JP6034779B2 - High durability functional molded sheet and decorative molded product obtained using the same - Google Patents

Description

  The present invention relates to a highly durable functional molded sheet and a decorative molded product obtained using the same.

  Conventionally, in-mold molding and insert mold molding (hereinafter also referred to as “in-mold molding”) are known as methods for obtaining a decorative molded product. On the other hand, the three-dimensional surface decoration molding method is a method that has a feature that it is possible to give higher designability and that a mold is unnecessary, and it is a housing for a home appliance such as a personal computer or a vehicle interior / exterior. Applications are expanding as a molding method for manufacturing parts. A general decorative sheet used in such a three-dimensional surface decorative molding method is a laminate including a thermoplastic guard film, a clear layer, an adhesive layer, and a separate film as constituent layers.

A general three-dimensional surface decoration molding method is performed, for example, according to the following steps (1) to (6).
(1) A decorative sheet is sandwiched between tables placed above the lower chamber box.
(2) Lower the upper chamber to make a sealed space.
(3) The chambers are evacuated.
(4) The decorative sheet is heated with an infrared heater.
(5) Raise the molded part installed in the lower chamber box.
(6) The upper chamber is opened to atmospheric pressure when the molded part comes into contact with the decorative sheet.

  The molding temperature in the three-dimensional surface decoration molding method is about 80 to 110 ° C., which is lower than the molding temperature in in-mold molding of about 120 to 200 ° C. For this reason, in the conventional technique (for example, refer to Patent Document 1) in which the active energy ray is irradiated before molding to cure the sheet, the elongation at the time of molding is insufficient, and the three-dimensional shape cannot be followed, and cracking occurs. In some cases, it became easier.

  On the other hand, in order to follow the elongation at the time of molding, the clear layer is formed of an ultraviolet curable uncured resin, and after the molding, the clear layer is cured by irradiating with ultraviolet rays, thereby achieving moldability and scratch resistance. There is technology that balances sex. However, such an uncured resin has a problem that it is difficult to handle because of its high fluidity and tackiness. In order to solve such a problem, for example, a method of half-curing the clear layer by irradiating ultraviolet rays is known (Patent Document 2). However, if the clear layer is cured too much, it is difficult to control the elongation at the time of molding.

  Further, Patent Document 3 proposes a (meth) acryloyl group-containing polyurethane resin for the purpose of achieving both scratch resistance and three-dimensional moldability. However, since an acryloyl group-containing polyol obtained by reacting propylene glycol and glycidyl acrylate for the purpose of introducing a (meth) acryloyl group into the polyurethane is used as a raw material, an ether bond exists in the main chain polyurethane structure. become. For this reason, heat resistance durability was inadequate.

JP 2005-292198 A Japanese Patent Application Laid-Open No. 6-134859 JP 2010-053357 A

  The present invention has been made in view of such problems of the prior art, and the object of the present invention is a surface having excellent three-dimensional formability and excellent scratch resistance and impact resistance. An object of the present invention is to provide a highly durable functional molded sheet capable of producing a decorative molded product having the above. Moreover, the place made into the subject of this invention provides the decorative molded product which has the surface (hardened layer) excellent in abrasion resistance and impact resistance manufactured using said highly durable functional molding sheet. There is.

That is, according to the present invention, the following highly durable functional molded sheet is provided.
[1] A guard film, a clear layer, and an adhesive layer are laminated in this order, and if necessary, a separate film is disposed on the surface of the adhesive layer, and the clear layer is a monool (A). And a photocurable resin composition containing a polyurethane resin represented by the following general formula (1), obtained by reacting polyisocyanate (B), polyamine (C), and polyol (D) as essential components. The ratio of the number of moles of isocyanate groups of the polyisocyanate (B) to the total number of moles of hydroxyl groups of the monool (A) and the number of moles of hydroxyl groups of the polyol (D) ((B) / ((A) + (D))) is 1.5 to 3, and the number of moles of hydroxyl groups of the monool (A) relative to the number of moles of isocyanate groups of the polyisocyanate (B). The total ratio (((A) + (C) + (D)) / (B)) of moles of amino groups of the polyamine (C) and moles of hydroxyl groups of the polyol (D) is 0.7 to 1.0 and at least one of the monool (A) and the polyol (D) has a (meth) acryloyloxy group, and the monool (A), the polyisocyanate (B), the polyamine ( C) and the proportion of (D) of the polyol not having a (meth) acryloyloxy group in the total of the polyol (D) is 30% by mass or less, and the weight average molecular weight of the polyurethane resin is 2, A highly durable functional molded sheet of 000 to 150,000.

（前記一般式（１）中、Ｒ₁はモノオール残基を示し、Ｒ₂はポリイソシアネート残基を示し、Ｒ₃はポリアミン残基を示し、Ｒ₄はポリオール残基を示し、ｍ及びｎは、それぞれ繰り返し数を示す）

(In the general formula (1), R ₁ represents a monool residue, R ₂ represents a polyisocyanate residue, R ₃ represents a polyamine residue, R ₄ represents a polyol residue, m and n Indicates the number of repetitions)

  [2] The highly durable functional molded sheet according to [1], wherein the polyisocyanate (B) is a polyisocyanate having a (meth) acryloyloxy group.

[3] The highly durable functional molded sheet according to [1] or [2], wherein the polyol (D) is a polycarbonate polyol.
[4] The double bond equivalent of the polyurethane resin is 130 to 1300 g / eq. The highly durable functional molded sheet according to any one of [1] to [3].
[5] The highly durable functional molded sheet according to any one of [1] to [4], wherein the photocurable resin composition further contains 0.01 to 10% by mass of a photopolymerization initiator.
[6] The highly durable functional molded sheet according to any one of [1] to [5], wherein a design is applied to the adhesive layer.
[7] The highly durable functional molded sheet according to any one of [1] to [6], wherein the adhesive layer is a resin layer to which a design is applied.
[8] The adhesive layer is an acrylic resin, an acrylic-modified polyolefin resin, a chlorinated or acid-modified polyolefin resin, a vinyl chloride-vinyl acetate copolymer, a thermoplastic urethane resin, a thermoplastic polyester resin, a polyamide resin, a rubber-based resin, And at least one thermoplastic resin selected from the group consisting of terpene-based resins, or any one of the above [1] to [7] including a thermosetting resin of at least one of a urethane resin and an epoxy resin Highly durable functional molded sheet as described in 1.
[9] The highly durable functional molded sheet according to any one of [1] to [8], wherein a design layer is disposed between the adhesive layer and the clear layer.

