JP7213840B2 - Decorative sheets and decorative moldings - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition, a decorative sheet, and a decorative molded product.

BACKGROUND ART Conventionally, an in-mold molding method and an insert molding method (hereinafter collectively referred to as an “in-mold molding method”) are known as methods of manufacturing a decorative molded product. On the other hand, the three-dimensional surface decorative molding method is characterized in that it is possible to manufacture a decorative molded product with excellent design and that no mold is required. For this reason, the three-dimensional surface decoration molding method is widely used as a method for manufacturing housings for home electric appliances such as personal computers, interior and exterior parts of vehicles, and the like. A typical decorative sheet used in a three-dimensional surface decoration molding method is a substrate sheet in which a design layer and a scratch-resistant skin layer are sequentially laminated on one side of the substrate sheet, and the other side of the substrate sheet is laminated. It is a laminate in which an adhesive layer and a separate film are sequentially laminated on the surface.

A general three-dimensional surface decoration molding method is carried out, for example, according to steps (1) to (6) shown below.
(1) Sandwiching the decorative sheet between the tables installed on the upper part of the lower chamber box.
(2) lowering the upper chamber to form a closed space;
(3) Make the inside of both chambers into a vacuum state.
(4) Heat the decorative sheet with an infrared heater.
(5) Raise the molded part (member to be decorated) installed in the lower chamber box.
(6) Opening the upper chamber to atmospheric pressure when the member to be decorated comes into contact with the decorative sheet.

Resin members are frequently used as members to be decorated because they are excellent in workability, lightweight and inexpensive. As a decorative sheet having three-dimensional moldability, for example, a decorative sheet provided with an adhesive layer formed of an olefin resin has been proposed (Patent Document 1). Also, a decorative sheet has been proposed in which resin layers whose polarities are gradually changed are successively laminated (Patent Document 2).

JP 2014-128920 A JP 2011-042175 A

Some low-polarity resins are known as difficult-to-adhere materials. For example, it is difficult to attach a decorative sheet to a member to be decorated made of a low-polarity resin such as an olefin resin by a three-dimensional surface decoration molding method. The decorative sheet proposed in Patent Document 1 has an adhesive layer made of an olefin-based resin, and thus has relatively good adhesion to a member to be decorated made of a low-polarity resin such as an olefin-based resin. Met. However, since the adhesiveness (interlayer adhesiveness) between the adhesive layer and other resin layers adjacent to the adhesive layer is lowered, there is a problem that the durability of the obtained decorative molded product is likely to be impaired.

On the other hand, in the decorative sheet proposed in Patent Document 2, the polarities of the laminated resin layers are gradually changed, so that the adhesiveness between the layers is maintained while the adhesiveness between the layers is maintained. It is possible to adhere the adhesive layer to the decorative member. However, since the number of resin layers to be laminated is very large, it becomes difficult to make the decorative sheet thin and the layer structure tends to be complicated.

The present invention has been made in view of the problems of the prior art, and an object of the present invention is to provide a member to be decorated made of a low-polarity and difficult-to-adhere resin such as an olefin resin. The object of the present invention is to provide a resin composition capable of forming an adhesive layer that adheres well to a substrate and has excellent interlayer adhesion.

In addition, an object of the present invention is to provide an adhesive that adheres well to a member to be decorated made of a low-polarity and difficult-to-adhere resin such as an olefin resin, and has excellent interlayer adhesion. An object of the present invention is to provide a decorative sheet having layers and applicable to a three-dimensional surface decorative molding method. A further object of the present invention is to provide a decorative molded product manufactured using the decorative sheet.

That is, according to the present invention, the following resin composition is provided.
[1] A resin composition for forming an adhesive layer of a decorative sheet having an adhesive layer that is brought into contact with at least a part of the surface of a member to be decorated, comprising a polycarbonate polyol, a dimer polyol, and a polyolefin polyol containing a urethane resin (C) having a structural unit (D) derived from at least one polyol selected from the group consisting of: the SP value of the polyol is 10.0 or less; A resin composition in which the content of the structural unit (D) is 20 to 98% by mass.
[2] Acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, acid-modified polyolefin resin, vinyl chloride-vinyl acetate copolymer, polyester resin, epoxy resin, polyamide resin, rubber-based resin, terpene-based resin, rosin-based resin and at least one resin selected from the group consisting of C5/C9 petroleum resins, and the content of the resin is 500 parts by mass or less with respect to 100 parts by mass of the urethane resin (C). The resin composition according to [1] above.
[3] The resin composition according to [2], wherein the haze value of the adhesive layer is 30 or less when the adhesive layer is formed to have a thickness of 20 μm.
[4] Any one of [1] to [3], which further contains a cross-linking agent, and the content of the cross-linking agent is 2 to 25 parts by mass with respect to 100 parts by mass of the urethane resin (C) The described resin composition.

Further, according to the present invention, the following decorative sheet is provided.
[5] A decorative sheet having a laminated structure comprising a skin layer and an adhesive layer formed of the resin composition according to any one of [1] to [4].
[6] The decorative sheet according to [5], wherein the adhesive layer has a haze value of 30 or less.
[7] The decorative sheet according to [5] or [6], wherein the skin layer is made of an active energy ray-curable resin composition.
[8] The decorative sheet according to [7], wherein the active energy ray-curable resin composition contains (A) a polycarbonate-based polyurethane having a (meth)acryloyloxy group and a non-yellowing polyisocyanate (B). .
[9] The skin layer has a breaking elongation of 250% or more at 80° C., and the hardened layer formed by ultraviolet curing the skin layer has a pencil hardness of 4B or more measured according to JIS K 5600. The decorative sheet according to any one of [5] to [8] above.
[10] The decorative sheet according to [5] or [6], wherein the skin layer is made of a thermosetting resin composition.
[11] The decorative sheet according to any one of [5] to [10], further comprising a guard film and having a laminated structure in which the guard film, the skin layer, and the adhesive layer are laminated in this order.
[12] The decorative sheet according to [11], further comprising a design layer disposed between the skin layer and the adhesive layer.
[13] The above [5] to [10], further comprising a base sheet and a design layer, and having a laminated structure in which the skin layer, the design layer, the base sheet, and the adhesive layer are laminated in this order. A decorative sheet according to any one of the above.

Furthermore, according to the present invention, the following decorative molded article is provided.
[14] A member to be decorated, and a decorative layer disposed on at least a part of the surface of the member to be decorated, wherein the decorative layer is any one of [5] to [13]. A decorator having a laminate structure including a cured layer derived from the skin layer of the decorative sheet according to 1, and an adhesive cured layer derived from the adhesive layer and disposed in contact with the surface of the member to be decorated. decorative moldings.

According to the present invention, it is possible to form an adhesive layer that adheres well to a member to be decorated that is formed of a low-polarity, difficult-to-adhere resin such as an olefin resin, and that has excellent interlayer adhesion. can provide a resin composition capable of

In addition, according to the present invention, it has an adhesive layer that adheres well to a member to be decorated made of a low-polarity and difficult-to-adhere resin such as an olefin resin, and has excellent interlayer adhesion. , a decorative sheet applicable to a three-dimensional surface decorative molding method can be provided. Furthermore, according to the present invention, it is possible to provide a decorative molded product manufactured using the decorative sheet.

1 is a cross-sectional view schematically showing one embodiment of a decorative sheet of the present invention; FIG. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows typically one Embodiment of the decorative molding of this invention. FIG. 4 is a cross-sectional view schematically showing another embodiment of the decorative sheet of the present invention; Fig. 2 is a cross-sectional view schematically showing another embodiment of the decorative molded product of the present invention;

<Resin composition>
Embodiments of the present invention will be described below, but the present invention is not limited to the following embodiments. The resin composition of the present invention is a composition for forming an adhesive layer of a decorative sheet having an adhesive layer that is brought into contact with at least a part of the surface of a member to be decorated, and comprises a polycarbonate polyol, a dimer polyol, and a polyolefin. It contains a urethane resin (C) having a structural unit (D) derived from at least one polyol selected from the group consisting of polyols. The SP value of the polyol is 10.0 or less, and the content of the structural unit (D) in the urethane resin (C) is 20 to 98% by mass.

(Urethane resin (C))
[Polyol]
The urethane resin (C) has a structural unit (D) derived from a polyol having an SP value of 10.0 or less. That is, the structural unit (D) is a structural unit derived from a low-polarity polyol (SP value: 10.0 or less). By containing the urethane resin (C) containing such a structural unit (D) in a predetermined ratio, it is possible to make the member to be decorated made of a low-polarity and difficult-to-adhere resin such as an olefin resin. It is possible to obtain a resin composition capable of forming an adhesive layer that can adhere well. Furthermore, since the urethane resin (C) is a resin having a highly polar urethane bond in its molecular structure, each layer constituting the decorative sheet formed of various materials such as polyester and urethane resin is excellent. It is possible to form an adhesive layer that adheres closely to and exhibits excellent interlayer adhesion.

