JP2021154706A - Decorative sheet and decorative molding - Google Patents

Abstract

To provide a decorative sheet which enables manufacturing of a decorative molding that is favorably adhered to a decorated member formed of various materials and is excellent in durability, and is applicable to a three-dimensional decorative molding method.SOLUTION: A decorative sheet 10 is used in a method for manufacturing a decorative molding. The decorative sheet has a laminated structure having a skin layer 2 and an adhesive layer 4, the adhesive layer 4 is formed of a resin composition for an adhesive layer containing an urethane resin (C) having a structural unit (D) derived from polycarbonate diol having a hydroxyl value of 80-250 mgKOH/g, the skin layer 2 is formed of an active energy curable resin composition for a skin layer, breaking elongation at 80°C of the skin layer 2 is 250% or more, and a pencil hardness measured according to JIS K 5600 of a cured layer formed by curing the skin layer 2 with ultraviolet rays is 4B or harder.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet and a decorative molded product.

Conventionally, an in-mold molding method and an insert-mold molding method (hereinafter, also referred to as "in-mold molding method") are known as methods for manufacturing a decorative molded product. On the other hand, the three-dimensional surface decorative molding method is a method having features that it is possible to manufacture a decorative molded product having more excellent design and that a mold is not required. For this reason, the three-dimensional surface decoration molding method is expanding its use as a method for manufacturing housings for home appliances such as personal computers and interior / exterior parts of vehicles. In a general decorative sheet used in a three-dimensional surface decorative molding method, a design layer and a scratch-resistant skin layer are sequentially laminated on one surface of the base sheet, and the other of the base sheets. It is a laminated body 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 the steps (1) to (6) shown below.
(1) The decorative sheet is sandwiched between the tables installed on the upper part of the lower chamber box.
(2) The upper chamber is lowered to form a closed space.
(3) Make the inside of both chambers vacuum.
(4) Heat the decorative sheet with an infrared heater.
(5) The molded part (decorated member) installed in the lower chamber box is raised.
(6) The upper chamber is opened to atmospheric pressure when the decorative member comes into contact with the decorative sheet.

Resin members are frequently used as decorative members because they are excellent in workability, lightweight, and inexpensive. As a sheet applied to the in-mold molding method, for example, a hard coat layer is formed on one surface of the base film, and an ink layer and an adhesive varnish layer are sequentially laminated on the other surface. (Patent Document 1) has been proposed. Further, 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 2).

Japanese Unexamined Patent Publication No. 2005-292198 Japanese Unexamined Patent Publication No. 2014-128920

The molding temperature in the in-mold molding method is about 120 to 200 ° C., whereas the molding temperature in the three-dimensional surface decoration molding method is about 80 to 110 ° C. Therefore, when the in-mold label proposed in Patent Document 1 is applied to the three-dimensional surface decoration molding method, sufficient adhesive strength cannot be obtained because the molding temperature is low.

On the other hand, if a three-dimensional surface decorative molding is performed using the decorative sheet proposed in Patent Document 2, a certain degree of adhesive strength can be exhibited. However, it has not yet achieved the high level of adhesive strength required in recent years, and there is room for further improvement. Further, there has been a demand for the development of a highly versatile decorative sheet that adheres well to a decorative member made of a resin such as ABS or PC or a metal such as various steel plates.

The present invention has been made in view of the problems of the prior art, and the subject thereof is that it adheres well to a decorative member made of various materials and is durable. It is an object of the present invention to provide a decorative sheet applicable to a three-dimensional surface decorative molding method capable of producing a decorative molded product having excellent properties. Another object of the present invention is to provide a decorative molded product manufactured by using the above-mentioned decorative sheet.

That is, according to the present invention, the decorative sheet shown below is provided.
[1] A decorative sheet used in a method for manufacturing a decorative molded product, which comprises a step of irradiating ultraviolet rays after three-dimensional decorative molding to form a cured layer, and has a laminated structure including a skin layer and an adhesive layer. The adhesive layer is formed of a resin composition for an adhesive layer containing a urethane resin (C) having a structural unit (D) derived from a polycarbonate polyol having a hydroxyl value of 80 to 250 mgKOH / g, and the skin layer. Is formed of an active energy ray-curable resin composition for an epidermis layer, the epidermis layer has a breaking elongation at 80 ° C. of 250% or more, and a cured layer formed by curing the epidermis layer with ultraviolet rays. A decorative sheet with a pencil hardness of 4B or more measured in accordance with JIS K 5600.
[2] The decorative sheet according to the above [1], wherein the structural unit (D) includes an alicyclic skeleton.
[3] The decorative sheet according to the above [1] or [2], wherein the urethane resin (C) has a weight average molecular weight of 2,000 to 500,000.
[4] The decorative sheet according to any one of [1] to [3], wherein the content of the structural unit (D) in the urethane resin (C) is 30 to 80% by mass.
[5] The resin composition for the adhesive layer further contains a cross-linking agent, and the content of the cross-linking agent in the resin composition for the adhesive layer is 2 with respect to 100 parts by mass of the urethane resin (C). The decorative sheet according to any one of the above [1] to [4], which is ~ 25 parts by mass.
[6] Any of the above [1] to [5], wherein the resin composition for the epidermis layer contains a polycarbonate-based polyurethane (A) containing a (meth) acryloyloxy group and a non-yellowing polyisocyanate (B). Decorative sheet described in.
[7] The decorative sheet according to any one of [1] to [6], 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.
[8] The decorative sheet according to the above [7], further comprising a design layer arranged between the skin layer and the adhesive layer.
[9] The above-mentioned [1] to [6], further comprising a base material sheet and a design layer, and having a laminated structure in which the skin layer, the design layer, the base material sheet, and the adhesive layer are laminated in this order. The decorative sheet described in either.

Moreover, according to this invention, the decorative molded article shown below is provided.
[10] The decorative layer includes a decorative member and a decorative layer arranged on the surface of at least a part of the decorative member, and the decorative layer is any one of the above [1] to [9]. The addition having a laminated structure including a cured layer derived from the skin layer of the decorative sheet according to the above and an adhesive cured layer derived from the adhesive layer arranged in contact with the surface of the decorative member. Decorative molded products.

According to the present invention, a three-dimensional surface decorative molding method capable of producing a decorative molded product having good adhesion to a decorative member made of various materials and having excellent durability. Applicable decorative sheets can be provided. Further, according to the present invention, it is possible to provide a decorative molded product manufactured by using the above-mentioned decorative sheet.

It is sectional drawing which shows typically one Embodiment of the decorative sheet of this invention. It is sectional drawing which shows typically one Embodiment of the decorative molded article of this invention. It is sectional drawing which shows typically the other embodiment of the decorative sheet of this invention. It is sectional drawing which shows typically the other embodiment of the decorative molded article of this invention.

<Decorative sheet>
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. The decorative sheet of the present invention is a decorative sheet used in a method for manufacturing a decorative molded product having a step of irradiating ultraviolet rays to form a cured layer after three-dimensional decorative molding, and includes a skin layer and an adhesive layer. It has a laminated structure. FIG. 1 is a cross-sectional view schematically showing an 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. It is preferable that the decorative sheet 10 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. It is also preferable to further include a design layer 8 arranged between the skin layer 2 and the adhesive layer 4. The adhesive layer 4 is formed of a resin composition for an adhesive layer containing a urethane resin (C) having a structural unit (D) derived from a specific polycarbonate polyol.

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 decorative sheet 30 preferably further includes a base sheet 5 and a design layer 18, and preferably has a laminated structure in which a skin layer 12, a design layer 18, a base sheet 5, and an adhesive layer 14 are laminated in this order. .. The adhesive layer 4 is formed of a resin composition for an adhesive layer containing a urethane resin (C) having a structural unit (D) derived from a specific polycarbonate polyol.