Moreover, according to this invention, the decorative molded product shown below is provided.
[10] A decorative molded product having a cured layer formed by UV-curing the clear layer, obtained using the highly durable functional molded sheet according to any one of [1] to [9].

  The highly durable functional molded sheet of the present invention is less susceptible to defects such as cracks during three-dimensional molding and has excellent three-dimensional moldability. And if the highly durable functional molding sheet of this invention is used, the decorative molded product which has the surface excellent in abrasion resistance and impact resistance can be manufactured simply. Moreover, the decorative molded product of the present invention is manufactured using the above highly durable functional molded sheet, and has a surface (cured layer) excellent in scratch resistance and impact resistance.

It is sectional drawing which shows typically one Embodiment of the highly durable functional molding sheet | seat of this invention.

(High durability functional molded sheet)
FIG. 1 is a cross-sectional view schematically showing one embodiment of a highly durable functional molded sheet of the present invention. As shown in FIG. 1, a functional molded sheet (hereinafter, also simply referred to as “functional molded sheet”) 10 of the present embodiment has a guard film 1, a clear layer 2, and an adhesive layer 4 laminated in this order. Yes. The clear layer 2 is a layer having scratch resistance and impact resistance. A separate film 5 may be disposed on the surface of the adhesive layer 4. A design layer 3 may be disposed between the adhesive layer 4 and the clear layer 2. A decorative molded product (surface layer) excellent in scratch resistance and impact resistance can be obtained by three-dimensionally decorating a molded part using the functional molded sheet 10 and then curing by ultraviolet irradiation.

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

(Clear layer)
The pencil hardness at a load of 500 g measured according to JIS K5400 of the cured layer formed by UV-curing the clear layer constituting the functional molded sheet of the present invention is preferably H or more, more preferably 2H or more. Especially preferably, it is 3H or more. That is, the functional molded sheet of the present invention produces a decorative molded product having a surface excellent in scratch resistance and impact resistance because the hardness of the cured layer formed by UV-curing the clear layer is sufficiently high. can do. Furthermore, the clear layer before UV curing has good elongation. That is, in the functional molded sheet of the present invention, the clear layer is sufficiently cured after UV irradiation while having excellent three-dimensional moldability before UV irradiation. For this reason, if the functional molding sheet of this invention is used, the decorative molded product which has the surface excellent in abrasion resistance and impact resistance can be simply manufactured, without producing malfunctions, such as a crack. In addition, although it does not specifically limit about the upper limit of the pencil hardness of a hardened layer, it is 5H or less substantially.

  The clear layer is formed of a photocurable resin composition containing a polyurethane resin represented by the following general formula (1) (hereinafter also simply referred to as “polyurethane”). This polyurethane can be obtained by reacting monool (A), polyisocyanate (B), polyamine (C), and polyol (D) as essential components.

（前記一般式（１）中、Ｒ₁はモノオール残基を示し、Ｒ₂はポリイソシアネート残基を示し、Ｒ₃はポリアミン残基を示し、Ｒ₄はポリオール残基を示し、ｍ及びｎは、それぞれ繰り返し数を示す）

(In the general formula (1), R ₁ represents a monool residue, R ₂ represents a polyisocyanate residue, R ₃ represents a polyamine residue, R ₄ represents a polyol residue, m and n Indicates the number of repetitions)

  Ratio of the number of moles of isocyanate groups of polyisocyanate (B) to the total number of moles of hydroxyl groups of monool (A) and the number of moles of hydroxyl groups of polyol (D) ((B) / ((A) + (D) )) Is preferably 1.45 to 3.1, and more preferably 1.5 to 3. When the value of (B) / ((A) + (D)) is less than 1.45, urea bonds in the polyurethane are reduced and the molecular weight of the polyurethane is also reduced. For this reason, the surface tack of the formed clear layer becomes strong, or cracks are likely to occur during molding due to insufficient strength. On the other hand, when the value of (B) / ((A) + (D)) exceeds 3.1, the molecular weight of the polyurethane becomes too large, and the coatability is lowered. Further, the ratio of the total number of moles of the hydroxyl group of the monool (A), the number of moles of the hydroxyl group of the polyol (D), and the number of moles of the amino group of the polyamine (C) to the number of moles of the isocyanate group of the polyisocyanate (B). (((A) + (C) + (D)) / (B)) is 0.7 to 1.0, preferably 0.75 to 1.0.

Moreover, the weight average molecular weight of polyurethane is 2,000-150,000. By using a polyurethane having a weight average molecular weight of 2,000 or more, the following effects (i) to (iii) can be obtained.
(I) Surface tack before UV curing is reduced and operability is improved.
(Ii) Three-dimensional formability is improved.
(Iii) A decorative molded product having a surface excellent in scratch resistance and impact resistance can be produced.

When the weight average molecular weight of the polyurethane is less than 2,000, the surface tack (surface adhesiveness) of the clear layer becomes strong and the operability is lowered. On the other hand, when the weight average molecular weight of polyurethane exceeds 150,000, the viscosity of the photocurable resin composition becomes high and it becomes difficult to apply. In addition, it is preferable that the weight average molecular weight of a polyurethane is 3,000-100,000 from a viewpoint of making scratch resistance, impact resistance, and three-dimensional moldability compatible suitably. In addition, the number average molecular weight and the weight average molecular weight in this specification are values in terms of polystyrene measured by gel permeation chromatography (GPC) unless otherwise specified. The molecular weight measurement conditions are as follows.
(1) Equipment: Product name “HLC-8020” (manufactured by Tosoh Corporation)
(2) Column: Trade names “TSKgel G2000HXL”, “G3000HXL”, “G4000GXL” (manufactured by Tosoh Corporation)
(3) Solvent: THF
(4) Flow rate: 1.0 ml / min
(5) Sample concentration: 2 g / L
(6) Injection volume: 100 μL
(7) Temperature: 40 ° C
(8) Detector: Model number “RI-8020” (manufactured by Tosoh Corporation)
(9) Standard material: TSK standard polystyrene (manufactured by Tosoh Corporation)

  The double bond equivalent of polyurethane is 130-1300 g / eq. It is preferable that it is 140-1200 g / eq. More preferably. When the double bond equivalent of polyurethane is within the above range, a clear layer excellent in scratch resistance, impact resistance, solvent resistance, and durability can be provided by ultraviolet curing. The polyurethane double bond equivalent was 130 g / eq. If it is less than this, the coating film after UV curing becomes brittle, or all the double bonds can no longer react, and the remaining double bonds tend to lower the weather resistance. On the other hand, the double bond equivalent of polyurethane is 1300 g / eq. If it exceeds 1, the crosslink density becomes low, the surface hardness is low, and the solvent resistance and durability tend to be inferior.