The SP value of a polyol is a physical property value (unit: (cal/cm ³ ) ^1/2 ) represented by the square root of the ratio of cohesive energy density to molecular volume, as shown in the following formula. The SP value is a physical property value calculated by Robert F, Fedors et al. F. Fedors: Polym. Eng. Sci. , 14[2], 147-154 (1974).
SP value = (ΣE _coh /ΣV) ^1/2
E _coh : Cohesive energy density V: Molecular volume

The content of the structural unit (D) in the urethane resin (C) is 20-98% by mass, preferably 40-98% by mass. If the content of the structural unit (D) in the urethane resin (C) is less than 20% by mass, the adhesion to a member to be decorated made of a difficult-to-adhere resin such as an olefinic resin is reduced. . On the other hand, if the content of the structural unit (D) is more than 98% by mass, the molecular weight of the urethane resin (C) may become too small, resulting in poor initial adhesiveness and durability. The molecular weight of the urethane resin (C) can be appropriately set, for example, by adjusting the ratio between the hydroxyl groups of the polyol and the isocyanate groups of the polyisocyanate.

The polyol whose SP value is 10.0 or less is at least one selected from the group consisting of polycarbonate polyols, dimer polyols and polyolefin polyols. Specific examples of polycarbonate polyols include polytrimethylene carbonate diol, polytetramethylene carbonate diol, polypentamethylene carbonate diol, polyneopentyl carbonate diol, poly(3-methyl-1,5-pentyl carbonate) diol, and polyhexamethylene. Carbonate diol, poly(1,4-cyclohexanedimethylene carbonate) diol, polynonamethylene carbonate diol, poly(2-methyl-1,8-octyl carbonate) diol, polydecamethylene carbonate diol, and random copolymers thereof and block copolymers.

Dimer polyols are polyols derived from dimer acids or from mixtures containing dimer and trimer acids. Dimer acid is a dicarboxylic acid having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, and is a plant-derived fatty acid. A representative structure of dimer acid is represented by the following formula (A). Trimer acid is a tricarboxylic acid having 54 carbon atoms obtained by trimerizing the unsaturated fatty acid having 18 carbon atoms, and is also produced as a by-product in the production of dimer acid. For this reason, commercially available dimer acids are usually mixtures containing dimer and trimer acids.

Dimer diol, which is a polyol derived from dimer acid, is a polyol having 36 carbon atoms obtained by reducing the carboxy group of the dimer acid to a hydroxyl group, and may or may not have an unsaturated bond in its molecule. good too. The trimer triol is also a polyol having 54 carbon atoms obtained by reducing a trimer acid similarly to the dimer diol, and may or may not have an unsaturated bond in its molecule. Commercially available dimer diols are usually mixtures containing dimer diols and trimer triols.

As the polyolefin polyol, generally available commercial products and synthetic products can be used. Examples of polyolefin diols include polyethylene butylene diol, polyisoprene diol, polybutadiene diol, hydrogenated polybutadiene diol, and random copolymers and block copolymers thereof.

The urethane resin (C) may further contain structural units derived from polyols other than polyols having an SP value of 10.0 or less (other polyols), if necessary. Other polyols include polycarbonate polyols, aromatic polyester polyols, aliphatic polyester polyols, alicyclic polyester polyols, polyether polyols, silicone polyols, acrylic polyols, epoxy polyols, etc., whose SP value is greater than 10.0. can be mentioned.

The number average molecular weight of polyols having an SP value of 10.0 or less and other polyols are not particularly limited. Specifically, the number average molecular weight of these polyols is usually about 500 to 4,000. These polyols can be used individually by 1 type or in combination of 2 or more types.

[Diisocyanate]
The urethane resin (C) can be produced, for example, by polymerizing the above-described polyol having hydroxyl groups at both ends, diisocyanate, chain extender (short-chain diol), diamine, and the like. A known polyisocyanate can be used as the diisocyanate. Specific examples of polyisocyanates include 4,4′-methylenebis(phenylene isocyanate) (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), aromatic polyisocyanates such as tetramethylxylylene diisocyanate; Aliphatic polyisocyanates such as methylene diisocyanate (HDI), trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, lysine diisocyanate; isophorone diisocyanate (IPDI), 4,4′-methylenebis(cyclohexyl isocyanate) (H12MDI) ), bis(isocyanatomethyl)cyclohexane (H6XDI), dimer diisocyanate (DDI) and other alicyclic polyisocyanates.

[Short-chain diol]
In order to adjust the viscosity of the resin composition, the strength of the adhesive layer to be formed, etc., a short-chain diol having 2 to 10 carbon atoms can be used as necessary. Short-chain diols include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol, 1,2-octanediol, 2- Ethyl-1,3-hexanediol, 1,9-nonanediol, 1,10-decanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like can be mentioned. . The content of structural units derived from short-chain diols in the urethane resin (C) is not limited. However, if the content of structural units derived from short-chain diols is too large, the polarity of the formed adhesive layer will be excessively increased, and the member to be decorated, etc., formed of a difficult-to-adhere resin such as an olefin resin, etc. It is preferable to adjust as appropriate because the adhesiveness to the adhesive may decrease.

A short-chain diol having a carboxyl group may be further used, if necessary, in order to improve adhesion and provide cross-linking points. That is, the urethane resin (C) may contain structural units derived from a short-chain diol having a carboxy group. Examples of short-chain diols having a carboxyl group include dimethylolpropanoic acid and dimethylolbutanoic acid. However, if the content of structural units derived from a short-chain diol having a carboxyl group is too high, the polarity of the formed adhesive layer will excessively increase, and the adhesive layer formed from a difficult-to-adhere resin such as an olefinic resin will Adhesiveness to the decorative member or the like may be lowered, so it is preferable to adjust as appropriate.

[Polyamine]
In order to adjust the viscosity of the resin composition, the strength of the adhesive layer to be formed, and the like, polyamine can be used as necessary. Polyamines include methylenediamine, ethylenediamine, trimethylenediamine, pentamethylenediamine, hexamethylenediamine, octamethylenediamine, decamethylenediamine, N-(2-hydroxyethyl)-1,3-diaminopropane, N-(2- hydroxyethyl)-ethylenediamine; phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4,4'-methylenebis(phenylamine), 4,4'-diaminodiphenyl ether, 4 ,4'-diaminodiphenylsulfone, xylylenediamine and other aromatic diamine compounds; cyclopentyldiamine, cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane , piperazine, 2,5-dimethylpiperazine, isophoronediamine, dimerdiamine, etc.; hydrazine; and derivatives thereof. However, if the content of structural units derived from polyamine is too high, the polarity of the formed adhesive layer will be excessively increased, and it will not adhere to the member to be decorated, etc., which is formed of a difficult-to-adhere resin such as an olefin resin. Adhesiveness may be lowered, so it is preferable to adjust as appropriate.

[Production of urethane resin (C)]
The conditions for the polymerization reaction (urethanization reaction) are not particularly limited, and ordinary conditions for urethanization reaction can be applied. For example, the polymerization reaction is carried out with the equivalent ratio of the number of functional groups of the diisocyanate to the sum of the number of functional groups of the active hydrogen-containing compounds polyol, chain extender (short-chain diol) and diamine being about 1.0. Also, the reaction may be carried out by either one-shot method or multi-step method. The temperature of the polymerization reaction is usually 20-150°C, preferably 60-110°C. Then, the desired urethane resin (C) can be obtained by carrying out a polymerization reaction until the isocyanate groups are almost eliminated.

(Other resins)
The resin composition preferably further contains a resin (other resin) other than the urethane resin (C) described above. By further containing other resins, it is possible to further improve the adhesiveness to the member to be decorated, etc., which is formed of a difficult-to-adhere resin such as an olefin resin. Furthermore, it is possible to form an adhesive layer that adheres well to each layer adjacent to the adhesive layer that constitutes the decorative sheet, and that exhibits even better interlayer adhesion. In addition, by appropriately selecting the type of other resin to be contained, it is possible to obtain a resin composition capable of forming an adhesive layer with further improved other properties such as water resistance, chemical resistance, and heat resistance. .

Other resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, acid-modified polyolefin resins, vinyl chloride-vinyl acetate copolymers, polyester resins, epoxy resins, polyamide resins, rubber-based resins, terpene-based resins, At least one selected from the group consisting of rosin-based resins and C5/C9-based petroleum resins can be used.

The content of other resins in the resin composition is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, and 210 parts by mass or less with respect to 100 parts by mass of the urethane resin (C). is particularly preferred. If the content of other resins is too high, the adhesiveness to decorative members made of resins that are difficult to adhere to, or the adhesion between the adhesive layer and adjacent layers (interlayer adhesion). However, in some cases, it tends to decrease. The lower limit of the content of other resins in the resin composition is not particularly limited.

If the compatibility between the urethane resin (C) contained in the resin composition and other resins is low, the adhesion with the member to be decorated made of a low-polarity and difficult-to-adhere resin such as an olefin resin. Also, the interlaminar adhesion between the adhesive layer and the adjacent design layer, substrate sheet, and resin layer such as the skin layer may be likely to decrease. Furthermore, if the urethane resin (C) has low compatibility with other resins, the handling property during coating may be lowered, or the formation of a coating film may become difficult. For this reason, it is preferable to use an appropriate amount of other resin having a certain degree of good compatibility with the urethane resin (C). As an indicator of the compatibility of other resins with the urethane resin (C), the haze value of the adhesive layer formed using the resin composition can be used. Specifically, when an adhesive layer having a thickness of 20 μm is formed using a resin composition containing a urethane resin (C) and other resins, the haze value of the adhesive layer is 30 or less. It is preferably 25 or less, and particularly preferably 15 or less.