(Adhesive layer)
[Urethane resin (C)]
The adhesive layer is formed of a resin composition for an adhesive layer containing a urethane resin (C) having a structural unit (D) derived from a polycarbonate polyol having a hydroxyl value of 80 to 250 mgKOH / g. Since the urethane resin (C) having such a structural unit (D) has a large amount of urethane bonds in its molecular structure, the cohesive force can be increased by using the resin composition containing the urethane resin (C). It is possible to improve and form an adhesive layer having high adhesive strength.

By setting the hydroxyl value of the polycarbonate polyol to 80 mgKOH / g or more, the amount of urethane bonds in the urethane resin (C) increases, so that the cohesive force is improved and the adhesive strength of the formed adhesive layer can be increased. At the same time, the affinity of the urethane bond improves the adhesion to the decorative member made of various materials. On the other hand, by setting the hydroxyl value of the polycarbonate polyol to 250 mgKOH / g or less, it can be softened at a low molding temperature of about 80 to 110 ° C., and excellent adhesive strength can be obtained. This makes it possible to obtain a decorative sheet applicable to the three-dimensional surface decorative molding method.

The weight average molecular weight of the urethane resin (C) is preferably 2,000 to 500,000, more preferably 5,000 to 250,000. By using polyurethane (C) having a weight average molecular weight within the above range, good adhesive strength and durability can be obtained. If the weight average molecular weight of the urethane resin (C) is less than 2,000, the durability may be inferior. On the other hand, if the weight average molecular weight of the urethane resin (C) is more than 500,000, good adhesiveness may not be obtained.

The urethane resin (C) can be produced, for example, by polymerizing a double-ended polyol (polycarbonate polyol) having a carbonate bond in the polymer main chain, a chain extender (low molecular weight diol), a diisocyanate, or the like.

The conditions of the polymerization reaction (urethanization reaction) are not particularly limited, and the conditions of the usual urethanization reaction can be applied. For example, the polymerization reaction is carried out with the equivalent ratio of the number of functional groups of diisocyanate to the sum of the number of functional groups of the active hydrogen-containing compound polycarbonate polyol and low molecular weight diol being about 1.0. Further, the reaction may be carried out by either a one-shot method or a multi-step method. The temperature of the polymerization reaction is usually 20 to 150 ° C, preferably 60 to 110 ° C. Then, the target urethane resin (C) can be obtained by carrying out the polymerization reaction until the isocyanate groups are almost eliminated.

As the polycarbonate polyol, it is preferable to mainly use a polycarbonate diol from the viewpoint of urethane synthesis. The use of a polyfunctional polycarbonate polyol may cause gelation or the like during the polymerization reaction. The content of the structural unit (D) derived from the polycarbonate polyol in the urethane resin (C) is preferably 30 to 80% by mass, more preferably 40 to 70% by mass. When the content of the structural unit (D) is less than 30% by mass, the content of the structural unit derived from each of the low molecular weight diol and the diisocyanate increases relatively. If the content of these structural units is large, the formed adhesive layer tends to be hard, so that it may be difficult to exert sufficient adhesive force at a molding temperature of about 80 to 110 ° C. On the other hand, when the content of the structural unit (D) is more than 80% by mass, the amount of urethane bonds is relatively reduced, so that the adhesive strength tends to be insufficient.

If a polyester polyol is used instead of the polycarbonate polyol, the hydrolysis resistance of the adhesive layer is lowered. Further, when a polyether polyol is used instead of the polycarbonate polyol, the heat resistance of the adhesive layer is lowered.

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

The structural unit (D) preferably includes an alicyclic skeleton. For example, by using a polycarbonate polyol having an alicyclic skeleton, a urethane resin (C) having a structural unit (D) containing an alicyclic skeleton can be obtained. Examples of the alicyclic skeleton include cyclopentane, cyclohexane, bicycloundecane, norbornene and the like. When the structural unit (D) contains an alicyclic skeleton, the cohesive force of the urethane resin (C) is increased, and the adhesive force of the adhesive layer can be further enhanced.

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

The low molecular weight diol can be used to adjust the total hydroxyl value of the polycarbonate polyol and the low molecular weight diol. The total hydroxyl value of the polycarbonate polyol and the low molecular weight diol is preferably 100 to 400.

Examples of the diisocyanate include aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI), trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, and lysine diisocyanate; isophorone diisocyanate (IPDI), 4,4'-methylenebis-. Alicyclic polyisocyanates such as cyclohexyldiisocyanate; aromatic polyisocyanates such as 4,4'-methylenebis (phenylene isocyanate) (MDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), tetramethylxylylene diisocyanate, etc. Can be mentioned. By using these aliphatic polyisocyanates and alicyclic polyisocyanates, a urethane resin (C) that is not easily yellowed by ultraviolet rays or heat can be obtained, so that an adhesive layer having better durability can be formed. .. From the viewpoint of the cohesive force of the obtained resin composition, it is preferable to use at least alicyclic polyisocyanates. It is also possible to use a trifunctional or higher polyfunctional isocyanate in combination. However, it is preferable to be careful because the resin solution may gel if the amount of the polyfunctional isocyanate used is too large.

The resin composition for the adhesive layer preferably further contains a cross-linking agent. The content of the cross-linking agent in the resin composition for the adhesive layer is preferably 2 to 25 parts by mass and further preferably 3 to 15 parts by mass with respect to 100 parts by mass of the urethane resin (C). preferable. By containing a cross-linking agent, it is possible to form an adhesive layer having further improved properties such as water resistance, chemical resistance, and heat resistance. Further, by containing a cross-linking agent, it is possible to form an adhesive layer having improved initial adhesion and adhesive strength at high temperature. As the cross-linking agent, known cross-linking agents such as isocyanate cross-linking agent, blocked isocyanate cross-linking agent, carbodiimide cross-linking agent, oxazoline cross-linking agent, epoxy cross-linking agent, aziridine cross-linking agent, silane coupling agent, and titanium coupling agent can be used. ..

Examples of the isocyanate cross-linking agent include MDI, TDI, HDI, IPDI, their trimethylolpropane adducts, burettes, and isocyanurates; polymeric MDIs, terminal isocyanate prepolymers, and the like. Examples of the blocked isocyanate cross-linking agent include a blocked product using the isocyanate cross-linking agent oxime or lactam, 3,5-dimethylpyrazole and the like. Examples of commercially available carbodiimide cross-linking agents include the trade name "carbodilite" (manufactured by Nisshinbo Chemical Co., Ltd.). Examples of commercially available oxazoline cross-linking agents include the trade name "Epocross" (manufactured by Nippon Shokubai Co., Ltd.). Examples of commercially available epoxy cross-linking agents include the trade name "jER" (manufactured by Mitsubishi Chemical Corporation). Examples of commercially available aziridine cross-linking agents include the trade name "Chemitite" (manufactured by Nippon Shokubai Co., Ltd.). Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane. Specific examples of the titanium coupling agent include titanium di2-ethylhexoxybis (2-ethyl-3-hydroxyhexoxide) and the like.

The resin composition for the adhesive layer usually contains a solvent. The solvent may be any solvent that can dissolve each component in the resin composition for the adhesive layer. Specific examples of the solvent 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 solvent such as dimethyl carbonate and the like. Among them, the ketone solvent alone, the mixed solvent in which the ketone solvent and other solvents are used in combination, and the mixed solvent in which the ketone solvent and the ester solvent are used in combination have good solubility and drying property. Is preferable.

Various additives can be added to the resin composition for the adhesive layer depending on the physical properties to be applied to the adhesive layer. Additives include weather resistance improvers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesive improvers, leveling agents, tincture imparting agents, coupling agents, and plasticizers. , Antifoaming agent, filler, coloring material and the like.

By designing the adhesive layer with a colorant such as silica, organic beads, pigment, dye, or an extender pigment, the designed resin layer can be used as the adhesive layer. Colorants include carbon black, iron black, titanium white, antimony white, chrome yellow, titanium yellow, petals, cadmium red, ultramarine blue, cobalt blue and other inorganic pigments; quinacridone red, isoindolinone yellow, phthalocyanine blue and the like. Organic pigments or dyes; metal pigments made of scaly foil pieces such as aluminum and brass; pearl luster (pearl) pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate can be used. Further, a metal thin film having a design property may be provided by vapor deposition, sputtering, foil transfer or the like using aluminum, chromium, gold, silver, copper or the like.

