrier layer in this order was obtained.

[0120] A composition containing acrylic polyol and hexamethylene diisocyanate was applied to the surface (barrier layer surface) of the obtained third member to form a primer layer. The first member and the third member were arranged so that the design layer of the first member of Example 1 and the barrier layer of the third member faced each other with the primer layer interposed between them. The transfer substrate was then peeled off from the third member. In this way, a fourth member having a substrate sheet (ABS resin film), a design layer, a primer layer, and a barrier layer in this order was obtained.

[0121] Next, a bifunctional urethane acrylate (weight average molecular weight 20,000) with a polycarbonate skeleton was applied to the barrier layer of the fourth component to form an uncured surface protective layer. The uncured surface protective layer was irradiated with an electron beam at an acceleration voltage of 165 kV and an exposure dose of 50 kGy (5 Mrad) to form a surface protective layer (thickness 10 μm after curing). In this way, a decorative sheet was obtained.

[0122] [Example 10] A decorative sheet was obtained in the same manner as in Example 1, except that the coating amount and composition of the barrier layer-forming composition were changed as shown in Table 1, and the uncured barrier layer was heated at 120°C for 2 minutes.

[0123] [Example 11] A decorative sheet was obtained in the same manner as in Example 1, except that the coating amount and composition of the barrier layer-forming composition were changed as shown in Table 1.

[0124] [Comparative Example 1] A decorative sheet was produced in the same manner as in Example 1, except that no vinyl alcohol resin was used in the barrier layer.

[0125] [Comparative Examples 2 to 6] Decorative sheets were produced in the same manner as in Example 1 and Examples 5 to 8, except that no polyurethane resin was used in the barrier layer.

[0126] [evaluation] (Solid fragrance resistant) A solid air freshener cut to a specified size was placed on the decorative sheet obtained in each Example and Comparative Example, and heated at 70°C for 4 hours under a 400g load. The solid air freshener was then removed, the surface was wiped clean with a wipe, and the appearance was visually inspected. The evaluation criteria were as follows. The results are shown in Tables 1 and 2. The solid air freshener was a commercially available product containing piperonal, vanillin, asarone, rosin, benzyl benzoate, and dipropylene glycol as aromatic components. 5: No trace 4: Slight traces on the paint film 3: Traces on the paint film 2: The base material of the base sheet is exposed 1: The solid air freshener cannot be removed from the base sheet while it is still sticky.

[0127] (Adhesion test) The adhesiveness of the decorative sheets obtained in each Example and Comparative Example was evaluated in accordance with the cross-cut test of JIS K 5400. Specifically, 11 cuts were made vertically and horizontally at 1 mm intervals on the surface of the decorative sheet facing the surface protection layer, creating 100 1 mm grids, and cellophane tape (manufactured by Nichiban Co., Ltd.) was applied on top of the cuts and quickly peeled off at a 90° angle. The adhesiveness was evaluated based on the state of the cross-cut surface. The evaluation criteria were as follows: 5: No peeling 4: Peeling occurs outside the grid 3: Minor peeling occurs within the grid 2: Peeling occurs in about 50% of the grid. 1: Complete peeling

[0128] (Three-dimensional formability) The decorative sheets obtained in each example and comparative example were subjected to vacuum forming to evaluate their three-dimensional formability. Specifically, the decorative sheets were heated to 160°C using an infrared heater and softened. Next, vacuum forming was performed using a vacuum forming mold (maximum stretch ratio 250%) to mold the sheet to fit the internal shape of the mold. After cooling, the decorative sheet was released from the mold. The appearance of the surface protective layer of the decorative sheet after release was evaluated. The evaluation criteria are as follows: 3: No peeling or other defects were observed. 2: Slight defects such as peeling were observed. 1: Defects such as peeling were clearly observed.

[0129] (sunscreen resistant) The sunscreen resistance of the decorative sheets obtained in Examples 1 to 3, 5 to 7, and Comparative Examples 1 to 5 was evaluated. Specifically, 50 mg of a commercially available sunscreen cosmetic (sunscreen cream) was uniformly applied to a 10 mm x 10 mm area on the surface of the decorative sheet. An aluminum plate was placed to cover the applied area, and the sheet was left in a 60°C oven for 1 hour while a 400 g load was applied. Next, the decorative sheet was removed, and the surface was rinsed with a neutral detergent solution. The condition of the applied area was visually observed, and the chemical resistance of the decorative sheet was evaluated according to the following criteria. The sunscreen cosmetic used was a commercially available product containing 2-ethylhexyl salicylate, homosalate, octocrylene, and phenoxyethanol as ingredients, and is highly corrosive to resin surfaces. The evaluation criteria were as follows. A rating of 3 or higher was considered to have sunscreen resistance. A hyphen (-) indicates unevaluated. 5: No traces were found on the coating. 4: Almost no traces were found on the coating. 3: Slight traces were observed on the coating. 2: Traces were clearly visible on the coating. 1: The base material of the base sheet was exposed.