  The conditions for the polymerization reaction (urethanization reaction) for obtaining polyurethane are not particularly limited, and known conditions for urethanization may be applied. For example, first, a polymerization reaction (prepolymer reaction) is performed using monool (A), polyisocyanate (B), and polyol (D) to synthesize a prepolymer having an isocyanate group at its terminal. Next, the target polyurethane can be obtained by adding polyamine (C) to the prepolymer until there is no isocyanate group and reacting it (amine elongation reaction). The temperature (polymerization temperature) during the prepolymer reaction is usually 20 to 120 ° C, preferably 50 to 80 ° C. Moreover, the temperature (polymerization temperature) at the time of amine extension reaction is 0-50 degreeC normally, Preferably it is 10-50 degreeC.

  The polyol (D) having no (meth) acryloyloxy group is preferably used from the viewpoint of improving impact resistance and appropriately adjusting photoreactivity. In addition, when using the polyol (D) which does not have a (meth) acryloyloxy group, the (meth) acryloyl which occupies for the sum total of monool (A), polyisocyanate (B), polyamine (C), and polyol (D). The proportion of the polyol (D) having no oxy group is preferably 30% by mass or less, and more preferably 0.1 to 25% by mass. Curing formed by curing the clear layer because the content of (meth) acryloyloxy groups is relatively reduced when the proportion of polyol (D) not containing (meth) acryloyloxy groups exceeds 30% by mass. The hardness of the layer tends to decrease.

  As the polyol (D), a low molecular diol or a high molecular polyol can be used. Specific examples of the low molecular polyol include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol. And aliphatic glycols such as 3-methyl-1,5-pentanediol; and alicyclic glycols such as 1,4-bishydroxymethylcyclohexane and 2-methyl-1,1-cyclohexanedimethanol. it can. A monomer containing a hydroxyl group and an ethylenically unsaturated group can be used as the low molecular diol. These low molecular diols can be used alone or in combination of two or more.

Specific examples of the polymer polyol include those belonging to the following groups (1) to (6).
(1) Polyether polyols such as those obtained by polymerizing or copolymerizing alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) and / or heterocyclic ethers (tetrahydrofuran, etc.), specifically polyethylene glycol , Polypropylene glycol, polyethylene glycol-polytetramethylene glycol (block or random), polytetramethylene ether glycol, polyhexamethylene glycol and the like.

  (2) Polyester polyol, for example, aliphatic dicarboxylic acids (for example, succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.) and / or aromatic dicarboxylic acids (for example, isophthalic acid, terephthalic acid, etc.) And low molecular weight glycols (for example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, neopentyl glycol, 1,4-bis And the like, such as polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentyl adipate diol, polyethylene / butylene adipate diol, polyneo Pentyl / hexyl adipate diol, poly-3-methylpentane adipate diol, polybutylene isophthalate diol.

  (3) Polylactone polyol, such as polycaprolactone diol or triol, poly-3-methylvalerolactone diol, and the like.

  (4) Specific examples of polycarbonate polyol and polycarbonate polyol include polytrimethylene carbonate diol, polytetramethylene carbonate diol, polypentamethylene carbonate diol, polyneopentyl carbonate diol, polyhexamethylene carbonate diol, poly (1,4- Cyclohexane dimethylene carbonate) diol, polydecamethylene carbonate diol, and random / block copolymers thereof.

  (5) Polyolefin polyol, such as polybutadiene glycol, polyisoprene glycol, or a hydride thereof.

(6) Polymethacrylate polyol, for example, α, ω-polymethyl methacrylate diol, α, ω-polybutyl methacrylate diol, and the like.
However, from the viewpoint of durability and heat resistance, it is preferable to mainly use polycarbonate polyol.

  Specific examples of the polyisocyanate (B) include aliphatic polyisocyanates such as hexamethylene diisocyanate, trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, pentamethylene diisocyanate, and lysine diisocyanate; isophorone diisocyanate, 4,4′-methylene bis -Cycloaliphatic polyisocyanates such as cyclohexyl diisocyanate can be mentioned. As an isocyanate group containing acrylate monomer, the brand name "Laromer LR9000" (made by BASF) which is a polymer of 2-hydroxyethyl acrylate and hexamethylene diisocyanate can be mentioned. Since this product name “Laromer LR9000” has both an isocyanate group and an acryloyl group in the molecule, a monofunctional acryloyl group can be randomly introduced into the polyurethane molecule. That is, since the UV reactivity of the clear layer formed when combined with polyfunctional (meth) acrylate is improved, a hardened layer with high surface hardness can be formed. It is also effective in eliminating warping due to strain relaxation. These polyisocyanates can be used singly or in combination of two or more.

  Specific examples of the polyamine (C) include aliphatic diamines such as ethylenediamine, N-hydroxyethylethylenediamine, tetramethylenediamine, hexamethylenediamine, and diethylenetriamine; 4,4-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, 1, Cycloaliphatic diamines such as 3-bis (aminomethyl) cyclohexane and isophoronediamine; Hydrazines such as hydrazine, carbodihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, and phthalic acid dihydrazide; Polyamines containing unsaturated groups such as diallylamine compounds Can be mentioned. From the viewpoint of reducing the fluidity of the photocurable resin composition and reducing the surface tack, alicyclic diamines are particularly preferable. These polyamines (C) can be used singly or in combination of two or more.