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 to 200 μm, preferably 5 to 100 μm.

(Epidermis layer)
The elongation at break of the epidermis layer at 80 ° C. (hereinafter, also referred to as “elongation at break at 80 ° C.”) is 250% or more, preferably 300% or more. That is, the decorative sheet of the present invention provided with a skin layer having a sufficiently high elongation at break at 80 ° C. is less likely to cause defects such as cracks during three-dimensional molding, and has excellent three-dimensional moldability. The upper limit of the elongation at break at 80 ° C. of the epidermis layer is not particularly limited, but is substantially 1,000% or less.

The pencil hardness of the cured layer formed by curing the epidermis layer with ultraviolet rays, as measured in accordance with JIS K 5600, is 4B or more, preferably 2B or more, and more preferably B or more. That is, by using the decorative sheet of the present invention having a skin layer capable of forming a sufficiently hard cured layer by ultraviolet curing, a decorative molded product having a surface having excellent scratch resistance can be produced. Further, the elongation at break at 80 ° C. of the epidermis layer before being cured by ultraviolet rays is sufficiently high as described above. That is, the epidermis layer before curing has excellent three-dimensional moldability, but the cured layer formed by curing the epidermis layer is sufficiently hard. Therefore, by using the decorative sheet of the present invention, it is possible to easily manufacture a decorative molded product having a surface having excellent scratch resistance without causing defects such as cracks by the three-dimensional surface decorative molding method. Can be done. The upper limit of the pencil hardness of the cured layer is not particularly limited, but is substantially 4H or less.

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

The epidermis layer is formed of an active energy ray-curable resin composition for the epidermis layer. The resin composition for the epidermis layer includes (meth) acryloyloxy group-containing polycarbonate-based polyurethane (hereinafter, also simply referred to as “polycarbonate-based polyurethane” or “polyurethane”) (A) and non-yellowing polyisocyanate (B). Is preferably contained.

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

The weight average molecular weight of the polyurethane (A) is preferably 1,000 or more, and more preferably 2,000 or more. By using polyurethane (A) having a weight average molecular weight of 1,000 or more, it is possible to further improve the three-dimensional moldability and produce a decorative molded product having a surface having more excellent scratch resistance. When the weight average molecular weight of the polyurethane (A) is less than 1,000, the surface adhesiveness of the epidermis 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) is more than 150,000, the viscosity of the resin composition tends to be high and it tends to be difficult to apply the polyurethane (A). From the viewpoint of more preferably achieving both scratch resistance and three-dimensional moldability, the weight average molecular weight of polyurethane (A) is particularly preferably 3,000 to 100,000.

Unless otherwise specified, the number average molecular weight and the weight average molecular weight in the present specification are polystyrene-equivalent values measured by gel permeation chromatography (GPC). The molecular weight measurement conditions are as shown below.
(1) Equipment Equipment: Product name "HLC-8020" (manufactured by Tosoh Corporation)
(2) Column: Product names "TSKgel G2000HXL", "G3000HXL", "G4000GXL" (manufactured by Tosoh Corporation)
(3) Solvent: THF
(4) Flow velocity: 1.0 ml / min
(5) Sample concentration: 2 g / L
(6) Injection amount: 100 μL
(7) Temperature: 40 ° C
(8) Detector: Model number "RI-8020" (manufactured by Tosoh Corporation)
(9) Standard substance: TSK standard polystyrene (manufactured by Tosoh Corporation)

The double bond equivalent of polyurethane (A) is 160-3,000 g / eq. It 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, a skin layer capable of forming a cured layer having better solvent resistance and durability can be formed. The double bond equivalent of polyurethane (A) is 160 g / eq. If it is less than, the cured layer formed by curing becomes brittle, or all the double bonds cannot react, so that the weather resistance may be easily lowered by the remaining double bonds. On the other hand, the double bond equivalent of polyurethane (A) is 3,000 g / eq. If it exceeds, the crosslink density of the formed cured layer becomes low, and the surface hardness may become low. Therefore, the solvent resistance and durability of the cured layer may decrease.

Polyurethane (A) can be used, for example, in a double-ended polyol (polypolypolyol) (V) having a carbonate bond in the polymer main chain, a chain extender (low molecular weight diol) (W), a diisocyanate (X), and a terminal or side chain. It can be produced by polymerizing a (meth) acrylate (Y) containing 1 or 2 hydroxy groups. The polyurethane (A) can be produced under the same conditions as those for producing the 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 a polyfunctional polycarbonate polyol may cause gelation or the like during the polymerization reaction. The content of the structural unit 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 the structural unit derived from the polycarbonate polyol (V) is less than 0.1% by mass, the composition derived from each of the low molecular weight diol (W), the diisocyanate (X), and the (meth) acrylate (Y). The content of the unit increases relatively. When the content of these constituent units is high, the formed epidermal layer tends to be brittle. Therefore, when the guard film forming the epidermis layer is wound, the epidermis layer may be easily cracked. Further, since the elongation at break at 80 ° C. of the epidermis layer before curing may be less than 250%, defects tend to occur easily during decorative molding.

On the other hand, when the content of the structural unit derived from the polycarbonate polyol (V) is more than 70% by mass, the content ratio of the structural unit derived from the (meth) acrylate (Y) is relatively reduced. Therefore, there is a tendency that the surface hardness, solvent resistance, and other performance of the cured layer formed by curing the epidermis layer cannot be ensured.

When a polyester polyol is used instead of the polycarbonate polyol (V), the hydrolysis resistance of the cured layer formed by curing the epidermis layer is lowered. Further, when a polyether polyol is used instead of the polycarbonate polyol (V), the heat resistance of the cured layer formed by curing the epidermis layer is lowered.

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

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

Examples of the low molecular weight diol (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).

Examples of the diisocyanate (X) include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, and lysine diisocyanate; isophorone diisocyanate, 4,4'-methylenebis-cyclohexyldiisocyanate, and the like. Examples of alicyclic polyisocyanates can be mentioned. By using these aliphatic polyisocyanates and alicyclic polyisocyanates, polyurethane (A) that is not easily yellowed by ultraviolet rays or heat can be obtained, so that a more durable epidermis layer can be formed. .. From the viewpoint of reducing the fluidity of the obtained resin composition and reducing the tack, it is preferable to use at least alicyclic polyisocyanates. It is also possible to use a trifunctional or higher polyfunctional isocyanate in combination. However, it is preferable to be careful because the resin solution may gel if the amount of the polyfunctional isocyanate used is too large.

As the (meth) acrylate (Y), any (meth) acrylate containing 1 or 2 hydroxy groups at the terminal or side chain can be used. The number of (meth) acryloyl groups (number of functional groups) in these molecules is preferably 1 or more, and further preferably 3 or more, from the viewpoint of further improving the scratch resistance of the obtained decorative molded product. preferable. These (meth) acrylates (Y) can be used as chain extenders and terminal terminators for polyurethane (A). Examples of the (meth) acrylate (Y) include 2-hydroxylethyl acrylate, 2-hydroxylethylmethacrylate, 2-hydroxylpropylacrylate, 2-hydroxylpropylmethacrate, N-methylolacrylamide, N-methylolmethacrylate, 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, Trimethylol Propane Diacrylate, Trimethylol Propane Dimethacrylate, Trimethylol Propane Monoacrylate, Trimethylol Propane Monomethacrylate, Pentaerythritol Triacrylate, Pentaerythritol Trimethacrylate, Pentaerythritol Diacrylate, Pentaerythritol Diacrylate Methacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetramethacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, 2-hydroxylbutylacrylate, 2- Examples thereof include hydroxylbutyl methacrylate and the like.