(crosslinking agent)
The resin composition preferably further contains a cross-linking agent. The content of the cross-linking agent in the resin composition is preferably 2 to 25 parts by mass, more preferably 3 to 15 parts by mass, based on 100 parts by mass of the urethane resin (C). By including a cross-linking agent, it is possible to obtain a resin composition capable of forming an adhesive layer having further improved properties such as water resistance, chemical resistance, and heat resistance. In addition, by including a cross-linking agent, it is possible to obtain a resin composition capable of forming an adhesive layer with improved initial adhesiveness and adhesive strength at high temperatures. As the cross-linking agent, known cross-linking agents such as isocyanate cross-linking agents, blocked isocyanate cross-linking agents, carbodiimide cross-linking agents, oxazoline cross-linking agents, epoxy cross-linking agents, aziridine cross-linking agents, silane coupling agents and titanium coupling agents can be used. .

Isocyanate cross-linking agents include MDI, TDI, HDI, IPDI, their trimethylolpropane adducts, biuret and isocyanurate; polymeric MDI, isocyanate-terminated prepolymers, and the like. The blocked isocyanate cross-linking agent includes an isocyanate cross-linking agent blocked by oxime, lactam, 3,5-dimethylpyrazole and the like. Examples of commercially available carbodiimide cross-linking agents include trade name "Carbodilite" (manufactured by Nisshinbo Chemical Co., Ltd.). Examples of commercially available oxazoline cross-linking agents include trade name "Epocross" (manufactured by Nippon Shokubai Co., Ltd.). Commercially available epoxy cross-linking agents include trade name “jER” (manufactured by Mitsubishi Chemical Corporation). Commercially available products of the aziridine cross-linking agent include the trade name “Kemitite” (manufactured by Nippon Shokubai Co., Ltd.). Specific examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane. Further, specific examples of the titanium coupling agent include titanium di-2-ethylhexoxybis(2-ethyl-3-hydroxyhexoxide) and the like.

(solvent)
A resin composition usually contains a solvent. Any solvent may be used as long as it can dissolve each component in the resin composition. Specific examples of solvents include alcohol solvents such as methanol, ethanol, isopropanol, butanol and octanol; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. , low-molecular-weight carbonate-based solvents such as dimethyl carbonate, and the like. Among them, ketone-based solvents alone, mixed solvents in which ketone-based solvents are used in combination with other solvents, and mixed solvents in which ketone-based solvents and ester-based solvents are used in combination have good solubility and drying properties. preferred.

<Decorative sheet>
The decorative sheet of the present invention is a decorative sheet that has a laminate structure comprising a skin layer and an adhesive layer formed from the resin composition described above, and that can be applied to, for example, a three-dimensional surface decoration molding method. FIG. 1 is a cross-sectional view schematically showing one embodiment of the decorative sheet of the present invention. As shown in FIG. 1, the decorative sheet 10 of the present embodiment is a sheet-like member having a laminated structure including a skin layer 2 and an adhesive layer 4. The adhesive layer 4 is made of the resin composition described above. layer. The decorative sheet 10 preferably further includes a guard film 6 and has a laminated structure in which the guard film 6, the skin layer 2, and the adhesive layer 4 are laminated in this order. Moreover, it is preferable to further include a design layer 8 arranged between the skin layer 2 and the adhesive layer 4 .

FIG. 3 is a cross-sectional view schematically showing another embodiment of the decorative sheet of the present invention. As shown in FIG. 3, the decorative sheet 30 of the present embodiment is a sheet-like member having a laminated structure including a skin layer 12 and an adhesive layer 14. The adhesive layer 14 is made of the resin composition described above. layer. The decorative sheet 30 preferably further includes the base sheet 5 and the design layer 18, and has a laminated structure in which the skin layer 12, the design layer 18, the base sheet 5, and the adhesive layer 14 are laminated in this order. .

(adhesion layer)
The adhesive layer is a layer formed of the resin composition described above. Therefore, this adhesive layer adheres well to a member to be decorated made of a low-polarity and difficult-to-adhere resin such as an olefin resin, and has excellent interlaminar adhesion.

The thickness of the adhesive layer can be appropriately set according to the purpose and the like. The thickness of the adhesive layer is usually 2-200 μm, preferably 5-100 μm.

As described above, by using a resin composition that further contains other resins such as acid-modified polyolefin resins together with the urethane resin (C), the adhesiveness to the members to be decorated made of resins that are difficult to adhere to can be improved. Alternatively, it is possible to form an adhesive layer with further improved adhesion (interlayer adhesion) to adjacent layers. The haze value of the adhesive layer formed using the resin composition further containing other resin is preferably 30 or less, more preferably 25 or less, and particularly preferably 15 or less.

(skin layer)
The skin layer is formed of, for example, a curable resin composition that is cured by irradiation with energy rays such as ultraviolet rays or by heating. For this reason, after three-dimensionally decorating the member to be decorated using the decorating sheet, by irradiating with active energy rays such as ultraviolet rays or by heat treatment, the resin composition constituting the skin layer is cured by cross-linking and the like. Then, a hardened layer having excellent abrasion resistance is formed. As a result, it is possible to obtain a decorative molded article having a cured layer with excellent scratch resistance as a surface layer.

The breaking elongation of the skin layer at 80° C. (hereinafter also referred to as “80° C. breaking elongation”) is preferably 250% or more, more preferably 300% or more. That is, since the 80° C. breaking elongation of the skin layer is sufficiently high, defects such as cracks are unlikely to occur during three-dimensional molding, and a decorative film having excellent three-dimensional moldability can be obtained. Although the upper limit of the 80° C. breaking elongation of the skin layer is not particularly limited, it is substantially 1,000% or less.

The cured layer formed by UV-curing the skin layer preferably has a pencil hardness measured according to JIS K 5600 of 4B or higher, more preferably 2B or higher, and B or higher. is particularly preferred. That is, since the cured layer formed by UV-curing the skin layer is sufficiently hard, the decorative film can be used to manufacture a decorative molded article having a surface with excellent scratch resistance. Furthermore, the 80° C. breaking elongation of the skin layer before UV curing is sufficiently high as described above. That is, the skin layer before curing has excellent three-dimensional moldability, but the cured layer formed by curing the skin layer is sufficiently hard. Therefore, by using the decorative sheet of the present invention, a decorative molded article having a surface with excellent scratch resistance can be easily produced by a three-dimensional surface decorative molding method without causing defects such as cracks. can be done. Although the upper limit of the pencil hardness of the cured layer is not particularly limited, it is substantially 4H or less.

The thickness of the skin layer can be appropriately set according to the purpose and the like. The thickness of the skin layer is usually 2-200 μm, preferably 5-100 μm.

The skin layer can be formed from an active energy ray-curable resin composition or a thermosetting resin composition. The active energy ray-curable resin composition includes, for example, a (meth)acryloyloxy group-containing polycarbonate-based polyurethane (hereinafter also simply referred to as “polycarbonate-based polyurethane” or “polyurethane”) (A) and a non-yellowing polyisocyanate (B) and.

The content of the non-yellowing polyisocyanate (B) in the active energy ray-curable resin composition is preferably 2 to 25 parts by mass, more preferably 3 to 15 parts by mass, with respect to 100 parts by mass of the polyurethane (A). is more preferable. If the content of the non-yellowing polyisocyanate (B) is more than 25 parts by mass with respect to 100 parts by mass of the polyurethane (A), it may become difficult to follow elongation during three-dimensional molding, and cracking may occur. On the other hand, when the content of the non-yellowing polyisocyanate (B) is less than 2 parts by mass with respect to 100 parts by mass of the polyurethane (A), the cured layer (surface layer) formed by curing has scratch resistance and chemical resistance. may be somewhat insufficient.

The weight average molecular weight of polyurethane (A) is preferably 1,000 or more, more preferably 2,000 or more. By using the polyurethane (A) having a weight average molecular weight of 1,000 or more, the three-dimensional moldability is further improved, and a decorative molded article having a surface with excellent scratch resistance can be produced. When the weight average molecular weight of the polyurethane (A) is less than 1,000, the surface adhesiveness of the skin layer may become strong, and the operability tends to be slightly lowered. On the other hand, when the weight average molecular weight of the polyurethane (A) exceeds 150,000, the viscosity of the resin composition tends to be high, and it tends to be difficult to apply. From the viewpoint of achieving both scratch resistance and three-dimensional moldability, it is particularly preferable that the polyurethane (A) has a weight average molecular weight of 3,000 to 100,000.

The number-average molecular weight and weight-average molecular weight in this specification are polystyrene-equivalent values measured by gel permeation chromatography (GPC), unless otherwise specified. The molecular weight measurement conditions are as follows.
(1) Equipment device: trade name “HLC-8020” (manufactured by Tosoh Corporation)
(2) Column: trade names "TSKgel G2000HXL", "G3000HXL", "G4000GXL" (manufactured by Tosoh Corporation)
(3) solvent: THF
(4) Flow rate: 1.0 ml/min
(5) Sample concentration: 2 g/L
(6) Injection volume: 100 μL
(7) Temperature: 40°C
(8) Detector: model number “RI-8020” (manufactured by Tosoh Corporation)
(9) Standard material: TSK standard polystyrene (manufactured by Tosoh Corporation)

The double bond equivalent of polyurethane (A) is 160 to 3,000 g/eq. is preferably 180 to 2,500 g/eq. is more preferable. When the double bond equivalent of the polyurethane (A) is within the above range, it is possible to form a skin layer capable of forming a cured layer having excellent solvent resistance and durability. The double bond equivalent of polyurethane (A) is 160 g/eq. If it is less than that, the cured layer formed by curing becomes brittle, or all the double bonds cannot react, so the remaining double bonds may tend to reduce the weather resistance. On the other hand, the double bond equivalent of polyurethane (A) is 3,000 g/eq. , the crosslink density of the formed cured layer may be low and the surface hardness may be low. As a result, the solvent resistance and durability of the cured layer may deteriorate.