  Any (meth) acrylate having a (meth) acryloyloxy group and containing one or two hydroxy groups at the terminal or side chain can be used as the monool (A) or polyol (D). The number of (meth) acryloyl groups (functional groups) in these molecules is preferably 1 or more, more preferably 3 or more, from the viewpoint of further improving the scratch resistance of the resulting decorative molded product. . These (meth) acrylates can be used as a chain extender or a terminal terminator for polyurethane. Specific examples include 2-hydroxylethyl acrylate, 2-hydroxylethyl methacrylate, 2-hydroxylpropyl acrylate, 2-hydroxylpropyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 2-hydroxy-3-phenoxy. Propyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-hydroxy-3-acryloyloxypropyl acrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol monoacrylate, glycerol Monomethacrylate, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, trimethylolprop Monoacrylate, trimethylolpropane monomethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetramethacrylate, pentaerythritol diacrylate, Examples include pentaerythritol dimethacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, 2-hydroxylbutyl acrylate, and 2-hydroxylbutyl methacrylate. These monools (A) and polyols (D) can be used singly or in combination of two or more.

  Specific examples of the monool (A) having no (meth) acryloyloxy group include methanol, ethanol, propanol, isopropyl alcohol and the like. These monools (A) may be used as a resin diluent or a reaction terminator.

  When the photocurable resin composition is an ultraviolet curable composition, it is preferable to further include a photopolymerization initiator in the photocurable resin composition. By including a photopolymerization initiator in the photocurable resin composition, the clear layer after three-dimensional molding can be more rapidly UV-cured. The amount of the photopolymerization initiator to be contained in the photocurable resin composition is preferably 0.01 to 10% by mass and preferably 0.1 to 5% by mass in 100% by mass of the photocurable resin composition. More preferably. In addition, when a photocurable resin composition is an electron beam (EB) hardening type composition, it is not necessary to make a photopolymerization initiator contain in a photocurable resin composition.

  As the photopolymerization initiator, conventionally known ones can be appropriately selected and used. Specific 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, and 2,2-dimethoxy-2-phenylacetophenone. 2,2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholino-propan-1-one, 4- (2-hydroxyethoxy) phenyl-2 (hydroxy-2-propyl) ketone, benzophenone, p-phenylbenzophenone, 4,4′-diethylamino Nzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2 , 4-diethylthioxanthone, benzyl dimethyl ketal, acetophenone dimethyl ketal and the like. The photocurable resin composition may further contain a photosensitizer such as p-dimethylbenzoic acid ester, tertiary amines, and thiol sensitizer. Moreover, it is preferable to add a polymerization inhibitor to the photocurable resin composition for the purpose of improving storage stability.

  The photocurable resin composition usually contains a solvent. The solvent is not particularly limited as long as it dissolves polyurethane. Specific examples of the solvent include a mixed solvent of an alcohol solvent such as methanol, ethanol, isopropanol, butanol, and octanol, and an ester solvent such as methyl acetate, ethyl acetate, and butyl acetate. It is preferable because it is good. Further, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, low molecular weight carbonate solvents such as dimethyl carbonate, and the like can be used.

  Various additives can be blended in the resin composition according to the physical properties to be applied to the cured layer formed by curing the clear layer with ultraviolet rays. Specific examples of additives include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, and a coupling agent. , Plasticizers, antifoaming agents, fillers, solvents, colorants and the like. In addition, as a weather resistance improving agent, hindered amine light stabilizers, such as HALS, an ultraviolet absorber, antioxidant, etc. can be used in the range which does not inhibit photocuring.

(Adhesive layer)
As a constituent material (binder resin) of the adhesive layer, a thermoplastic resin and a curable resin such as a thermosetting resin and an ultraviolet curable resin are used depending on the material of the member to which the functional molded sheet of the present invention is attached. Can be used. Specific examples of thermoplastic resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated or acid-modified polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins. And terpene resins. These thermoplastic resins can be used individually by 1 type or in combination of 2 or more types. Specific examples of the curable resin include a urethane resin, an acrylic resin, and an epoxy resin.

  Moreover, the resin layer to which the design was given can be made into an adhesive layer by giving a design to these resins using coloring agents, extender pigments, etc., such as a silica, an organic bead, a pigment, and dye. As colorants, inorganic pigments such as carbon black, iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine blue, cobalt blue; quinacridone red, isoindolinone yellow, phthalocyanine blue, etc. Organic pigments or dyes; metal pigments composed of scaly foil pieces such as aluminum and brass; nacreous (pearl) pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate can be used. Moreover, you may provide the metal thin film to which the design property was provided by carrying out vapor deposition, sputtering, foil transfer, etc. using aluminum, chromium, gold | metal | money, silver, copper, etc.

(Design layer)
Furthermore, it is also preferable to provide a design layer provided with a design similar to the design applied to the adhesive layer or another design between the adhesive layer and the clear layer for the purpose of providing a high degree of design. Examples of the material for forming such a design layer include the same materials as those for the adhesive layer.

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

(Production method of functional molded sheet)
Hereinafter, an example of a method for producing the functional molded sheet of the present invention will be described. First, a clear layer forming resin composition (hereinafter also referred to as “clear layer coating material”) is applied on the surface of a guard film serving as a base sheet by a normal coating method to form a coating layer. . Examples of methods for applying the clear layer coating on the surface of the guard film (printing method) include gravure coating, gravure reverse coating, gravure offset coating, spinner coating, roll coating, reverse roll coating, kiss coating, wheeler coating, and dip. The usual printing methods such as coating, solid coating with silk screen, wire bar coating, flow coating, comma coating, spray coating and the like can be mentioned. The drying temperature of the clear layer is usually 60 to 100 ° C, preferably 70 to 90 ° C. Further, it is possible to paint on the surface of the coating layer formed by obtaining the clear layer paint by an ink jet method. For painting, for example, UV curable ink-jet ink can be used. The UV curable ink-jet ink usually does not contain water or an organic solvent, and therefore does not require drying.

  Further, a design layer previously formed on the transfer sheet may be transferred onto the clear layer. At this time, in order to improve the adhesion between the design layer and the clear layer, a primer layer may be provided therebetween. In order to improve the designability of the design layer, a metal thin film or the like may be formed, or may be laminated to form a design layer having a multilayer 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, an adhesive layer coating material (adhesive layer resin composition) is applied to the formed clear layer or design layer by an ordinary coating method to form an adhesive layer. If the formed adhesive layer is dried, the adhesive layer can be formed. Examples of the method for applying the adhesive layer coating (coating method) include the same method as the method for applying the clear layer forming resin composition described above. The drying temperature of the adhesive layer coating is usually 60 to 100 ° C, preferably 70 to 90 ° C.