It is preferable that the resin composition for the epidermis layer further contains a photopolymerization initiator. By including the photopolymerization initiator in the resin composition for the epidermis layer, the epidermis layer after three-dimensional molding can be cured by ultraviolet rays more quickly. The amount of the photopolymerization initiator contained in the resin composition for the epidermis layer is preferably 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the entire resin composition. More preferred. When the resin composition for the epidermis layer is an electron beam (EB) curing type composition, it is not necessary to include the photopolymerization initiator in the resin composition.

As the photopolymerization initiator, conventionally known ones can be appropriately selected and used. Examples of the photopolymerization initiator 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-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2- Morphorino-Propane-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone , 2-Ethylanthraquinone, 2-Terrary butyl anthraquinone, 2-Aminoanthraquinone, 2-Methylthioxanthone, 2-Ethylthioxanthone, 2-Chlorothioxanthone, 2,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, benzyldimethylketal , Acetphenone dimethyl ketal and the like. The resin composition for the epidermis layer may further contain a photosensitizer such as p-dimethylbenzoic acid ester, tertiary amines, and a thiol-based sensitizer.

As the non-yellowing polyisocyanate (B), conventionally known polyfunctional isocyanate compounds having a plurality of isocyanate groups, such as isocyanurate, burette, adduct, and polypeptide, can be used. Examples of the non-yellowing polyisocyanate (B) include block-type polyisocyanates such as polyfunctional alicyclic isocyanates, polyfunctional aliphatic isocyanates, fatty acid-modified polyfunctional aliphatic isocyanates, and blocked polyfunctional aliphatic isocyanates, and polyisocyanate prepolymers. And so on.

Examples of the aliphatic isocyanate include modified products such as hexamethylene diisocyanate. Further, as the alicyclic isocyanate, there is a modified product 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. Further, an adduct of a polyisocyanate multimer or an adduct with another compound, a urethane prepolymer obtained by reacting a low molecular weight polyol or polyamine so as to become a terminal isocyanate, or the like is also preferable. Examples of the non-yellowing polyisocyanate (B) include compounds represented by the following general formulas (1) to (4).

The resin composition for the epidermis layer usually contains a solvent. The solvent may be any solvent that can dissolve each component in the resin composition. Specific examples of the solvent 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 solvent such as dimethyl carbonate and the like. Among them, the ketone solvent alone, the mixed solvent in which the ketone solvent and other solvents are used in combination, and the mixed solvent in which the ketone solvent and the ester solvent are used in combination have good solubility and drying property. Is preferable.

Various additives can be added to the resin composition for the epidermis layer depending on the physical properties to be applied to the cured layer formed by curing. Additives include weather resistance improvers, abrasion resistance improvers, polymerization inhibitors, cross-linking agents, infrared absorbers, antistatic agents, adhesive improvers, leveling agents, tincture imparting agents, coupling agents, and plasticizers. , Antifoaming agent, filler, coloring material and the like. As the weather resistance improving agent, a hindered amine-based light stabilizer such as HALS, an ultraviolet absorber, an antioxidant and the like can be used as long as the photocuring is not inhibited.

(Design layer)
Examples of the material constituting the design layer include thermoplastic resins and curable resins such as thermosetting and ultraviolet curable. Examples of the thermoplastic resin include acrylic resin, acrylic-modified polyolefin resin, chlorinated polyolefin resin, acid-modified polyolefin resin, vinyl chloride-vinyl acetate copolymer, thermoplastic urethane resin, thermoplastic polyester resin, polyamide resin, and rubber-based resin. Can be mentioned. Examples of the curable resin include urethane resin, acrylic resin, and epoxy resin. A design layer can be formed by applying a design to these resins using a colorant such as silica, organic beads, pigments, dyes, or an extender pigment. Colorants include carbon black, iron black, titanium white, antimony white, chrome yellow, titanium yellow, petals, cadmium red, ultramarine blue, cobalt blue and other inorganic pigments; quinacridone red, isoindolinone yellow, phthalocyanine blue and the like. Organic pigments or dyes; metal pigments made of scaly foil pieces such as aluminum and brass; pearl luster (pearl) pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate. Further, 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 may be used as the design layer.

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

In addition, for the purpose of imparting a high degree of design, a second design layer to which a design similar to the design given to the design layer or another design is given is provided between the skin layer and the design layer. Is also preferable. Further, in order to improve the adhesion between the base sheet and the design layer, a primer layer may be provided between them.

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

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 to 3000 μm, preferably 50 to 2000 μm.

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

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 to 500 μm, preferably 10 to 300 μm.

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

(Manufacturing method of decorative sheet (1))
Hereinafter, an example of a method for manufacturing a decorative sheet will be described. First, a resin composition for an epidermis layer (hereinafter, also referred to as "paint for an epidermis layer") is applied onto the surface of a guard film by a usual coating method to form a coating layer. Examples of the method (printing method) of applying the skin layer paint on the surface of the guard film include gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, and depp. Examples thereof include ordinary printing methods such as coating, solid coating with silk screen, wire bar coating, flow coating, comma coating, and spray coating. The drying temperature of the epidermis layer is usually 60 to 100 ° C, preferably 70 to 90 ° C. Further, the surface of the coating layer formed by obtaining the coating material for the epidermis layer can be painted by an inkjet method. For painting, for example, UV curable inkjet ink can be used. UV curable inkjet inks usually do not contain water or organic solvents and therefore do not require special drying.

Aging is preferred, if necessary, to complete the cross-linking reaction between the polyurethane (A) and the non-yellowing polyisocyanate (B). The aging conditions are usually about 1 to 3 days at 30 to 60 ° C. The aging of the epidermis layer may be performed at the time of forming the epidermis layer or the adhesive layer on the guard film, or may be performed after the epidermis layer or the adhesive layer is formed. At this time, in order to improve the adhesion between the design layer and the skin layer, a primer layer may be provided 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 design layer having a multi-layer structure. The 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 resin composition for the adhesive layer (paint for the adhesive layer) is applied onto the formed skin layer or the design layer by a usual coating method to form a coating layer. An adhesive layer can be formed by drying the formed coating layer. Examples of the method of applying the adhesive layer paint (coating method) include the same method as the above-mentioned method of applying the resin composition for forming the skin layer. The drying temperature of the adhesive layer coating material is usually 60 to 100 ° C., preferably 70 to 90 ° C. Alternatively, the adhesive layer previously formed on the transfer sheet may be transferred. A decorative sheet can be obtained by attaching a separate film for protecting the adhesive layer on the formed adhesive layer.

(Manufacturing method of decorative sheet (2))
Next, another example of the method of manufacturing the decorative sheet will be described. First, a resin composition for forming a design layer or the like is applied onto the surface of the base material sheet by a usual coating method to form a coating layer. The base sheet may be surface-modified by performing a primer treatment or a corona discharge treatment. These treatments may be performed on the back surface if necessary. Examples of the method of applying the resin composition for forming the design layer on the surface of the base sheet include a gravure coat, a gravure reverse coat, a gravure offset coat, a spinner coat, a roll coat, a reverse roll coat, a kiss coat, and a wheeler coat. , Dep coat, silk screen coat, wire bar coat, flow coat, comma coat, spray coat and the like. The drying temperature of the design layer is usually 60 to 100 ° C., preferably 70 to 90 ° C. Further, the design layer can also be formed by the inkjet method. In particular, a design layer can be formed by applying a UV curable inkjet ink by an inkjet method. As the inkjet ink, it is mainstream to use an ink that does not contain water or an organic solvent, and when such an ink is used, drying is not particularly required.

Further, the design layer previously formed on the transfer sheet may be transferred to the base sheet. At this time, in order to improve the adhesion between the design layer and the base sheet, a primer layer may be provided 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 design layer having a multi-layer structure. The 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 skin layer paint is applied onto the surface of the formed design layer by a usual coating method to form a coating layer. The epidermis layer can be formed by drying the formed coating layer. Examples of the method of applying the paint for the skin layer (coating method) include the same method as the method of applying the resin composition for forming the design layer described above. The drying temperature of the skin layer coating material is usually 60 to 100 ° C., preferably 70 to 90 ° C.