Polyurethane (A) includes, for example, a double-ended polyol (polycarbonate polyol) (V) having a carbonate bond in the polymer main chain, a chain extender (low-molecular-weight diol) (W), a diisocyanate (X), and It can be produced by polymerizing a (meth)acrylate (Y) containing 1 to 2 hydroxy groups. Polyurethane (A) can be produced under the same conditions as those for producing urethane resin (C) described above.

As the polycarbonate polyol (V), it is preferable to mainly use a polycarbonate diol from the viewpoint of urethane synthesis. The use of polyfunctional polycarbonate polyol may cause gelation or the like during the polymerization reaction. The content of structural units derived from the polycarbonate polyol (V) in the polyurethane (A) is preferably 0.1 to 70% by mass, more preferably 10 to 60% by mass. When the content of structural units derived from the polycarbonate polyol (V) is less than 0.1% by mass, the structures derived from each of the low-molecular-weight diol (W), the diisocyanate (X), and the (meth)acrylate (Y) Unit content is relatively increased. If the content of these structural units is high, the formed skin layer tends to be brittle. Therefore, when the guard film having the skin layer formed thereon is wound, the skin layer may be easily cracked. In addition, since the 80° C. breaking elongation of the skin layer before curing may be less than 250%, there is a tendency that problems tend to occur during decorative molding.

On the other hand, when the content of structural units derived from polycarbonate polyol (V) exceeds 70% by mass, the content of structural units derived from (meth)acrylate (Y) relatively decreases. For this reason, there is a tendency that performance such as surface hardness and solvent resistance of the cured layer formed by curing the skin layer cannot be ensured.

If a polyester polyol is used instead of the polycarbonate polyol (V), the hydrolysis resistance of the cured layer formed by curing the skin layer is lowered. Also, if a polyether polyol is used instead of the polycarbonate polyol (V), the heat resistance of the cured layer formed by curing the skin layer is lowered.

The type of polycarbonate polyol is not particularly limited, and generally available commercial products and synthesis can be used. Polycarbonate diols include polytrimethylene carbonate diol, polytetramethylene carbonate diol, polypentamethylene carbonate diol, polyneopentyl carbonate diol, polyhexamethylene carbonate diol, poly(1,4-cyclohexanedimethylene carbonate) diol, polydeca Examples include methylene carbonate diol, and random copolymers and block copolymers thereof.

Although the number average molecular weight of the polycarbonate polyol (V) is not particularly limited, it is usually about 500 to 4,000.

Low-molecular-weight diols (W) include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and neopentyl glycol. , 3-methyl-1,5-pentanediol and other aliphatic glycols; 1,4-bishydroxymethylcyclohexane, 2-methyl-1,1-cyclohexanedimethanol and other alicyclic glycols. can. A monomer containing a hydroxyl group and an ethylenically unsaturated group can be used as the low-molecular-weight diol (W).

Diisocyanate (X) includes aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate and lysine diisocyanate; isophorone diisocyanate, 4,4′-methylenebis-cyclohexyl diisocyanate and the like. alicyclic polyisocyanates can be mentioned. By using these aliphatic polyisocyanates and alicyclic polyisocyanates, it is possible to obtain a polyurethane (A) that is resistant to yellowing due to ultraviolet rays and heat, so that a skin layer with better durability can be formed. . At least alicyclic polyisocyanates are preferably used from the viewpoint of reducing the fluidity of the resulting resin composition to reduce tackiness. In addition, it is also possible to use a trifunctional or more polyfunctional isocyanate together. However, if the amount of polyfunctional isocyanate used is too large, the resin solution may gel, so caution should be exercised.

As the (meth)acrylate (Y), any (meth)acrylate containing 1 to 2 hydroxyl groups at the terminals or side chains can be used. The number of (meth)acryloyl groups (number of functional groups) in these molecules is preferably 1 or more, more preferably 3 or more, from the viewpoint of further improving the scratch resistance of the resulting decorative molded article. preferable. These (meth)acrylates (Y) can be used as a chain extender or terminal terminator for polyurethane (A). (Meth)acrylates (Y) include 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 2-hydroxylpropyl acrylate, 2-hydroxylpropyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 2- hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, glycerin diacrylate, glycerin dimethacrylate, Glycerin monoacrylate, glycerin monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolpropane monoacrylate, trimethylolpropane monomethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate Methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetramethacrylate, isocyanurate EO-modified diacrylate, isocyanurate EO-modified dimethacrylate, 2-hydroxyl butyl acrylate, 2- Hydroxyl butyl methacrylate and the like can be mentioned.

The active energy ray-curable resin composition preferably further contains a photopolymerization initiator. By including a photopolymerization initiator in the active energy ray-curable resin composition, the skin layer after three-dimensional molding can be cured with ultraviolet rays more rapidly. The amount of the photopolymerization initiator to be contained in the active energy ray-curable resin composition is preferably 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total resin composition. is more preferred. When the active energy ray-curable resin composition is an electron beam (EB)-curable composition, the resin composition may not contain a photopolymerization initiator.

As the photopolymerization initiator, conventionally known ones can be appropriately selected and used. Photopolymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2- Morpholino-propan-1-one, 4-(2-hydroxyethoxy)phenyl-2(hydroxy-2-propyl)ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone , 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal , acetophenone dimethyl ketal, and the like. The active energy ray-curable resin composition may further contain photosensitizers such as p-dimethylbenzoic acid esters, tertiary amines, and thiol-based sensitizers.

As the non-yellowing polyisocyanate (B), conventionally known polyfunctional isocyanate compounds having a plurality of isocyanate groups, such as isocyanurate, biuret, adduct, and polymeric compounds can be used. Non-yellowing polyisocyanates (B) include blocked polyisocyanates such as polyfunctional alicyclic isocyanates, polyfunctional aliphatic isocyanates, fatty acid-modified polyfunctional aliphatic isocyanates, blocked polyfunctional aliphatic isocyanates, and polyisocyanate prepolymers. etc. can be mentioned.

Aliphatic isocyanates include modified products such as hexamethylene diisocyanate. Alicyclic isocyanates include modified products such as isophorone diisocyanate. These isocyanates may be used alone, or a plurality of isocyanates may be mixed to form a non-yellowing polyisocyanate. Among them, those having two or more isocyanate groups in the molecule are preferable. Polyisocyanate polymers, adducts with other compounds, and urethane prepolymers obtained by reacting low-molecular-weight polyols or polyamines to form terminal isocyanates are also preferred. Examples of the non-yellowing polyisocyanate (B) include compounds represented by the following general formulas (1) to (4).

The skin layer may be formed of a resin composition containing a thermosetting resin (thermosetting resin composition). Examples of curable resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, acid-modified polyolefin resins, vinyl chloride-vinyl acetate copolymers, urethane resins, polyester resins, epoxy resins, polyamide resins, and the like. .

The resin composition for forming the skin layer usually contains a solvent. Any solvent may be used as long as it can dissolve each component in the resin composition. Specific examples of solvents include alcohol solvents such as methanol, ethanol, isopropanol, butanol and octanol; ester solvents such as methyl acetate, ethyl acetate and butyl acetate; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. , low-molecular-weight carbonate-based solvents such as dimethyl carbonate, and the like. Among them, ketone-based solvents alone, mixed solvents in which ketone-based solvents are used in combination with other solvents, and mixed solvents in which ketone-based solvents and ester-based solvents are used in combination have good solubility and drying properties. preferred.

Various additives can be added to the resin composition for forming the skin layer depending on the physical properties to be imparted to the cured layer formed by curing. Additives include weather resistance improvers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, and plasticizers. , antifoaming agents, fillers, coloring agents, and the like. As the weather resistance improver, hindered amine light stabilizers such as HALS, ultraviolet absorbers, antioxidants, and the like can be used as long as they do not inhibit photocuring.

(design layer)
Examples of the material forming the design layer include thermoplastic resins and curable resins such as thermosetting and ultraviolet curable resins. Thermoplastic resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated polyolefin resins, acid-modified polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber-based resins, etc. can be mentioned. Examples of curable resins include urethane resins, acrylic resins, and epoxy resins. A design layer can be formed by applying a design to these resins using coloring agents such as silica, organic beads, pigments and dyes, and extender pigments. Examples of coloring agents include inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes; metal pigments consisting of scale-like foils such as aluminum and brass; pearlescent (pearl) pigments consisting of scale-like foils such as titanium dioxide-coated mica and basic lead carbonate. The design layer may also be a metal thin film provided by vapor deposition, sputtering, foil transfer, or the like using a metal such as aluminum, chromium, gold, silver, or copper.

The thickness of the design layer can be appropriately set according to the purpose and the like. The thickness of the design layer when resin or metal foil is used is usually 2 to 500 μm, preferably 5 to 300 μm. The thickness of the design layer when the metal is deposited or sputtered is usually 0.001 to 1 μm, preferably 0.005 to 0.5 μm.