  If the separate film for protecting this contact bonding layer is stuck on the formed contact bonding layer, the functional molding sheet of this invention can be obtained.

(Decorated molding)
The decorative molded product of the present invention is obtained using the functional molded sheet of the present invention. That is, the decorative molded product of the present invention has a cured layer formed by curing the above-described clear layer with ultraviolet rays, and thus has excellent scratch resistance and impact resistance. In addition, the decorative molded product of this invention can be manufactured by using the above-mentioned functional molded sheet and performing general three-dimensional decorative molding (vacuum molding).

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified.

<Preparation of polyurethane (A)>
(Synthesis Example 1: Synthesis of polyurethane 1)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 400.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) and polyhexamethylene carbonate diol (trade name “Placcel CD220”) ", Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 3.0 g was charged. Next, 187 g of ethyl acetate was charged as a solvent. After the system became uniform, 61.9 g of hexamethylene diisocyanate (HDI) and 96.5 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 75 ° C. using dibutyltin laurate as a catalyst. For 4 hours to obtain a prepolymer. Next, the mixture was cooled to 30 ° C., diluted with 187 g of isopropyl alcohol, and 62.6 g of isophoronediamine was gradually added dropwise to eliminate 2,270 cm ⁻¹ absorption due to free isocyanate groups as measured by infrared absorption spectrum analysis. The reaction was allowed to proceed until Dilution was performed until the mass ratio of ethyl acetate and isopropyl alcohol was 1: 1 and the solid content was 40% to obtain a resin solution 1 containing polyurethane 1. The resulting resin solution 1 has a viscosity of 200 mPa · s / 20 ° C. and a double bond equivalent of 162 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 1 measured by GPC was 3900.

(Synthesis Example 2: Synthesis of Polyurethane 2)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 400.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) and polyhexamethylene carbonate diol (trade name “Placcel CD220”) ", Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 3.0 g was charged. Next, 174 g of ethyl acetate was charged as a solvent. After the system became uniform, 46.4 g of hexamethylene diisocyanate (HDI) and 72.4 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C., and 75 ° C. using dibutyltin laurate as a catalyst. For 4 hours to obtain a prepolymer. Next, the mixture was cooled to 30 ° C., diluted with 174 g of isopropyl alcohol, and 31.3 g of isophoronediamine was gradually added dropwise to eliminate 2,270 cm ⁻¹ absorption due to free isocyanate groups as measured by infrared absorption spectrum analysis. The reaction was allowed to proceed until Dilution was performed until the mass ratio of ethyl acetate to isopropyl alcohol was 1: 1 and the solid content was 40%, to obtain a resin solution 2 containing polyurethane 2. The obtained resin solution 2 has a viscosity of 160 mPa · s / 20 ° C. and a double bond equivalent of 145 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 2 measured by GPC was 3500.

(Synthesis Example 3: Synthesis of polyurethane 3)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 400.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) and polyhexamethylene carbonate diol (trade name “Placcel CD220”) 20.0 g of Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000). Next, 186 g of ethyl acetate was charged as a solvent. After the system became uniform, 63.3 g of hexamethylene diisocyanate (HDI) and 98.7 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 75 ° C. using dibutyltin laurate as a catalyst. For 4 hours to obtain a prepolymer. Next, the mixture was cooled to 30 ° C., diluted with 186 g of isopropyl alcohol, and 64.1 g of isophorone diamine was gradually added dropwise to eliminate 2,270 cm ⁻¹ absorption due to free isocyanate groups as measured by infrared absorption spectrum analysis. The reaction was allowed to proceed until Dilution was performed until the mass ratio of ethyl acetate and isopropyl alcohol was 1: 1 and the solid content was 40%, whereby a resin solution 3 containing polyurethane 3 was obtained. The obtained resin solution 3 had a viscosity of 280 mPa · s / 20 ° C. and a double bond equivalent of 168 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 3 measured by GPC was 4500.

(Synthesis Example 4: Synthesis of Polyurethane 4)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 400.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) and polyhexamethylene carbonate diol (trade name “Placcel CD220”) ", Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 3.0 g was charged. Next, 191 g of ethyl acetate was charged as a solvent. After the system became uniform, 61.9 g of hexamethylene diisocyanate (HDI), 86.9 g of 4,4′-methylenebis-cyclohexyl diisocyanate, and a polymer of 2-hydroxyethyl acrylate and hexamethylene diisocyanate at 50 ° C., Laromer 20.4 g of LR9000 (manufactured by BASF, both-end isocyanate prepolymer, NCO% = 15.1) was charged and reacted at 75 ° C. for 4 hours using dibutyltin laurate as a catalyst to obtain a prepolymer. Next, the mixture was cooled to 30 ° C., diluted with 191 g of isopropyl alcohol, and 62.6 g of isophoronediamine was gradually added dropwise to eliminate 2,270 cm ⁻¹ absorption due to free isocyanate groups as measured by infrared absorption spectrum analysis. The reaction was allowed to proceed until Dilution was performed until the mass ratio of ethyl acetate and isopropyl alcohol was 1: 1 and the solid content was 40%, whereby a resin solution 4 containing polyurethane 4 was obtained. The obtained resin solution 4 has a viscosity of 240 mPa · s / 20 ° C. and a double bond equivalent of 162 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 4 measured by GPC was 4000.

(Comparative Synthesis Example 1: Synthesis of polyurethane 5)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 400.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) was charged. Next, 186 g of ethyl acetate was charged as a solvent. After the system became uniform, 61.6 g of hexamethylene diisocyanate (HDI) and 96.1 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 75 ° C. using dibutyltin laurate as a catalyst. For 4 hours to obtain a prepolymer. Next, the mixture was cooled to 30 ° C., diluted with 186 g of isopropyl alcohol, 62.4 g of isophoronediamine was gradually added dropwise, and 2,270 cm ⁻¹ absorption due to free isocyanate groups measured by infrared absorption spectrum analysis disappeared. The reaction was allowed to proceed until Dilution was performed until the mass ratio of ethyl acetate and isopropyl alcohol was 1: 1 and the solid content was 40% to obtain a resin solution 5 containing polyurethane 5. The resulting resin solution 5 has a viscosity of 200 mPa · s / 20 ° C. and a double bond equivalent of 161 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 5 measured by GPC was 3800.