An adhesive layer paint is applied on 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. Examples of the method of applying the adhesive layer paint (coating method) include the same method as the above-mentioned method of applying the resin composition for forming a design layer. The drying temperature of the adhesive layer coating material is usually 60 to 100 ° C., preferably 70 to 90 ° C. Further, the adhesive layer previously formed on the transfer sheet may be transferred to the base sheet. A decorative sheet can be obtained by attaching a separate film for protecting the adhesive layer on the formed adhesive layer.

<Decorative molded products>
By using the above-mentioned decorative sheet, a decorative molded product can be manufactured. That is, the decorative molded article of the present invention includes a decorative member and a decorative layer arranged on the surface of at least a part of the decorative member. Then, this decorative layer has a laminated structure including a cured layer derived from the skin layer of the decorative sheet described above and an adhesive cured layer derived from the adhesive layer, which is arranged in contact with the surface of the member to be decorated. Has. FIG. 2 is a cross-sectional view schematically showing an embodiment of the decorative molded article of the present invention. The decorative molded article 100 of the embodiment shown in FIG. 2 includes a decorative member 40 and a decorative layer 60 arranged on the surface of at least a part of the decorative member 40. The decorative layer 60 has a laminated structure including a cured layer 23, a design layer 8, and an adhesive cured 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 adhesive hardening layer 25 is a layer derived from the adhesive layer 4 of the decorative sheet 10 shown in FIG. 1, and is arranged in contact with the surface of the decorative member 40.

FIG. 4 is a cross-sectional view schematically showing another embodiment of the decorative molded article of the present invention. The decorative molded article 200 of the embodiment shown in FIG. 4 includes a decorative member 50 and a decorative layer 70 arranged on the surface of at least a part of the decorative member 50. The decorative layer 70 has a laminated structure including a cured layer 33, a design layer 18, a base sheet 5, and an adhesive cured 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. 3, and is arranged in contact with the surface of the decorative member 50.

Since the decorative molded product has an adhesive cured layer formed by curing the above-mentioned adhesive layer that exhibits excellent adhesion to various materials, the decorative layer and the member to be decorated are firmly adhered to each other. At the same time, the layers constituting the decorative layer are also strongly adhered to each other, and have excellent interlayer adhesion. Further, since the decorative molded product has a cured layer formed by curing the above-mentioned skin layer, it is excellent in scratch resistance.

The decorative molded product of the present invention can be produced by a general three-dimensional surface decorative molding method (vacuum forming method) using the above-mentioned decorative sheet. As the decorative member, in addition to general resin members such as ABS and PC, metal decorative members such as various steel plates can be used.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.

<Synthesis of polyurethane (A)>
(Synthesis Example 1: Polyurethane 1)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, polyhexamethylene carbonate diol (trade name "Placel CD220", manufactured by Daicel Chemical Industries, Ltd., hydroxyl value = 56.1 mgKOH / g) 400.0 g, 1,4-butanediol 80 .0 g and 160.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mgKOH / g) were charged. Then, 226 g of methyl ethyl ketone (MEK) was charged. After the inside of the system became uniform, 103.8 g of hexamethylene diisocyanate (HDI) and 161.9 g of 4,4'-methylenebis-cyclohexyldiisocyanate were charged at 50 ° C., and dibutyltin laurylate was used as a catalyst at 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 ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin solution 1 containing polyurethane 1. The viscosity of the obtained resin solution 1 was 500 dPa · s / 20 ° C., and the solid content was 45%. The double bond equivalent of polyurethane 1 is 588 g / eq. The weight average molecular weight measured by GPC was 46,000, and the content of the structural unit derived from the polycarbonate polyol was about 44%.

<Synthesis of urethane resin (C)>
(Synthesis Example 2: Urethane Resin 2)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. Polyhexamethylene carbonate diol (trade name "ETERNACOLLUH-50", manufactured by Ube Industries, Ltd., hydroxyl value = 224.4 mgKOH / g) 300.0 g, 1,3-butanediol 20 while replacing the inside of the reaction vessel with air. .0 g and MEK 214.4 g were charged. After the inside of the system became uniform, 180.2 g of isophorone diisocyanate (IPDI) was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurilate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 2 for an adhesive layer containing urethane resin 2. The obtained resin composition 2 for an adhesive layer had a viscosity of 300 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 2 measured by GPC was 34,000, and the content of the structural unit (D) in the urethane resin 2 was 60%.

(Synthesis Example 3: Urethane Resin 3)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. Polyhexamethylene carbonate diol (trade name "ETERNACOLLUH-100", manufactured by Ube Industries, Ltd., hydroxyl value = 112.2 mgKOH / g) 300.0 g, 1,3-butanediol 20 while replacing the inside of the reaction vessel with air. .0 g and MEK186.6 g were charged. After the inside of the system became uniform, 114.2 g of IPDI was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 3 for an adhesive layer containing urethane resin 3. The obtained resin composition 3 for an adhesive layer had a viscosity of 40 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 3 measured by GPC was 41,000, and the content of the structural unit (D) in the urethane resin 3 was 69%.

(Synthesis Example 4: Urethane Resin 4)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. Polycyclohexanedimethanol / hexanediol copolymerized carbonatediol (trade name "ETERNACOLLM-90 (3/1)", manufactured by Ube Industries, Ltd., hydroxyl value = 112.2 mgKOH / g) while replacing the inside of the reaction vessel with air. 300.0 g, 20.0 g of 1,3-butanediol, and 186.6 g of MEK were charged. After the inside of the system became uniform, 114.2 g of IPDI was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 4 for an adhesive layer containing urethane resin 4. The obtained resin composition 4 for an adhesive layer had a viscosity of 100 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 4 measured by GPC was 39,000, and the content of the structural unit (D) in the urethane resin 4 was 69%.

(Synthesis Example 5: Urethane Resin 5)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. Polycyclohexanedimethanol / hexanediol copolymerized carbonatediol (trade name "ETERNACOLLM-90 (3/1)", manufactured by Ube Industries, Ltd., hydroxyl value = 112.2 mgKOH / g) while replacing the inside of the reaction vessel with air. 300.0 g, 20.0 g of 1,3-butanediol, and 181.7 g of MEK were charged. After the inside of the system became uniform, 103.9 g of IPDI was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 5 for an adhesive layer containing urethane resin 5. The obtained resin composition 5 for an adhesive layer had a viscosity of 5 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 5 measured by GPC was 12,000, and the content of the structural unit (D) in the urethane resin 5 was 71%.

(Synthesis Example 6: Urethane Resin 6)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. Polycyclohexanedimethanol / hexanediol copolymerized carbonatediol (trade name "ETERNACOLLM-90 (3/1)", manufactured by Ube Industries, Ltd., hydroxyl value = 112.2 mgKOH / g) while replacing the inside of the reaction vessel with air. 300.0 g, 1,3-butanediol, and MEK 194.9 g were charged. After the inside of the system became uniform, 134.9 g of dicyclohexylmethane diisocyanate (hydrogenated MDI) was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyltin laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 6 for an adhesive layer containing urethane resin 6. The obtained resin composition 6 for an adhesive layer had a viscosity of 470 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 6 measured by GPC was 42,000, and the content of the structural unit (D) in the urethane resin 6 was 66%.

(Synthesis Example 7: Urethane Resin 7)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, polypentanediol / hexanediol copolymerized carbonate diol (trade name "Duranol T5650E", manufactured by Asahi Kasei Corporation, hydroxyl value = 224.4 mgKOH / g) 300.0 g, 1,3- 20.0 g of butanediol and 214.4 g of MEK were charged. After the inside of the system became uniform, 180.2 g of IPDI was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 7 for an adhesive layer containing urethane resin 7. The obtained resin composition 7 for an adhesive layer had a viscosity of 70 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 7 measured by GPC was 31,000, and the content of the structural unit (D) in the urethane resin 7 was 60%.