By applying a design to the adhesive layer using a coloring agent such as silica, organic beads, a pigment, a dye, or an extender pigment, the adhesive layer can be made to have a design. Examples of coloring agents include inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; Organic pigments or dyes; metal pigments consisting of scale-like foils such as aluminum and brass; pearlescent (pearl) pigments consisting of scale-like foils such as titanium dioxide-coated mica and basic lead carbonate can be used. Also, a metal thin film imparted with a design may be provided by vapor deposition, sputtering, foil transfer, or the like using aluminum, chromium, gold, silver, copper, or the like.

(base material sheet)
The material and the like of the base sheet are appropriately selected in consideration of suitability for three-dimensional molding (vacuum molding). Generally, a resin film (sheet) made of a thermoplastic resin is used as the base sheet. Examples of thermoplastic resins include PET, polycarbonate, ABS resin, urethane resin, polyolefin resin, acrylic resin, and alloy resin.

The thickness of the base sheet can be appropriately set according to the purpose and the like. The thickness of the base sheet is usually 20-3,000 μm, preferably 50-2,000 μm.

(guard film)
The material and the like of the guard film are appropriately selected in consideration of suitability for three-dimensional molding (vacuum molding). Generally, a resin film (sheet) made of thermoplastic resin is used as a guard film. Examples of thermoplastic resins include PET, polycarbonate, ABS resin, urethane resin, polyolefin resin, acrylic resin, and alloy resin.

The thickness of the guard film can be appropriately set according to the purpose and the like. The thickness of the guard film is usually 3-500 μm, preferably 10-300 μm.

(separate film)
A separate film is a film (layer) provided mainly for the purpose of protecting the adhesive layer. A film made of a thermoplastic resin is used as the separate film. The thickness and material of the separate film are not particularly limited, but generally a PET film having a thickness of about 50 to 100 μm is suitable.

(Decorative sheet manufacturing method (1))
An example of a method for manufacturing a decorative sheet will be described below. First, a coating layer is formed by applying a skin layer-forming resin composition (hereinafter also referred to as "skin layer coating material") to the surface of the guard film by a conventional coating method. Examples of the method (printing method) for applying the coating for the skin layer on the surface of the guard film include gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheeler coating, and dip coating. Ordinary printing methods such as coating, solid coating by silk screen, wire bar coating, flow coating, comma coating and spray coating can be used. The drying temperature of the skin layer is usually 60-100°C, preferably 70-90°C. Moreover, the surface of the coating layer formed by obtaining the coating material for the skin layer can be painted by an inkjet method. For example, UV curable inkjet ink can be used for painting. UV curable inkjet inks usually do not contain water or organic solvents and do not require drying.

When forming a skin layer using an active energy ray-curable resin composition containing polyurethane (A) and non-yellowing polyisocyanate (B), crosslinking between polyurethane (A) and non-yellowing polyisocyanate (B) Aging is preferred as necessary to complete the reaction. The aging conditions are usually 30 to 60° C. for about 1 to 3 days. The aging of the skin layer may be performed at the time of forming the skin layer and the adhesive layer on the guard film, or may be performed after the skin layer and the adhesive layer are formed. At this time, a primer layer may be provided between the design layer and the skin layer in order to improve the adhesion between them. In order to improve the design property of the design layer, a metal thin film or the like may be formed, or the design layer may be laminated to form a multilayer structure. A metal thin film can be formed by a method such as vacuum deposition, sputtering, or foil transfer using a metal such as aluminum, chromium, gold, silver, or copper.

Next, a coating layer is formed by applying a resin composition for forming an adhesive layer (adhesive layer paint) onto the formed skin layer or design layer by a conventional coating method. An adhesive layer can be formed by drying the formed coating layer. As the method of applying the coating material for the adhesive layer (coating method), the same method as the method of applying the resin composition for forming the skin layer can be used. The drying temperature of the adhesive layer coating is usually 60 to 100°C, preferably 70 to 90°C. Alternatively, an adhesive layer previously formed on a transfer sheet may be transferred. A decorative sheet can be obtained by sticking a separate film for protecting the adhesive layer on the formed adhesive layer.

(Decorative sheet manufacturing method (2))
Next, another example of the method of manufacturing the decorative sheet will be described. First, a coating layer is formed by applying a resin composition or the like for forming a design layer on the surface of a substrate sheet by a conventional coating method. The base sheet may be surface-modified by performing primer treatment or corona discharge treatment. These treatments may be performed on the back surface as needed. Examples of the method of applying the resin composition for forming the design layer on the surface of the substrate sheet include gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, and wheeler coating. , dip coating, silk screen coating, wire bar coating, flow coating, comma coating, spray coating and the like. The drying temperature for the design layer is usually 60 to 100°C, preferably 70 to 90°C. The design layer can also be formed by an inkjet method. In particular, the design layer can be formed by applying a UV curable inkjet ink by an inkjet method. Inkjet inks that do not contain water or organic solvents are generally used, and drying is not particularly required when such inks are used.

Also, a design layer previously formed on a transfer sheet may be transferred to the base sheet. At this time, a primer layer may be provided between the design layer and the base sheet in order to improve the adhesion between them. In order to improve the design property of the design layer, a metal thin film or the like may be formed, or the design layer may be laminated to form a multilayer structure. A metal thin film can be formed by a method such as vacuum deposition, sputtering, or foil transfer using a metal such as aluminum, chromium, gold, silver, or copper.

Next, the surface of the formed design layer is coated with a coating for skin layer by a normal coating method to form a coating layer. A skin layer can be formed by drying the formed coating layer. As the method of applying the coating material for the skin layer (coating method), the same method as the method of applying the resin composition or the like for forming the design layer described above can be used. The drying temperature of the coating for the skin layer is usually 60 to 100°C, preferably 70 to 90°C.

An adhesive layer paint is applied to the back surface of the base sheet (the surface opposite to the surface on which the design layer and the skin layer are formed) to form a coating layer. An adhesive layer can be formed by drying the formed coating layer. As the method of applying the coating material for the adhesive layer (coating method), the same method as the method of applying the resin composition or the like for forming the design layer described above can be used. The drying temperature of the adhesive layer coating is usually 60 to 100°C, preferably 70 to 90°C. Alternatively, an adhesive layer previously formed on a transfer sheet may be transferred to the base sheet. A decorative sheet can be obtained by sticking a separate film for protecting the adhesive layer on the formed adhesive layer.

<Decorative molding>
A decorative molded product can be produced by using the decorative sheet described above. That is, the decorated molded product of the present invention includes a member to be decorated and a decorating layer arranged on at least a part of the surface of the member to be decorated. The decorative layer has a laminated structure including a cured layer derived from the skin layer of the decorative sheet and an adhesive cured layer derived from the adhesive layer placed in contact with the surface of the member to be decorated. have FIG. 2 is a cross-sectional view schematically showing one embodiment of the decorative molded product of the present invention. A decorated molded product 100 of the embodiment shown in FIG. The decorative layer 60 has a laminate structure including the hardening layer 23 , the design layer 8 and the adhesive hardening layer 25 . The cured layer 23 is a layer formed by curing the skin layer 2 of the decorative sheet 10 shown in FIG. The design layer 8 is a layer corresponding to the design layer 8 of the decorative sheet 10 shown in FIG. The hardening adhesive layer 25 is a layer derived from the adhesive layer 4 of the decorative sheet 10 shown in FIG.

FIG. 4 is a cross-sectional view schematically showing another embodiment of the decorative molded product of the present invention. A decorated molded product 200 of the embodiment shown in FIG. The decorative layer 70 has a laminate structure including the hardening layer 33 , the design layer 18 , the base sheet 5 and the adhesive hardening layer 35 . The cured layer 33 is a layer formed by curing the skin layer 12 of the decorative sheet 30 shown in FIG. The design layer 18 is a layer corresponding to the design layer 18 of the decorative sheet 30 shown in FIG. The base sheet 5 is a layer corresponding to the base sheet 5 of the decorative sheet 30 shown in FIG. The adhesive hardening layer 35 is a layer derived from the adhesive layer 14 of the decorative sheet 30 shown in FIG.

The decorative molded product has an adhesive cured layer formed by curing the above-mentioned adhesive layer that exhibits excellent adhesion even to resins such as olefin resins that have low polarity and are difficult to adhere to, so the decorative layer and the member to be decorated are firmly adhered to each other, and the layers constituting the decorative layer are also strongly adhered to each other, resulting in excellent interlayer adhesion. In addition, since the decorative molded product has a cured layer formed by curing the above-described skin layer, it is excellent in scratch resistance.

The decorative molded product of the present invention can be produced by using the aforementioned decorative sheet and by a general three-dimensional surface decorative molding method (vacuum forming method). A general resin member can be used as the member to be decorated. Among them, a member to be decorated made of a low-polarity resin such as an olefin-based resin is preferable because the decorative sheet used has an adhesive layer that can adhere well even to the surface of a resin that is difficult to adhere to. can be used for

EXAMPLES The present invention will be specifically described below based on Examples, but the present invention is not limited to these Examples. "Parts" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Synthesis of urethane resin (C)>
(Synthesis Example C1: Urethane resin C1)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. 120 g of dimer diol (trade name “Pripol 2033”, manufactured by Croda Japan, OHv=211 mgKOH/g, SP value 9.9) and 72 g of methyl ethyl ketone (MEK) were charged while replacing the inside of the reaction vessel with air. After the system became homogeneous, 50.1 g of isophorone diisocyanate (IPDI) was charged at 50°C and reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm ⁻¹ due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Toluene was added until the mass ratio of MEK and toluene was 1:1 to obtain a solution of urethane resin C1. The obtained solution had a viscosity of 143 dPa·s/20° C. and a solid content of 40%. The weight average molecular weight of the urethane resin C1 measured by GPC was 38,000, and the content of the structural unit (D) in the urethane resin C1 was 70.5%.