(Comparative Synthesis Example 2: Synthesis of polyurethane 6)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 400.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) and polyhexamethylene carbonate diol (trade name “Placcel CD220”) ", Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 3.0 g was charged. Next, 170 g of ethyl acetate was charged as a solvent. After the system became uniform, 37.1 g of hexamethylene diisocyanate (HDI) and 57.7 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 75 ° C. using dibutyltin laurate as a catalyst. For 4 hours to obtain a prepolymer. Next, the mixture was cooled to 30 ° C., diluted with 170 g of isopropyl alcohol, and 12.5 g of isophoronediamine was gradually added dropwise to eliminate 2,270 cm ⁻¹ absorption due to free isocyanate groups measured by infrared absorption spectrum analysis. The reaction was allowed to proceed until Dilution was carried out until the mass ratio of ethyl acetate and isopropyl alcohol was 1: 1 and the solid content was 40%, whereby a resin solution 6 containing polyurethane 6 was obtained. The obtained resin solution 6 had a viscosity of 60 mPa · s / 20 ° C. and a double bond equivalent of 133 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 6 measured by GPC was 1800.

(Comparative Synthesis Example 3: Synthesis of polyurethane 7)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 400 g of a compound containing a hydroxyl group and a methacrylooxy group (epoxy ester 40EM, manufactured by Kyoeisha Chemical Co., Ltd., molecular weight 346), polyhexamethylene carbonate diol (trade name “Placcel CD220”, 3.0 g of Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group quantification = 2,000) was charged. Next, 251 g of ethyl acetate was charged as a solvent. After the system became uniform, 272.3 g of hexamethylene diisocyanate (HDI) was charged at 50 ° C. and reacted at 75 ° C. for 4 hours using dibutyltin laurate as a catalyst to obtain a prepolymer. Next, the mixture was cooled to 30 ° C., diluted with 251 g of isopropyl alcohol, and 78.7 g of isophorone diamine was gradually added dropwise to eliminate 2,270 cm ⁻¹ absorption due to free isocyanate groups as measured by infrared absorption spectrum analysis. The reaction was allowed to proceed until Dilution was performed until the mass ratio of ethyl acetate to isopropyl alcohol was 1: 1 and the solid content was 40%, whereby a resin solution 7 containing polyurethane 7 was obtained. The obtained resin solution 6 had a viscosity of 160 dPa · s / 20 ° C. and a double bond equivalent of 327 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 7 measured by GPC was 15,000. In addition, the structure of the compound (epoxy ester 40EM) containing the used hydroxyl group and methacrylooxy group is shown below.

(Comparative Synthesis Example 4: Synthesis of polyurethane 8)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, 400.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) and polyhexamethylene carbonate diol (trade name “Placcel CD220”) ", Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 3.0 g was charged. Next, 186 g of ethyl acetate was charged as a solvent. After the system became uniform, 61.9 g of hexamethylene diisocyanate (HDI) and 96.5 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 75 ° C. using dibutyltin laurate as a catalyst. For 4 hours to obtain a prepolymer. Subsequently, the mixture was cooled to 30 ° C., diluted with 186 g of isopropyl alcohol, and 18.8 g (30% of equivalent) of isophorone diamine was gradually added dropwise. Then, it diluted until solid content became 40%, and the resin solution 8 containing the polyurethane 8 was obtained. The obtained resin solution 8 had a viscosity of 45 mPa · s / 20 ° C. and a double bond equivalent of 148 g / eq. Met. The weight average molecular weight of polyurethane 8 measured by GPC was 1500.

  Table 1 shows the composition (composition) of each component used in the above synthesis examples, the weight average molecular weight and the double bond equivalent of each obtained polyurethane.

<Preparation of clear layer coating>
(Clear layer paint 1)
To 100 g of the resin solution 1 obtained in Synthesis Example 1, 2 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) is blended, and ethyl acetate and isopropanol are blended at a mass ratio of 1: 1. Thus, a clear layer coating material 1 having a solid content of 40% was obtained.

(Clear layer paint 2)
2 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) is blended with 100 g of the resin solution 2 obtained in Synthesis Example 2, and ethyl acetate and isopropanol are blended at a mass ratio of 1: 1. Thus, a clear layer coating material 2 having a solid content of 40% was obtained.

(Clear layer paint 3)
To 100 g of the resin solution 3 obtained in Synthesis Example 3, 2 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) is blended, and ethyl acetate and isopropanol are blended at a mass ratio of 1: 1. Thus, a clear layer coating material 3 having a solid content of 40% was obtained.

(Clear layer paint 4)
To 100 g of the resin solution 4 obtained in Synthesis Example 4, 2 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) is blended, and ethyl acetate and isopropanol are blended at a mass ratio of 1: 1. Thus, a clear layer coating material 4 having a solid content of 40% was obtained.

(Comparative clear layer paint 1)
2 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) is blended with 100 g of the resin solution 5 obtained in Comparative Synthesis Example 1, and ethyl acetate and isopropanol are blended at a mass ratio of 1: 1. Thus, a comparative clear layer coating material 1 having a solid content of 40% was obtained.

(Comparison for clear layer 2)
2 g of photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) is blended with 100 g of the resin solution 6 obtained in Comparative Synthesis Example 2, and ethyl acetate and isopropanol are blended at a mass ratio of 1: 1. Thus, a comparative clear layer coating material 2 having a solid content of 40% was obtained.

(Comparison for clear layer 3)
2 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) is blended with 100 g of the resin solution 7 obtained in Comparative Synthesis Example 3, and ethyl acetate and isopropanol are blended at a mass ratio of 1: 1. Thus, a comparative clear layer coating material 3 having a solid content of 40% was obtained.

(Comparison for clear layer 4)
2 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) is blended with 100 g of the resin solution 8 obtained in Comparative Synthesis Example 4, and ethyl acetate and isopropanol are blended at a mass ratio of 1: 1. Thus, a comparative clear layer coating material 4 having a solid content of 40% was obtained.

  Table 2 shows the composition of each component used in preparing the clear layer coating composition.