[0130] (Infrared Spectroscopy) The infrared absorption spectrum (IR spectrum) of the barrier layer of the decorative sheet obtained in each example was measured. The barrier layer was exposed on the surface by scraping and removing the surface protective layer of the decorative sheet with a cutter knife. The IR spectrometer used was an FT / IR6100 manufactured by JASCO Corporation. The IR spectrum measurement was performed using the attenuated total reflection method (ATR method). The results of a representative example (Example 3) are shown in Figure 2. The column "Presence or absence of crystalline peaks (IR)" in Tables 1 and 2 also indicates the presence or absence of peaks associated with the crystallization of the vinyl alcohol resin.

[0131] [Table 1]

[0132] [Table 2]

[0133] As shown in Tables 1 and 2, it was confirmed that the barrier layer containing the vinyl alcohol resin exhibited good resistance to solid fragrances. This was confirmed by the fact that the 1141 cm -1 As shown in Example 10, a peak at 1141 cm was observed in the infrared absorption spectrum, which is thought to be due to the crystallization of polyvinyl alcohol. -1 Even when no clear peak is observed, it is assumed that polyvinyl alcohol has a structure similar to that of a crystal, and it was confirmed that sufficient barrier properties can be provided by adjusting the film thickness of the barrier layer. Furthermore, in each example, since the barrier layer contains a polyurethane resin, adhesion and formability were also good. In addition, the surface protection layer of the decorative sheet in each example had a Martens hardness of 40 N / mm 2 It was as follows.

[0134] Furthermore, Examples 1 to 3 and 7 had higher sunscreen resistance than Examples 5 and 6. This is thought to be because Examples 1 to 3 and 7 used PVA1 or 4, which has a hydrophobic group other than an acetate group, as the vinyl alcohol resin, and the barrier layer had high hydrophobicity. [Explanation of symbols]

[0135] 1...Base sheet 2...Picture layer 3...Primer layer 4...Barrier layer 5…Surface protective layer 10...Decorative sheet

Claims

1. The film has at least a base sheet, a barrier layer, and a surface protective layer in this order, the barrier layer contains a vinyl alcohol-based resin and a polyurethane resin, The thickness of the base sheet is 0.05 mm or more and 1.0 mm or less, At least one layer in direct contact with the barrier layer contains a polyurethane resin; The decorative sheet, wherein the vinyl alcohol resin is a modified polyvinyl alcohol resin having a hydrophobic group other than an acetate group.

2. The barrier layer has a wavelength of 1130 cm in an infrared absorption spectrum. －１ 1160cm or more －１ The decorative sheet according to claim 1 , which has a peak in the following range:

3. 3. The decorative sheet according to claim 1, wherein in the barrier layer, a proportion of the polyurethane resin with respect to the total of the vinyl alcohol-based resin and the polyurethane resin is 5% by mass or more and 40% by mass or less.

4. The decorative sheet according to claim 1 , wherein the hydrophobic group has a reactive group.

5. The decorative sheet according to claim 4 , wherein the reactive group is a reactive carbonyl group.

6. The decorative sheet according to claim 5 , wherein the modified polyvinyl alcohol resin has, as the hydrophobic group, an acetoacetyl group having the reactive carbonyl group.

7. The decorative sheet according to any one of claims 1 to 6, wherein the surface protective layer contains a polyurethane resin.

8. The surface protective layer has a Martens hardness of 40 N / mm ２ The decorative sheet according to any one of claims 1 to 7, wherein:

9. The decorative sheet according to claim 1 , wherein the surface protective layer and the barrier layer are in direct contact with each other.

10. A decorated resin molded product having a resin molded product and a decorative sheet located on a surface of the resin molded product, the decorative sheet has at least a base sheet, a barrier layer, and a surface protective layer in this order; the barrier layer contains a vinyl alcohol-based resin and a polyurethane resin, The thickness of the base sheet is 0.05 mm or more and 1.0 mm or less, At least one layer in direct contact with the barrier layer contains a polyurethane resin; The vinyl alcohol resin is a modified polyvinyl alcohol resin having a hydrophobic group other than an acetate group.

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