(Synthesis Example C2: Urethane resin C2)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. 150 g of hydrogenated polybutadiene polyol (trade name “GI-1000” manufactured by Nippon Soda Co., Ltd., OHv=68.8 mgKOH/g, SP value 8.6) was charged while replacing the inside of the reaction vessel with air. and 74 g of MEK were charged. After the inside of the system became homogeneous, 20.4 g of IPDI was charged at 50°C and reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm ⁻¹ due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Toluene was added until the mass ratio of MEK and toluene was 1:1 to obtain a solution of urethane resin C2. The obtained solution had a viscosity of 150 dPa·s/20° C. and a solid content of 40%. The weight average molecular weight of urethane resin C2 measured by GPC was 42,000, and the content of the structural unit (D) in urethane resin C2 was 88.0%.

(Synthesis Example C3: Urethane resin C3)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. 150 g of C9 polycarbonate polyol (trade name “C-1065N”, manufactured by Kuraray Co., Ltd., OHv=116 mgKOH/g, SP value 10.0) and 79 g of MEK were charged while replacing the inside of the reaction vessel with air. After the inside of the system became homogeneous, 34.4 g of IPDI was charged at 50°C and reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm ⁻¹ due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Toluene was added until the mass ratio of MEK and toluene was 1:1 to obtain a solution of urethane resin C3. The obtained solution had a viscosity of 210 dPa·s/20° C. and a solid content of 40%. The weight average molecular weight of urethane resin C3 measured by GPC was 38,000, and the ratio of the structural unit (D) in urethane resin C3 was 81.3%.

(Synthesis Example C4: Urethane resin C4)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 150 g of dimer diol (trade name “Pripol 2033”, manufactured by Croda Japan, OHv = 211 mg KOH / g, SP value 9.9), 7.5 g of 1,3-butanediol, and MEK101 .6 g was charged. After the inside of the system became homogeneous, 81.1 g of IPDI was charged at 50°C and reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm ⁻¹ due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Toluene was added until the mass ratio of MEK and toluene was 1:1 to obtain a solution of urethane resin C4. The obtained solution had a viscosity of 60.0 dPa·s/20° C. and a solid content of 40%. The weight average molecular weight of urethane resin C4 measured by GPC was 31,000, and the content of the structural unit (D) in urethane resin C4 was 62.9%.

(Synthesis Example C5: Urethane resin C5)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, C9-based polycarbonate polyol (trade name “C-1065N”, manufactured by Kuraray Co., Ltd., OHv = 116 mg KOH / g, SP value 10.0) 50 g, polyhexamethylene carbonate diol (trade name “ ETERNA COLLUH-50", manufactured by Ube Industries, Ltd., hydroxyl value = 219.6 mg KOH/g, SP value 10.9) 120 g, and MEK 101.6 g were charged. After the inside of the system became homogeneous, 63.6 g of IPDI was charged at 50°C and reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm ⁻¹ due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Toluene was added until the mass ratio of MEK and toluene was 1:1 to obtain a solution of urethane resin C5. The obtained solution had a viscosity of 100 dPa·s/20° C. and a solid content of 50%. The weight average molecular weight of urethane resin C5 measured by GPC was 35,000, and the content of the structural unit (D) in urethane resin C5 was 21.4%.

(Comparative Synthesis Example C6: Urethane resin C6)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 1,4-butanediol and 1,4-butanediol/adipic acid-based polyester polyol derived from adipic acid (trade name “HOKOKUOL HT-110”, manufactured by Toyokuni Oil Co., Ltd. , OHv112=mgKOH/g, SP value 11.0) and 78.5 g of MEK were charged. After the inside of the system became homogeneous, 33.2 g of IPDI was charged at 50°C and reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm ⁻¹ due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Toluene was added until the mass ratio of MEK and toluene was 1:1 to obtain a solution of urethane resin C6. The obtained solution had a viscosity of 210 dPa·s/20° C. and a solid content of 40%. The weight average molecular weight of urethane resin C6 measured by GPC was 38,000, and the content of structural unit (D) in urethane resin C6 was 0%.

(Comparative Synthesis Example C7: Urethane resin C7)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 1,4-butanediol / neopentyl glycol copolymer polycarbonate polyol (trade name "NL1005B", manufactured by Mitsubishi Chemical Corporation, OHv = 113.3 mgKOH / g, SP value 10.8) ) and 78.7 g of MEK were charged. After the inside of the system became homogeneous, 33.6 g of IPDI was charged at 50°C and reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm ⁻¹ due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Toluene was added until the mass ratio of MEK and toluene was 1:1 to obtain a solution of urethane resin C7. The resulting solution had a viscosity of 160 dPa·s/20° C. and a solid content of 40%. The weight average molecular weight of urethane resin C7 measured by GPC was 39,000, and the content of the structural unit (D) in urethane resin C7 was 0%.

<Synthesis of urethane resin (A)>
(Synthesis Example A1: Urethane resin A1)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, polyhexamethylene carbonate diol (trade name “PLAXEL CD220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight determined by terminal functional group quantification: 2,000) 400.0 g, 1,4 -80.0 g of butanediol, 160.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value: 102.9 mg KOH/g), and 226 g of MEK were charged. After the inside of the system became homogeneous, 103.8 g of hexamethylene diisocyanate (HDI) and 161.9 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50° C., and dibutyltin laurate was used as a catalyst to raise the temperature to 80° C. reacted with The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm ⁻¹ due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1:1 to obtain a solution of urethane resin A1. The obtained solution had a viscosity of 500 dPa·s/20° C. and a solid content of 45%. The double bond equivalent of urethane resin A1 is 588 g/eq. The weight average molecular weight measured by GPC was 46,000, and the content of structural units derived from polycarbonate polyol was about 44%.

<Preparation of adhesive layer resin compositions 1 to 22>
Adhesive layer resin compositions 1 to 22 (Examples 1 to 14, Comparative Examples 1 to 8) were prepared by blending each component according to the formulation shown in the middle of Tables 1-1 and 1-2. The compounding amount (unit: parts) shown in the middle of Tables 1-1 and 1-2 is the solid content. Details of the resins in Tables 1-1 and 1-2 are shown below.
・Acid-modified olefin resin: Product name “Aurolen 550S”, manufactured by Nippon Paper Industries ・Chlorinated olefin resin: Product name “Hardren 14-CE”, manufactured by Toyobo ・Terpene resin: Product name “YS Polyster G125”, Yasuhara Chemical Rosin-based resin: trade name “Harimac R-80”, manufactured by Harima Kasei Co., Ltd. Isocyanate cross-linking agent: trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd.

<Preparation of paint for skin layer>
(Skin layer paint A1)
2.25 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was added to 100 g of the urethane resin A1 solution. In addition, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Corporation, solid content 100%, containing 23.1% isocyanate), MEK and cyclohexanone are blended at a mass ratio of 1:1. As a result, a skin layer coating material 1 having a solid content of 30% was obtained.

<Preparation of composition for design layer>
(Design layer composition 1)
A reaction vessel equipped with a stirrer, reflux condenser, thermometer, nitrogen blower, and manhole was provided. While purging the inside of the reaction vessel with nitrogen, polyhexamethylene carbonate diol (trade name “PLAXEL CD220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight determined by terminal functional group determination: 2,000) 400.0 g, 1,4 - 40.0 g of butanediol and 146 g of MEK were charged. After the system became homogeneous, 143.0 g of IPDI was charged at 50°C and reacted at 80°C using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption at 2,270 cm ⁻¹ due to free isocyanate groups as measured by infrared absorption spectroscopy disappeared. Cyclohexanone was added until the mass ratio of MEK and cyclohexanone reached 1:1 to obtain a design layer resin solution 1 containing a urethane resin. The resulting resin solution had a viscosity of 420 dPa·s/20° C. and a solid content of 40%. The weight average molecular weight of the urethane resin measured by GPC was 44,000. To 100.0 g of the obtained design layer resin solution 1, 12.0 g of a non-leafing type aluminum paste (trade name “MH-6601”, manufactured by Asahi Kasei Corporation, solid content 65%), MEK and cyclohexanone at a mass ratio of 1 :1 to obtain a design layer composition 1 having a solid content of 30%.

(Design layer composition 2)
Design layer composition 2 was aluminum for vapor deposition.

(Design layer composition 3)
Design layer composition 3 was a UV ink for inkjet printers containing a UV-reactive monomer, a pigment, and a polymerization initiator.

(Design layer composition 4)
20.0 g of black pigment dispersion colorant (trade name “Seika Seven SS01-323 Black”, manufactured by Dainichiseika Kogyo Co., Ltd., solid content 25%, solvent: MEK, pigment: carbon black) to 100 g of design layer resin solution 1 , MEK and cyclohexanone were blended at a mass ratio of 1:1 to obtain a design layer composition 4 having a solid content of 30%.