<Preparation of resin composition for adhesive layer>
(Adhesive layer resin composition 1)
A modified polyolefin (trade name "Aurolen 150S", manufactured by Nippon Paper Chemicals Co., Ltd.) is dissolved in a mixed solvent containing methylcyclohexane and MEK at a mass ratio of 9: 1 to obtain a solid content of 15%. Resin composition 1 was obtained.

(Adhesive layer resin composition 2)
Adhesive layer resin composition 1 20.0 g of black pigment dispersion colorant (trade name “Seika Seven SS01-323 Black”, manufactured by Dainichi Seika Kogyo Co., Ltd., solid content 25%, solvent: MEK, pigment: carbon black) As a solvent, MEK and cyclohexanone were blended at a mass ratio of 1: 1 to obtain a resin composition 2 for an adhesive layer having a solid content of 30%.

(Adhesive layer resin composition 3)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen blowing tube, and a manhole was prepared. While replacing the interior of the reaction vessel with nitrogen, polyhexamethylene carbonate diol (trade name “Placcel CD220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 400.0 g, 1,4 -Butanediol 10.0 g was charged. Next, 118 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became uniform, 62.2 g of isophorone diisocyanate was charged at 50 ° C. and reacted at 80 ° C. using dibutyltin laurate as a catalyst. The viscosity of the reaction solution was adjusted by solvent dilution, and the reaction was allowed to proceed until 2,270 cm ⁻¹ absorption due to free isocyanate groups measured by infrared absorption spectrum analysis disappeared. Cyclohexanone was added until the mass ratio of MEK to cyclohexanone was 1: 1 to obtain a resin composition 3 for an adhesive layer containing polyurethane. The obtained resin composition 3 for an adhesive layer had a viscosity of 610 dPa · s / 20 ° C. and a solid content of 55%. Moreover, the weight average molecular weight measured by GPC of the polyurethane contained in the resin composition 3 for the adhesive layer was 21,000.

(Adhesive layer resin composition 4)
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 methyl ethyl ketone (MEK) and 50.0 g of methyl methacrylate were charged and heated to 60 ° C. in a nitrogen atmosphere. A mixture of 50.0 g of butyl acrylate and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was prepared. Half of the mixture was added to the reaction vessel, and the other half was dropped into the reaction vessel with a dropping funnel over 1 hour. After dripping, it was made to react for 6 hours as it was, and the resin composition 4 for contact bonding layers which consists of an acrylic polymer was obtained. The obtained adhesive layer resin composition 4 had a viscosity of 80 dPa · s / 20 ° C. and a solid content of 55%. Moreover, the weight average molecular weight measured by GPC of the acrylic polymer contained in the resin composition 4 for adhesive layers was 35,000.

<Production of functional molded sheet>
Example 1
As a guard film to be a base sheet, an amorphous PET film having a thickness of 200 μm (trade name “Novaclear”, manufactured by Mitsubishi Chemical Corporation) was prepared. The surface of the guard film was coated with the clear layer coating 1 with a bar coater and then dried at 90 ° C. for 2 minutes to form a clear layer having a thickness of 15 μm. The adhesive layer resin composition 2 was applied to the surface of the formed clear layer with a bar coater and dried at 90 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. A separate film (PET film having a thickness of 80 μm) was stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 1).

(Example 2)
As a guard film to be a base sheet, an amorphous PET film having a thickness of 200 μm (trade name “Novaclear”, manufactured by Mitsubishi Chemical Corporation) was prepared. The surface of the guard film was coated with the clear layer coating 1 with a bar coater and then dried at 90 ° C. for 2 minutes to form a clear layer having a thickness of 15 μm. A UV ink containing a UV-reactive monomer, a pigment, and an initiator was applied to the surface of the formed clear layer using a UV inkjet printer, and a design was printed to form a design layer. The adhesive layer resin composition 2 was applied to the surface of the formed design layer with a bar coater and dried at 90 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. A separate film (PET film having a thickness of 80 μm) was stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 2).

Example 3
As a guard film to be a base sheet, an amorphous PET film having a thickness of 200 μm (trade name “Novaclear”, manufactured by Mitsubishi Chemical Corporation) was prepared. The surface of the guard film was coated with the clear layer coating 1 with a bar coater and then dried at 90 ° C. for 2 minutes to form a clear layer having a thickness of 15 μm. A design layer made of an aluminum thin film was formed on the surface of the formed clear layer by vapor deposition. The adhesive layer resin composition 2 was applied to the surface of the formed design layer with a bar coater and dried at 90 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. A separate film (PET film having a thickness of 80 μm) was stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 3).

(Examples 4-9 and Comparative Examples 1-4)
Functional molded sheets (Examples 4 to 9 and Examples 4 and 9), except that the clear layer was formed using the clear layer paint or comparative clear layer paint shown in Table 1. Comparative Examples 1 to 4) were obtained.

<Production of decorative molded products>
Using a vacuum molding machine (trade name “NGF-0404-S”, manufactured by Fuse Vacuum Co., Ltd.), the surface of the decorated member (thickness 3.5 mm) made of PP resin heated to 80 ° C. is heated to 100 ° C. The heated functional molded sheets of Examples 1 to 9 and Comparative Examples 1 to 3 were each stuck by vacuum molding. Using a UV irradiator (trade name “UNICURE UVC-02512S1AA01”, manufactured by USHIO INC.), The functional molded sheet affixed to the surface of the member was irradiated with UV so that the accumulated light amount was 2000 mJ / cm ^2. The clear layer was cured to form a cured layer to obtain a decorative molded product.

<Evaluation method>
(1) Three-dimensional formability (vacuum formability)
The appearance of the decorative molded product produced using the functional molded sheet (before UV curing) was observed, and the three-dimensional moldability (vacuum moldability) was evaluated according to the evaluation criteria shown below. The results are shown in Table 3.
A: No cracking or whitening of the coating layer was observed in the clear layer and the design layer, and the shape of the mold was satisfactorily followed.
○: Fine coating cracking or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion, but it was at a level causing no problem in practice.
Δ: Slight coating cracking or whitening was observed in a part of the three-dimensional shape portion or the maximum stretched portion.
X: The clear layer and the design layer could not follow the shape of the mold, and cracking of the coating film or whitening was observed.