(Comparative Synthesis Example 1: Urethane Resin 8)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, polycaprolactone diol (trade name "Plaxel 205", manufactured by Daicel Chemical Industries, Ltd., hydroxyl value = 224.4 mgKOH / g) 300.0 g, 1,3-butanediol 20.0 g , And MEK21.4 g were charged. After the inside of the system became uniform, 180.2 g of IPDI was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 8 for an adhesive layer containing urethane resin 8. The obtained resin composition 8 for an adhesive layer had a viscosity of 130 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 8 measured by GPC was 36,000, and the content of the structural unit (D) in the urethane resin 8 was 0%.

(Comparative Synthesis Example 2: Urethane Resin 9)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. Polyhexamethylene carbonate diol (trade name "ETERNACOLLUH-200", manufactured by Ube Industries, Ltd., hydroxyl value = 56.1 mgKOH / g) 300.0 g, 1,3-butanediol 20 while replacing the inside of the reaction vessel with air. .0 g and MEK171.9 g were charged. After the inside of the system became uniform, 81.3 g of IPDI was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 9 for an adhesive layer containing urethane resin 9. The obtained resin composition 9 for an adhesive layer had a viscosity of 560 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 9 measured by GPC was 51,000, and the content of the structural unit (D) in the urethane resin 9 was 74.8%.

(Comparative Synthesis Example 3: Urethane Resin 10)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, polypentanediol / hexanediol copolymerized carbonate diol (trade name "Duranol T5652", manufactured by Asahi Kasei Corporation, hydroxyl value = 56.1 mgKOH / g) 300.0 g, 1,3- 20.0 g of butanediol and 171.9 g of MEK were charged. After the inside of the system became uniform, 81.3 g of IPDI was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 10 for an adhesive layer containing a urethane resin 10. The obtained resin composition 10 for an adhesive layer had a viscosity of 210 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 10 measured by GPC was 49,000, and the content of the structural unit (D) in the urethane resin 10 was 74.8%.

(Comparative Synthesis Example 4: Urethane Resin 11)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blow tube, and a manhole was prepared. Polyhexamethylene carbonate diol (trade name "ETERNACOLLUH-200", manufactured by Ube Industries, Ltd., hydroxyl value = 56.1 mgKOH / g) 300.0 g, 1,3-butanediol 72 while replacing the inside of the reaction vessel with air. .0 g and MEK249.8 g were charged. After the inside of the system became uniform, 210.9 g of IPDI was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin composition 11 for an adhesive layer containing urethane resin 11. The obtained resin composition 11 for an adhesive layer had a viscosity of 440 dPa · s / 20 ° C. and a solid content of 35%. The weight average molecular weight of the urethane resin 11 measured by GPC was 46,000, and the content of the structural unit (D) in the urethane resin 11 was 51.5%.

<Synthesis of acrylic polymer>
(Comparative Synthesis Example 5: Acrylic Polymer 1)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. After replacing the inside of the reaction vessel with nitrogen gas, 100 g of MEK and 50.0 g of methyl methacrylate were charged and heated to 60 ° C. under a nitrogen atmosphere. On the other hand, a mixture of 50.0 g of butyl acrylate and 2 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was prepared. Half of the prepared mixture was added into the reaction vessel, and the other half was added dropwise to the reaction vessel over 1 hour with a dropping funnel. After the dropping, the reaction was carried out as it was for 6 hours to obtain a resin composition 12 for an adhesive layer containing the acrylic polymer 1. The obtained resin composition 12 for an adhesive layer had a viscosity of 80 dPa · s / 20 ° C. and a solid content of 55%. The weight average molecular weight of the acrylic polymer 1 measured by GPC was 35,000.

<Preparation of paint for epidermis layer>
(Paint for epidermis layer 1)
2.25 g of a photopolymerization initiator (trade name "Irgacure 184", manufactured by BASF) was added to 1 100 g of the resin solution. Furthermore, 2.25 g of non-yellowing polyisocyanate (trade name "Duranate TPA-100", manufactured by Asahi Kasei Corporation, containing 100% solid content and 23.1% isocyanate), and MEK and cyclohexanone in a mass ratio of 1: 1 By blending, a skin layer coating material 1 having a solid content of 30% was obtained.

<Preparation of composition for adhesive layer with design>
(Resin composition for adhesive layer 13)
Resin composition for adhesive layer 2 100 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) 20.0 g , MEK and cyclohexanone were blended in a mass ratio of 1: 1 to obtain a resin composition 13 for an adhesive layer having a design property with a solid content of 20%.

<Preparation of composition for design layer>
(Composition for design layer 1)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. While substituting 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 by quantification of terminal functional groups: 2,000) 400.0 g, 1,4 -Butandiol 40.0 g and MEK 146 g were charged. After the inside of the system became uniform, 143.0 g of IPDI was charged at 50 ° C., and the reaction was carried out at 80 ° C. using dibutyl phthalate laurylate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until the absorption ^{of 2,270 cm-1 by the free isocyanate group measured by infrared absorption spectrum analysis disappeared.} Cyclohexanone was added until the mass ratio of MEK and cyclohexanone was 1: 1 to obtain a resin solution 1 for a design layer containing a urethane resin. The viscosity of the obtained resin solution was 420 dPa · s / 20 ° C., and the solid content was 40%. The weight average molecular weight of the urethane resin measured by GPC was 44,000. Non-leafing type aluminum paste (trade name "MH-6601", manufactured by Asahi Kasei Kogyo Co., Ltd., solid content 65%) 12.0 g, MEK and cyclohexanone by mass ratio 1 to 100.0 g of the obtained resin solution for design layer The composition 1 for a design layer having a solid content of 30% was obtained by blending at a ratio of 1.

(Composition for design layer 2)
Aluminum for vapor deposition was used as the design layer composition 2.

(Composition for design layer 3)
A UV ink for an inkjet printer containing a UV-reactive monomer, a pigment, and a polymerization initiator was used as the design layer composition 3.

(Composition for design layer 4)
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) 20.0 g in 100 g of resin solution for design layer , MEK and cyclohexanone were blended in a mass ratio of 1: 1 to obtain a composition 4 for a design layer having a solid content of 30%.

<Manufacturing of decorative sheets (1)>
(Example 1)
The surface of the guard film (trade name "Novaclear", manufactured by Mitsubishi Chemical Corporation, amorphous PET film with a thickness of 200 μm) is coated with the skin layer paint 1 with a bar coater, and then dried at 90 ° C. for 2 minutes. An epidermis layer having a thickness of 15 μm was formed. The resin composition 2 for an adhesive layer was applied to the surface of the formed epidermis layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. A separate film (a PET film having a thickness of 80 μm) was attached to the surface of the formed adhesive layer, and then aged at 45 ° C. for 1 day to obtain a decorative sheet (Example 1).

(Example 2)
The surface of the guard film (trade name "Novaclear", manufactured by Mitsubishi Chemical Corporation, amorphous PET film with a thickness of 200 μm) is coated with the skin layer paint 1 with a bar coater, and then dried at 90 ° C. for 2 minutes. An epidermis layer having 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 a skin layer formed using a UV inkjet printer, and a pattern was printed to form a design layer. The resin composition 2 for an adhesive layer was applied to the surface of the formed design layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. A separate film (a PET film having a thickness of 80 μm) was attached to the surface of the formed adhesive layer, and then aged at 45 ° C. for 1 day to obtain a decorative sheet (Example 2).

(Example 3)
The surface of the guard film (trade name "Novaclear", manufactured by Mitsubishi Chemical Corporation, amorphous PET film with a thickness of 200 μm) is coated with the skin layer paint 1 with a bar coater, and then dried at 90 ° C. for 2 minutes. An epidermis layer having a thickness of 15 μm was formed. On the surface of the formed clear layer, a design layer made of a thin film of aluminum was formed by a thin film deposition method. The resin composition 2 for an adhesive layer was applied to the surface of the formed design layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. A separate film (a PET film having a thickness of 80 μm) was attached to the surface of the formed adhesive layer, and then aged at 45 ° C. for 1 day to obtain a decorative sheet (Example 3).