<Production of decorative sheet (1)>
(Example 15)
After coating the surface of the guard film (trade name “Novaclear”, manufactured by Mitsubishi Chemical Corporation, an amorphous PET film with a thickness of 200 μm) with the skin layer paint 1 with a bar coater, it is dried at 90 ° C. for 2 minutes, A skin layer with a thickness of 15 μm was formed. The adhesive layer resin composition 1 was applied to the surface of a separate film (80 μm thick PET film) using a bar coater and then dried at 90° C. for 2 minutes to form a 20 μm thick adhesive layer. After laminating the adhesive layer and the clear layer under a temperature condition of 80° C. by dry lamination, they were aged at 45° C. for 1 day to obtain a decorative sheet.

(Example 16)
After coating the surface of the guard film (trade name “Novaclear”, manufactured by Mitsubishi Chemical Corporation, an amorphous PET film with a thickness of 200 μm) with the skin layer paint 1 with a bar coater, it is dried at 90 ° C. for 2 minutes, A skin layer with a thickness of 15 μm was formed. A UV ink containing a UV-reactive monomer, a pigment, and an initiator was applied to the surface of the formed skin layer with a UV inkjet printer to print a pattern, thereby forming a design layer having a thickness of 5 μm. After coating the adhesive layer resin composition 1 on the surface of the formed design layer with a bar coater, it was dried at 90° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. A separate film (PET film having a thickness of 80 μm) was adhered to the surface of the formed adhesive layer, and then aged at 45° C. for 1 day to obtain a decorative sheet.

(Example 17)
After coating the surface of the guard film (trade name “Novaclear”, manufactured by Mitsubishi Chemical Corporation, an amorphous PET film with a thickness of 200 μm) with the skin layer paint 1 with a bar coater, it is dried at 90 ° C. for 2 minutes, A skin layer with a thickness of 15 μm was formed. A 0.03 μm-thick design layer made of an aluminum thin film was formed on the surface of the formed clear layer by vapor deposition. After coating the adhesive layer resin composition 1 on the surface of the formed design layer with a bar coater, it was dried at 90° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. A separate film (PET film having a thickness of 80 μm) was adhered to the surface of the formed adhesive layer, and then aged at 45° C. for 1 day to obtain a decorative sheet.

(Examples 18-30 and Comparative Examples 9-16)
A decorative sheet was obtained in the same manner as in Example 15 above, except that the adhesive layer was formed using the adhesive layer resin composition shown in Tables 2-1 and 2-2.

<Production of decorative sheet (2)>
(Example 31)
Adhesive layer resin composition 1 is applied to the surface of a substrate sheet (trade name “Tough Ace R EAR802”, manufactured by Sumitomo Bakelite Co., Ltd., acrylonitrile-butadiene-styrene copolymer (ABS) sheet with a thickness of 1 mm) with a bar coater. After that, it was dried at 90° C. for 2 minutes to form a primer layer having a thickness of 5 μm. Design layer composition 4 was applied to the surface of the formed primer layer using a bar coater and then dried at 90° C. for 2 minutes to form a design layer having a thickness of 20 μm. After coating the surface of the formed design layer with the skin layer coating material 1 using a bar coater, it was dried at 90° C. for 2 minutes to form a skin layer with a thickness of 15 μm, and aged at 45° C. for 1 day. The adhesive layer resin composition 1 was applied to the surface of a separate film (80 μm thick PET film) using a bar coater and then dried at 90° C. for 2 minutes to form a 20 μm thick adhesive layer. After laminating the adhesive layer and the back surface of the base sheet under a temperature condition of 80° C. by dry lamination, they were aged at 45° C. for 1 day to obtain a decorative sheet.

(Examples 32-46 and Comparative Examples 17-24)
A decorative sheet was obtained in the same manner as in Example 31, except that the adhesive layer was formed using the adhesive layer resin composition of the type shown in Tables 3-1 and 3-2.

(Example 47)
Adhesive layer resin composition 1 is applied to the surface of a substrate sheet (trade name “Tough Ace R EAR802”, manufactured by Sumitomo Bakelite Co., Ltd., acrylonitrile-butadiene-styrene copolymer (ABS) sheet with a thickness of 1 mm) with a bar coater. After that, it was dried at 90° C. for 2 minutes to form a primer layer having a thickness of 5 μm. Design layer composition 1 was applied to the surface of the formed primer layer using a bar coater and then dried at 90° C. for 2 minutes to form a design layer having a thickness of 20 μm. After coating the surface of the formed design layer with the skin layer coating material 1 using a bar coater, it was dried at 90° C. for 2 minutes to form a skin layer having a thickness of 15 μm. After aging at 45° C. for one day, processing (roughness processing) was performed using an embossing roll with grains heated to 100° C. to form a rough pattern on the surface of the skin layer. The adhesive layer resin composition 1 was applied to the surface of a separate film (80 μm thick PET film) using a bar coater and then dried at 90° C. for 2 minutes to form a 20 μm thick adhesive layer. After laminating the adhesive layer and the back surface of the base sheet under a temperature condition of 80° C. by dry lamination, they were aged at 45° C. for 1 day to obtain a decorative sheet.

(Example 48)
Adhesive layer resin composition 1 is applied to the surface of a substrate sheet (trade name “Tough Ace R EAR802”, manufactured by Sumitomo Bakelite Co., Ltd., acrylonitrile-butadiene-styrene copolymer (ABS) sheet with a thickness of 1 mm) with a bar coater. After that, it was dried at 90° C. for 2 minutes to form a primer layer having a thickness of 5 μm. Aluminum for vapor deposition (design layer composition 2) was vapor-deposited on the surface of the formed primer layer to form a design layer having a thickness of 0.03 μm. After coating the surface of the formed design layer with the skin layer coating material 1 using a bar coater, it was dried at 90° C. for 2 minutes to form a skin layer with a thickness of 15 μm, and aged at 45° C. for 1 day. The adhesive layer resin composition 1 was applied to the surface of a separate film (80 μm thick PET film) using a bar coater and then dried at 90° C. for 2 minutes to form a 20 μm thick adhesive layer. After laminating the adhesive layer and the back surface of the base sheet under a temperature condition of 80° C. by dry lamination, they were aged at 45° C. for 1 day to obtain a decorative sheet.

(Example 49)
Adhesive layer resin composition 1 is applied to the surface of a substrate sheet (trade name “Tough Ace R EAR802”, manufactured by Sumitomo Bakelite Co., Ltd., acrylonitrile-butadiene-styrene copolymer (ABS) sheet with a thickness of 1 mm) with a bar coater. After that, it was dried at 90° C. for 2 minutes to form a primer layer having a thickness of 5 μm. A UV ink (design layer composition 3) was applied to the surface of the formed primer layer using an inkjet printer to form a design layer having a thickness of 5 μm. After coating the surface of the formed design layer with the skin layer coating material 1 using a bar coater, it was dried at 90° C. for 2 minutes to form a skin layer with a thickness of 15 μm, and aged at 45° C. for 1 day. The adhesive layer resin composition 1 was applied to the surface of a separate film (80 μm thick PET film) using a bar coater and then dried at 90° C. for 2 minutes to form a 20 μm thick adhesive layer. After laminating the adhesive layer and the back surface of the base sheet under a temperature condition of 80° C. by dry lamination, they were aged at 45° C. for 1 day to obtain a decorative sheet.

(Example 50)
After coating the adhesive layer resin composition 1 on the surface of a base sheet (polycarbonate (PC) sheet with a thickness of 0.5 mm) with a bar coater, it is dried at 90 ° C. for 2 minutes to form a primer layer with a thickness of 5 μm. formed. Design layer composition 4 was applied to the surface of the formed primer layer using a bar coater and then dried at 90° C. for 2 minutes to form a design layer having a thickness of 20 μm. After coating the surface of the formed design layer with the skin layer coating material 1 using a bar coater, it was dried at 90° C. for 2 minutes to form a skin layer with a thickness of 15 μm, and aged at 45° C. for 1 day. The adhesive layer resin composition 1 was applied to the surface of a separate film (80 μm thick PET film) using a bar coater and then dried at 90° C. for 2 minutes to form a 20 μm thick adhesive layer. After laminating the adhesive layer and the back surface of the base sheet under a temperature condition of 80° C. by dry lamination, they were aged at 45° C. for 1 day to obtain a decorative sheet.

<Manufacturing of decorative molded products>
Using a vacuum forming machine (trade name "NGF-0404-S", manufactured by Fuse Vacuum Co., Ltd.), the surface of the member to be decorated made of corona-treated PP resin heated to 80 ° C. was heated to 100 ° C. Adhesive layers of heated decorative sheets shown in Tables 2-1, 2-2, 3-1 and 3-2 were adhered by vacuum forming. Using an ultraviolet irradiator (trade name “Unicure UVC-02512S1AA01”, manufactured by Ushio Inc.), the decorative sheet attached to the surface of the member to be decorated is irradiated with UV so that the cumulative light amount is 2,000 mJ / cm ² . Then, the skin layer was cured to form a cured layer to obtain a decorated molded product.