(2) Blocking resistance The clear layer coating material and the comparative clear layer coating material were each coated on a PET film so as to have a dry film thickness of about 30 μm to form a clear layer. An untreated PET film was overlaid on the formed clear layer and cut into a 7 × 7 cm square to prepare a sample. The prepared sample was sandwiched between glass plates and stored at 45 ° C. for one day under a load of 20 kg / 49 cm ² . After cooling to 25 ° C., the untreated PET film was peeled off. The clear layer was visually observed, and blocking resistance was evaluated according to the following evaluation criteria. The results are shown in Table 3.
○: No significant change occurred in the clear layer.
X: Breaking or cracking occurred in the clear layer due to blocking.

(3) Pencil Hardness Based on JIS K5400, the pencil hardness of the surface (ultraviolet-cured cured layer) of the produced decorative molded product was measured under the condition of a load of 500 g. The results are shown in Table 3.

(4) Solvent resistance Using an absorbent cotton containing xylene, observe the appearance after rubbing the surface (cured layer after UV curing) of the produced decorative molded product 50 times with a load of 50 g / cm ^2. The solvent resistance was evaluated according to the following evaluation criteria. The results are shown in Table 3.
○: No significant change was observed in the cured layer.
X: Swelling or peeling of the cured layer was observed.

(5) Impact resistance The appearance of a steel ball having a weight of 500 g dropped from a height of 35 cm on the surface (cured layer after UV curing) of the produced decorative molded product was observed, and the following evaluations were made. Impact resistance was evaluated according to standards. The results are shown in Table 3.
○: No crack was observed in the cured layer.
X: Cracks were observed in the cured layer.

(6) Heat resistance The produced decorative molded product (ultraviolet-cured) was put in an oven, and a heat resistance test was carried out at 120 ° C for 400 hours. The appearance of the cured layer after the test was observed, and the heat resistance was evaluated according to the evaluation criteria shown below. The results are shown in Table 3.
○: No yellowing, choking, cracking, cracking or the like occurred in the cured layer.
X: Yellowing, choking, cracking, cracking, etc. occurred in the cured layer.

(7) Hydrolysis resistance The produced decorative molded product (ultraviolet-cured) was put into a hydrolysis tank, and a hydrolysis resistance test was performed for 20 weeks at 70 ° C / 95% RH. The appearance of the cured layer after the test was observed, and the hydrolysis resistance was evaluated according to the following evaluation criteria. The results are shown in Table 3.
◯: No cracking or cracking occurred in the cured layer.
X: Cracks, cracks, etc. occurred in the cured layer.

  As is clear from the results shown in Table 3, the functional molded sheets of Examples 1 to 9 had good three-dimensional moldability without generating cracks or cracks. Furthermore, the decorative molded products obtained using the functional molded sheets of Examples 1 to 9 are excellent in scratch resistance, impact resistance, solvent resistance, light resistance, heat resistance, and hydrolysis resistance. It was confirmed that

  The highly durable functional molded sheet of the present invention includes, for example, interior materials or exterior materials for vehicles such as automobiles; housings for home appliances such as televisions, personal computers, and mobile phones; interior materials for buildings such as walls, floors, and ceilings. It is suitably used as a material for producing a decorative molded product such as a container.

1: Guard film 2: Clear layer 3: Design layer 4: Adhesive layer 5: Separate film 10: High durability functional molded sheet

Claims (10)

A guard film, a clear layer, and an adhesive layer are laminated in this order, and if necessary, a separate film is disposed on the surface of the adhesive layer,
A polyurethane resin represented by the following general formula (1), wherein the clear layer is obtained by reacting monool (A), polyisocyanate (B), polyamine (C), and polyol (D) as essential components. It consists of a photocurable resin composition that contains,
Ratio of the number of moles of isocyanate groups of the polyisocyanate (B) to the total number of moles of hydroxyl groups of the monool (A) and the number of moles of hydroxyl groups of the polyol (D) ((B) / ((A) + (D))) is 1.5 to 3, and the number of moles of hydroxyl groups of the monool (A) relative to the number of moles of isocyanate groups of the polyisocyanate (B), the number of amino groups of the polyamine (C) The ratio of the number of moles and the total number of moles of hydroxyl groups of the polyol (D) (((A) + (C) + (D)) / (B)) is 0.7 to 1.0,
At least one of the monool (A) and the polyol (D) has a (meth) acryloyloxy group, and the monool (A), the polyisocyanate (B), the polyamine (C), and the polyol The proportion of (D) in the polyol having no (meth) acryloyloxy group in the total of (D) is 30% by mass or less,
A highly durable functional molded sheet, wherein the polyurethane resin has a weight average molecular weight of 2,000 to 150,000.

(In the general formula (1), R ₁ represents a monool residue, R ₂ represents a polyisocyanate residue, R ₃ represents a polyamine residue, R ₄ represents a polyol residue, m and n Indicates the number of repetitions)   The highly durable functional molded sheet according to claim 1, wherein the polyisocyanate (B) is a polyisocyanate having a (meth) acryloyloxy group.   The highly durable functional molded sheet according to claim 1 or 2, wherein the polyol (D) is a polycarbonate polyol.   The double bond equivalent of the polyurethane resin is 130-1300 g / eq. The highly durable functional molded sheet according to any one of claims 1 to 3.   The highly durable functional molding sheet as described in any one of Claims 1-4 in which the said photocurable resin composition contains 0.01-10 mass% of photoinitiators further.   The highly durable functional molded sheet according to any one of claims 1 to 5, wherein a design is applied to the adhesive layer.   The highly durable functional molded sheet according to any one of claims 1 to 6, wherein the adhesive layer is a resin layer provided with a design. The adhesive layer is an acrylic resin, an acrylic modified polyolefin resin, a chlorinated or acid modified polyolefin resin, a vinyl chloride-vinyl acetate copolymer, a thermoplastic urethane resin, a thermoplastic polyester resin, a polyamide resin, a rubber resin, and a terpene system. Contains at least one thermoplastic resin selected from the group consisting of resins, or
The highly durable functional molding sheet as described in any one of Claims 1-7 containing the thermosetting resin of at least any one of a urethane resin and an epoxy resin.   The highly durable functional molded sheet according to any one of claims 1 to 8, wherein a design layer is disposed between the adhesive layer and the clear layer.   A decorative molded product having a cured layer formed by UV-curing the clear layer, obtained using the highly durable functional molded sheet according to any one of claims 1 to 9.

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