(Examples 4 to 12 and Comparative Examples 1 to 5)
The epidermis layer was formed using the types of skin layer paints shown in Tables 1-1 to 1-3, and the adhesive layer was used to use the types of adhesive layer resin compositions shown in Tables 1-1 to 1-3. Decorative sheets (Examples 4 to 12 and Comparative Examples 1 to 5) were obtained in the same manner as in the case of Example 1 described above, except that the above-mentioned case was formed.

<Manufacturing of decorative sheets (2)>
(Example 13)
The resin composition 2 for the adhesive layer is coated on the surface of the base sheet (trade name "Tough Ace R EAR802", manufactured by Sumitomo Bakelite, Inc., 1 mm thick acrylonitrile-butadiene-styrene copolymer (ABS) sheet) with a bar coater. Then, it was dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. The composition 4 for the design layer was coated on the surface of the formed primer layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. After applying the skin layer paint 1 to the surface of the formed design layer with a bar coater, the skin layer was dried at 90 ° C. for 2 minutes to form a skin layer having a thickness of 15 μm, and aged at 45 ° C. for 1 day. The resin composition 2 for an adhesive layer was applied to the back surface of the base sheet with a bar coater, and then dried at 80 ° 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 attached to the surface of the formed adhesive layer to obtain a decorative sheet (Example 13).

(Examples 14 to 21 and Comparative Examples 6 to 10)
Decorative sheets (Examples 14 to 21) in the same manner as in Example 1 described above, except that the adhesive layer was formed using the types of resin compositions for adhesive layers shown in Tables 2-1 to 2-3. And Comparative Examples 6 to 10) were obtained.

(Example 22)
The resin composition 2 for the adhesive layer is coated on the surface of the base sheet (trade name "Tough Ace R EAR802", manufactured by Sumitomo Bakelite, Inc., 1 mm thick acrylonitrile-butadiene-styrene copolymer (ABS) sheet) with a bar coater. Then, it was dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. The composition 4 for the design layer was coated on the surface of the formed primer layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The skin layer paint 1 was applied to the surface of the formed design layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form a skin layer having a thickness of 15 μm. After aging at 45 ° C. for 1 day, processing (concavo-convex processing) was performed using an embossed roll with wrinkles heated to 100 ° C. to form an uneven pattern on the surface of the epidermis layer. The resin composition 2 for an adhesive layer was applied to the back surface of the base sheet with a bar coater, and then dried at 80 ° 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 attached to the surface of the formed adhesive layer to obtain a decorative sheet (Example 22).

(Example 23)
The resin composition 2 for the adhesive layer is coated on the surface of the base sheet (trade name "Tough Ace R EAR802", manufactured by Sumitomo Bakelite, Inc., 1 mm thick acrylonitrile-butadiene-styrene copolymer (ABS) sheet) with a bar coater. Then, it was dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. The composition for the design layer 1 was applied to the surface of the formed primer layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. After applying the skin layer paint 1 to the surface of the formed design layer with a bar coater, the skin layer was dried at 90 ° C. for 2 minutes to form a skin layer having a thickness of 15 μm, and aged at 45 ° C. for 1 day. The resin composition 2 for an adhesive layer was applied to the back surface of the base sheet with a bar coater, and then dried at 80 ° 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 attached to the surface of the formed adhesive layer to obtain a decorative sheet (Example 23).

(Example 24)
The resin composition 2 for the adhesive layer is coated on the surface of the base sheet (trade name "Tough Ace R EAR802", manufactured by Sumitomo Bakelite, Inc., 1 mm thick acrylonitrile-butadiene-styrene copolymer (ABS) sheet) with a bar coater. Then, it was dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. Aluminum for vapor deposition (composition for design layer 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 applying the skin layer paint 1 to the surface of the formed design layer with a bar coater, the skin layer was dried at 90 ° C. for 2 minutes to form a skin layer having a thickness of 15 μm, and aged at 45 ° C. for 1 day. The resin composition 2 for an adhesive layer was applied to the back surface of the base sheet with a bar coater, and then dried at 80 ° 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 attached to the surface of the formed adhesive layer to obtain a decorative sheet (Example 24).

(Example 25)
The resin composition 2 for the adhesive layer is coated on the surface of the base sheet (trade name "Tough Ace R EAR802", manufactured by Sumitomo Bakelite, Inc., 1 mm thick acrylonitrile-butadiene-styrene copolymer (ABS) sheet) with a bar coater. Then, it was dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. UV ink (composition 3 for design layer) 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 applying the skin layer paint 1 to the surface of the formed design layer with a bar coater, the skin layer was dried at 90 ° C. for 2 minutes to form a skin layer having a thickness of 15 μm, and aged at 45 ° C. for 1 day. The resin composition 2 for an adhesive layer was applied to the back surface of the base sheet with a bar coater, and then dried at 80 ° 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 attached to the surface of the formed adhesive layer to obtain a decorative sheet (Example 25).

(Example 26)
A polypropylene (PP) sheet having a thickness of 0.5 mm (surface energy: 30 mN / m) was prepared. Both the front and back surfaces of this PP sheet were subjected to corona discharge treatment to obtain a base sheet having a surface energy of 37 mN / m. The surface of the obtained base sheet was coated with the resin composition 2 for an adhesive layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. The composition 4 for the design layer was coated on the surface of the formed primer layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. After applying the skin layer paint 1 to the surface of the formed design layer with a bar coater, the skin layer was dried at 90 ° C. for 2 minutes to form a skin layer having a thickness of 15 μm, and aged at 45 ° C. for 1 day. The resin composition 2 for an adhesive layer was applied to the back surface of the base sheet with a bar coater, and then dried at 80 ° 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 attached to the surface of the formed adhesive layer to obtain a decorative sheet (Example 26).

(Example 27)
A resin composition 2 for an adhesive layer is applied to the surface of a base sheet (polycarbonate (PC) sheet having a thickness of 0.5 mm) with a bar coater, dried at 90 ° C. for 2 minutes, and a primer layer having a thickness of 5 μm. Was formed. The composition 4 for the design layer was coated on the surface of the formed primer layer with a bar coater, and then dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. After applying the skin layer paint 1 to the surface of the formed design layer with a bar coater, the skin layer was dried at 90 ° C. for 2 minutes to form a skin layer having a thickness of 15 μm, and aged at 45 ° C. for 1 day. The resin composition 2 for an adhesive layer was applied to the back surface of the base sheet with a bar coater, and then dried at 80 ° 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 attached to the surface of the formed adhesive layer to obtain a decorative sheet (Example 27).

<Manufacturing of decorative molded products>
Using a vacuum forming machine (trade name "NGF-0404-S type", manufactured by Fuse Vacuum Co., Ltd.), the types shown in Tables 1-1 to 1-3 and 2-1 to 2-3 were heated to 100 ° C. An adhesive layer of a decorative sheet heated to 100 ° C. was attached to the surface of the decorative member by vacuum forming. Using an ultraviolet irradiator (trade name "UNICURE UVC-02512S1AA01", manufactured by Ushio, Inc.), UV irradiation is applied to the decorative sheet attached to the surface of the decorative member so that the cumulative light amount is 2,000 mJ / cm ^2. Then, the epidermis layer was cured to form a cured layer to obtain a decorative molded product.

<Evaluation method>
(1) Adhesive strength An adhesive layer of a decorative sheet heated to 100 ° C is attached to the surface of the types of decorative members shown in Tables 1-1 to 1-3 heated to 100 ° C with a rubber roller. After that, a notch with a width of 10 mm was made in the decorative sheet. Using a tensile tester (model name "Autograph AGS-100A", manufactured by Shimadzu Corporation), the decorative sheet is peeled 180 ° at 25 ° C and a tensile speed of 100 mm / min to measure the adhesive strength of the adhesive layer. Then, the adhesive strength was evaluated according to the evaluation criteria shown below. The results are shown in Tables 1-1 to 1-3 and 2-1 to 2-3.
⊚: The decorative sheet was torn.
◯: The decorative sheet was not broken, but the adhesive strength was 5 N or more.
Δ: Adhesive strength was 5 N or less.
X: Could not be adhered.