<Evaluation method>
(1) Adhesion The adhesive layer resin composition was applied to a 100 μm-thick PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) using a bar coater and dried at 90° C. for 2 minutes to form a 20 μm-thick adhesive film. formed a layer. An adhesive layer of a PET film heated to 100°C was adhered to the surface of the member to be decorated (corona-treated PP) heated to 100°C with a rubber roller. The PET film adhered to the member to be decorated was cut together with the adhesive layer into 2 mm×2 mm, 100 squares (in a grid pattern). A peeling test was performed by sticking a cellophane tape to a PET film and then peeling it off, and the adhesion of the adhesive layer to the PP surface was evaluated according to the evaluation criteria shown below. The results are shown in Tables 2-1, 2-2, 3-1 and 3-2.
◯: The adhesive layer was not peeled off from the PP surface.
Δ: Part of the adhesive layer was peeled off from the PP surface.
x: All of the adhesive layer was peeled off from the PP surface.

(2) Interlayer adhesion A resin composition for an adhesive layer was applied to a 100 μm thick PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) with a bar coater and dried at 90° C. for 2 minutes to obtain a 20 μm thick film. An adhesive layer was formed. The adhesive layer and the skin layer or the base sheet (ABS) were laminated by dry lamination under a temperature condition of 80°C. The peeled state of the bonded adhesive layer and the skin layer or base sheet was observed, and the interlayer adhesion was evaluated according to the evaluation criteria shown below. The results are shown in Tables 2-1, 2-2, 3-1 and 3-2.
◯: Cohesive failure occurred.
x: Interfacial peeling (between the skin layer or base sheet and the adhesive layer) occurred.

(3) Haze value of adhesive layer A resin composition for adhesive layer (resin composition for adhesive layer 6 to 13 and 18 to 21) was applied to a 100 μm thick PET film (trade name “Lumirror”, manufactured by Toray Industries, Inc.) using a bar coater. and dried at 90° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm to obtain a laminate (test piece). Using a haze meter (trade name "Haze Meter HM-150", manufactured by Murakami Color Research Laboratory), the haze value (= measured value - base The haze value of the material) was measured, and the average value was calculated. The results are shown in Tables 2-1, 2-2, 3-1 and 3-2.

(4) Three-dimensional formability (vacuum formability)
The appearance of the manufactured decorative molded article was observed, and the three-dimensional formability (vacuum formability) was evaluated according to the evaluation criteria shown below. The results are shown in Tables 2-1, 2-2, 3-1 and 3-2.
⊚: No coating film cracking or whitening was observed in the skin layer, the design layer, and the adhesive layer, and the shape of the mold was well followed.
◯: Fine coating film cracks or whitening were observed in a part of the three-dimensional shape part or the maximum stretched part, but it was at a practically non-problematic level.
x: The skin layer and the design layer could not follow the shape of the mold, or cracking or whitening of the coating film was observed in part of the three-dimensional shape.

(5) 80°C breaking elongation (adhesive layer)
The adhesive layer resin composition was applied onto release paper so that the dry film thickness was about 30 μm, and then aged at 45° C. for 1 day to form a coating film. After confirming that the absorption derived from the 2,270 cm ^-1 isocyanate group (isocyanate cross-linking agent) has disappeared using an infrared spectrophotometer, the coating film is cut into a size of 15 mm in width and 60 mm in length. Then, a test piece was produced. Using an autograph (trade name "AGS-J 500N", manufactured by Shimadzu Corporation) and a constant temperature tester (trade name "TCR1-200", manufactured by Shimadzu Corporation), a temperature of 80 ° C., a distance between chucks of 20 mm, and tension The 80° C. breaking elongation of the test piece produced under conditions of a speed of 200 mm/min was measured, and the 80° C. breaking elongation was evaluated according to the evaluation criteria shown below. The results are shown in Tables 2-1, 2-2, 3-1 and 3-2.
○: 80% breaking elongation was 250% or more.
x: 80% breaking elongation was less than 250%.

(6) Light Resistance Based on JASO M346-1993, an accelerated test of the decorated molded product was carried out using a xenon weatherometer under the conditions shown below. The appearance of the decorated molded article after the accelerated test was observed, and the light resistance was evaluated according to the evaluation criteria shown below. The results are shown in Tables 2-1, 2-2, 3-1 and 3-2.
・Irradiance: 48 to 162 W/m ²
・Wavelength: 300 to 400 nm
・Black panel temperature: 89±3℃
・Irradiation time: 8 weeks ・Heat: 2,000kJ
◯: No discoloration, chalking, cracks, cracks, etc. occurred in the decorative molded product.
x: Discoloration, chalking, cracking, cracking, etc. occurred in the decorative molded product.

(7) Heat resistance A heat resistance test was conducted by placing the manufactured decorative molded product in an oven and maintaining it at 80°C for 400 hours. After the test, the appearance of the decorated molded article was observed, and the heat resistance was evaluated according to the evaluation criteria shown below. The results are shown in Tables 2-1, 2-2, 3-1 and 3-2.
Good: No yellowing, chalking, cracks, cracks, or other appearance abnormalities occurred in the decorative molded product.
x: Appearance abnormalities such as yellowing, chalking, cracks, and cracks occurred in the decorative molded product.

(8) Water resistance A water resistance test was conducted by immersing the decorative molded product in water at 40°C for 3 days. The appearance of the decorated molded article after the test was observed, and the water resistance was evaluated according to the evaluation criteria shown below. The results are shown in Tables 2-1, 2-2, 3-1 and 3-2.
⊚: No abnormality in appearance such as white discoloration, chalking, cracks, or cracks occurred in the decorative molded product.
◯: Some appearance abnormalities such as white discoloration, chalking, cracks, and cracks occurred in the decorative molded product, but the level was practically acceptable.
x: Appearance abnormalities such as white discoloration, chalking, cracks, and cracks occurred in the decorative molded product.

(9) 80°C breaking elongation (skin layer)
The skin layer coating material 1 was coated on a release paper so that the dry film thickness was about 30 μm, and then aged at 45° C. for 1 day to form a coating film. After aging, an infrared spectrophotometer was used to confirm that the absorption derived from the isocyanate group (non-yellowing polyisocyanate) at 2,270 cm ^-1 had disappeared, and then the coating film was measured at a width of 15 mm and a length of 15 mm. A test piece was prepared by cutting it into a size of 60 mm. Autograph (trade name "AGS-J 500N", manufactured by Shimadzu Corporation) and a constant temperature tester (trade name "TCR1-200", manufactured by Shimadzu Corporation) were used for the prepared test piece, and the temperature was 80 ° C. The elongation at break at 80° C. was measured under the conditions of a distance between chucks of 20 mm and a tensile speed of 200 mm/min. As a result, the 80° C. breaking elongation was 300%.

(10) Pencil Hardness Based on JIS K 5600, the pencil hardness of the surface (ultraviolet-cured cured layer) of the produced decorative molding was measured. As a result, the pencil hardness was "2B".

Examples of the decorative sheet of the present invention include interior and exterior materials for vehicles such as automobiles; housings for home electric appliances such as televisions, personal computers and mobile phones; interior materials for buildings such as walls, floors and ceilings; It is useful as a material for producing the decorated molded product of by the three-dimensional surface decoration molding method.

2, 12: skin layers 4, 14: adhesive layer 5: base sheet 6: guard films 7, 17: separate films 8, 18: design layers 10, 30: decorative sheets 23, 33: cured layers 25, 35: Adhesive hardening layers 40, 50: members to be decorated 60, 70: decorative layers 100, 200: decorative moldings

Claims (8)

Having a laminated structure comprising a skin layer and an adhesive layer formed of a resin composition and brought into contact with at least a part of the surface of the member to be decorated ,
The resin composition contains a urethane resin (C) having a structural unit (D) derived from at least one polyol selected from the group consisting of polycarbonate polyols, dimer polyols, and polyolefin polyols,
The SP value of the polyol is 10.0 or less,
The content of the structural unit (D) in the urethane resin (C) is 20 to 98% by mass,
The decorative sheet , wherein the skin layer is formed of a thermosetting resin composition . 2. The decorative sheet according to claim 1 , wherein the adhesive layer has a haze value of 30 or less. The resin composition is an acrylic resin, an acrylic-modified polyolefin resin, a chlorinated polyolefin resin, an acid-modified polyolefin resin, a vinyl chloride-vinyl acetate copolymer, a polyester resin, an epoxy resin, a polyamide resin, a rubber-based resin, a terpene-based resin, Further containing at least one resin selected from the group consisting of rosin-based resins and C5/C9-based petroleum resins,
The decorative sheet according to claim 1 or 2, wherein the content of the resin is 500 parts by mass or less with respect to 100 parts by mass of the urethane resin (C). The resin composition further contains a cross-linking agent,
The decorative sheet according to any one of claims 1 to 3, wherein the content of the cross-linking agent is 2 to 25 parts by mass with respect to 100 parts by mass of the urethane resin (C). Equipped with a guard film,
The decorative sheet according to any one of claims 1 to 4 , having a laminated structure in which the guard film, the skin layer and the adhesive layer are laminated in this order. 6. The decorative sheet according to claim 5 , further comprising a design layer arranged between said skin layer and said adhesive layer. Further comprising a base sheet and a design layer,
5. The decorative sheet according to any one of claims 1 to 4 , having a laminated structure in which the skin layer, the design layer, the base sheet and the adhesive layer are laminated in this order. A member to be decorated, and a decoration layer arranged on at least a part of the surface of the member to be decorated,
The adhesive, wherein the decorative layer is arranged in contact with a hardened layer derived from the skin layer of the decorative sheet according to any one of claims 1 to 7 and the surface of the member to be decorated. A decorative molded article having a laminated structure including an adhesive curing layer derived from the layer.

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