(2) Heat-resistant creep An adhesive layer of a decorative sheet heated to 100 ° C is attached to the surface of the types of decorative members shown in Tables 1-1 to 1-3 heated to 100 ° C with a rubber roller. After that, a notch having a width of 5 mm and a length of 12 mm was made in the decorative sheet. A weight of 100 g was attached to a portion of the decorative sheet that was not attached to the surface of the member to be decorated, and the weight was held in an atmosphere of 100 ° C. for 25 minutes. The state of the decorative film after holding was visually observed, and the heat-resistant creep was evaluated according to the evaluation criteria shown below. The results are shown in Tables 1-1 to 1-3 and 2-1 to 2-3.
⊚: The notch was not misaligned at all.
◯: The deviation of the notch was less than 5 mm.
Δ: The deviation of the notch was 5 mm or more, but the weight did not fall.
X: The notch is largely misaligned and the weight has fallen.

(3) Three-dimensional moldability (vacuum formability)
The appearance of the manufactured decorative molded product was observed, and the three-dimensional moldability (vacuum formability) was evaluated according to the evaluation criteria shown below. The results are shown in Tables 1-1 to 1-3 and 2-1 to 2-3.
⊚: No cracking or whitening of the coating film 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 cracking or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion, but the level was not a problem in practical use.
Δ: Minor coating film cracking or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion.
X: The skin layer and the design layer could not follow the shape of the mold and could not be adhered.

(4) Light resistance In accordance with JASO M346-1993, an accelerated test of a decorative molded product was carried out using a xenon weather meter according to the following conditions. The appearance of the decorative molded product 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 1-1 to 1-3 and 2-1 to 2-3.
・ Irradiance: 48-162 W / m ²
-Wavelength: 300-400 nm
・ Black panel temperature: 89 ± 3 ℃
・ Irradiation time: 8 weeks ・ Calorie: 2,000kJ
⊚: No yellowing, whitening, cracks, cracks, wrinkles, etc. occurred in the adhesive layer.
◯: Fine yellowing, whitening, cracks, cracks, wrinkles, etc. occurred in a part of the three-dimensional shape portion or the maximum stretched portion, but the level was not a problem in practical use.
X: Yellowing, whitening, cracks, cracks, wrinkles, etc. occurred in the adhesive layer.

(5) Heat resistance The manufactured decorative molded product was placed in an oven and held at 120 ° C. for 400 hours in a heat resistance test. The appearance of the adhesive layer after the test was observed, and the heat resistance was evaluated according to the evaluation criteria shown below. The results are shown in Tables 1-1 to 1-3 and 2-1 to 2-3.
⊚: No yellowing, whitening, cracks, cracks, wrinkles, etc. occurred in the adhesive layer.
◯: Fine yellowing, whitening, cracks, cracks, wrinkles, etc. occurred in a part of the three-dimensional shape portion or the maximum stretched portion, but the level was not a problem in practical use.
X: Yellowing, whitening, cracks, cracks, wrinkles, etc. occurred in the adhesive layer.

(6) Hydrolysis resistance A jungle test was conducted in which the manufactured decorative molded product was held at a temperature of 70 ° C. and a relative humidity of 95% for 8 weeks. The appearance of the adhesive layer after the test was observed, and the hydrolysis resistance was evaluated according to the evaluation criteria shown below. The results are shown in Tables 1-1 to 1-3 and 2-1 to 2-3.
⊚: No yellowing, whitening, cracks, cracks, wrinkles, etc. occurred in the adhesive layer.
◯: Fine yellowing, whitening, cracks, cracks, wrinkles, etc. occurred in a part of the three-dimensional shape portion or the maximum stretched portion, but the level was not a problem in practical use.
X: Yellowing, whitening, cracks, cracks, wrinkles, etc. occurred in the adhesive layer.

(7) 80 ° C. Breaking Elongation The skin layer coating material 1 was applied onto 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, after ^{confirming that the absorption derived from the 2,270 cm-1} isocyanate group (non-yellowing polyisocyanate) has disappeared using an infrared spectrophotometer, the coating film is 15 mm wide x long. A test piece was prepared by cutting into a size of 60 mm. For the prepared test piece, an autograph (trade name "AGS-J 500N", manufactured by Shimadzu Corporation) and a constant temperature test device (trade name "TCR1-200", manufactured by Shimadzu Corporation) were used, 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 elongation at break at 80 ° C. was 300%.

(8) Pencil hardness The pencil hardness of the surface (ultraviolet-cured cured layer) of the produced decorative molded product was measured according to JIS K 5600. As a result, the pencil hardness was "2B".

The decorative sheet of the present invention is, for example, an interior material and an exterior material of a vehicle such as an automobile; a housing of a home electric appliance such as a television, a personal computer, and a mobile phone; an interior material of a building such as a wall, a floor, and a ceiling; a container, etc. It is useful as a material for manufacturing the decorative molded product of No. 1 by the three-dimensional surface decorative molding method.

2,12: Skin layer 4,14: Adhesive layer 5: Base sheet 6: Guard film 7,17: Separate film 8,18: Design layer 10, 30: Decorative sheet 23, 33: Hardened layer 25, 35: Adhesive hardening layer 40, 50: Decorative member 60, 70: Decorative layer 100, 200: Decorative molded product

Claims (10)

A decorative sheet used in a method for manufacturing a decorative molded product, which comprises a step of irradiating ultraviolet rays after three-dimensional decorative molding to form a cured layer.
It has a laminated structure with a skin layer and an adhesive layer,
The adhesive layer is formed of a resin composition for an adhesive layer containing a urethane resin (C) having a structural unit (D) derived from a polycarbonate polyol having a hydroxyl value of 80 to 250 mgKOH / g.
The epidermis layer is formed of an active energy ray-curable resin composition for the epidermis layer.
The elongation at break of the epidermis layer at 80 ° C. is 250% or more.
A decorative sheet having a pencil hardness of 4B or more measured in accordance with JIS K 5600, which is a cured layer formed by curing the skin layer with ultraviolet rays. The decorative sheet according to claim 1, wherein the structural unit (D) includes an alicyclic skeleton. The decorative sheet according to claim 1 or 2, wherein the urethane resin (C) has a weight average molecular weight of 2,000 to 500,000. The decorative sheet according to any one of claims 1 to 3, wherein the content of the structural unit (D) in the urethane resin (C) is 30 to 80% by mass. The resin composition for the adhesive layer further contains a cross-linking agent, and the resin composition further contains a cross-linking agent.
The item according to any one of claims 1 to 4, wherein the content of the cross-linking agent in the resin composition for an adhesive layer is 2 to 25 parts by mass with respect to 100 parts by mass of the urethane resin (C). Decorative sheet. The addition according to any one of claims 1 to 5, wherein the resin composition for the epidermis layer contains a polycarbonate-based polyurethane (A) containing a (meth) acryloyloxy group and a non-yellowing polyisocyanate (B). Decorative sheet. With more guard film
The decorative sheet according to any one of claims 1 to 6, which has a laminated structure in which the guard film, the skin layer, and the adhesive layer are laminated in this order. The decorative sheet according to claim 7, further comprising a design layer arranged between the skin layer and the adhesive layer. Further provided with a base sheet and a design layer,
The decorative sheet according to any one of claims 1 to 6, which has a laminated structure in which the skin layer, the design layer, the base material sheet, and the adhesive layer are laminated in this order. A decorative member and a decorative layer arranged on the surface of at least a part of the decorated member are provided.
The adhesion in which the decorative layer is arranged in contact with the cured layer derived from the skin layer of the decorative sheet according to any one of claims 1 to 9 and the surface of the decorated member. A decorative molded product having a laminated structure including an adhesive hardening layer derived from the layer.

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