JP5889179B2 - Manufacturing method of decorative molded products - Google Patents

Description

The present invention relates to decorative molding manufacturing how to use a highly durable functional molded sheet.

  Conventionally, as a method of obtaining a decorative molded product, an in-mold molding method in which a resin is injection-molded and transferred to a resin surface on which a decorative film is molded has been performed. According to this in-mold molding method, not only scratch resistance but also design properties are given to resin molded products such as portable information terminals such as mobile phones, personal computers, home appliances, and vehicle interior / exterior parts. can do.

  In-mold molding methods are roughly classified into an in-mold transfer (IMD) method and an in-mold lamination (IML) method. In the IMD method, a decorative film in which a base material sheet, a skin layer for imparting scratch resistance, a design layer, and an adhesive layer are laminated is placed in a mold for injection molding. This is a decoration method in which a design layer, an adhesive layer and the like are transferred to the surface of a molded product. In the case of this IMD method, the skin layer and the base sheet constituting the decorative film are finally peeled off and do not remain on the surface of the resulting decorative molded product.

  In addition, the IML method uses a decorative film in which a skin layer is formed on one surface of a base sheet, an adhesive layer is formed on the other surface, and a design layer is provided on the surface of either layer. This is a decoration method in which a skin layer, a base sheet, and an adhesive layer are placed on the surface of a molded product at the same time as injection molding. A film insert molding method is similar to the IML method. In this film insert molding method, a pre-molded product obtained by molding a heated decorative film by press molding or vacuum / pneumatic molding is placed in a mold for injection molding, and the pre-molded product and a resin molded product are formed by injection molding. This is a method of bonding objects together. In the IML method and the film insert molding method, the skin layer, the base material sheet, and the adhesive layer are integrated with the resin molded product, so that a deep-drawn decorative molded product can be manufactured as compared with the IMD method.

  In the in-mold molding method, since the resin in a high temperature and high pressure state is injected and pushed into a mold having a decorative film disposed therein, the followability of the decorative film to the resin surface is good. However, the decorative film is required to have heat resistance that can withstand the molding temperature (120 to 250 ° C.) of the in-mold molding method. In addition, if the elongation at the time of molding is insufficient, it becomes impossible to follow the three-dimensional shape of the molded resin, so that cracking may easily occur.

  Further, in order to impart scratch resistance to the surface of the molded resin, the decorative film is provided with a skin layer having a high surface hardness (pencil hardness). However, since the surface hardness of the skin layer and the three-dimensional formability of the decorative film are in a trade-off relationship, it is generally difficult to achieve both of these characteristics.

  On the other hand, in order to follow the elongation at the time of molding, the skin layer is formed of an ultraviolet curable uncured resin, and after molding, the skin layer is cured by irradiating with ultraviolet rays, so that moldability and scratch resistance are achieved. 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 skin layer by irradiating ultraviolet rays is known (Patent Document 1). However, if the skin layer is excessively hardened, it is difficult to control because it is difficult to follow the elongation at the time of molding and a problem such as cracking occurs easily.

Japanese Patent Application Laid-Open No. 6-134859

The present invention has been made in view of such problems of the prior art, and the subject is a decorative molded product having a complex surface shape and a surface excellent in scratch resistance. the invention is to provide a manufacturing how the decorated molded article that can be easily manufactured.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors contain a polycarbonate-based polyurethane (A) containing a (meth) acryloyloxy group and a non-yellowing polyisocyanate (B) as a crosslinking agent in a predetermined ratio. The above-mentioned problem can be achieved by using a highly durable functional sheet having a skin layer formed from a reaction cured product of the resin composition to be cured and irradiating ultraviolet rays after in-mold molding to cure the skin layer. As a result, the present invention has been completed.

That is, according to this invention, the manufacturing method of the decorative molded product shown below is provided.
[1] Injecting a raw material resin into the mold in a state where a highly durable functional molded sheet having a laminated structure including an adhesive layer, a design layer, a skin layer, and a base sheet is placed in an injection mold An injection molding step, and a cured layer forming step of curing the skin layer by irradiating ultraviolet rays to form a cured layer, and the following conditions (1) to ( 3) A method for producing a decorative molded product using a material satisfying the above requirements.
(1) The skin layer has a double bond equivalent containing a (meth) acryloyloxy group of 160 to 3000 g / eq. Polycarbonate-based polyurethane (A), and comprises a reaction cured product of the resin composition containing a non-yellowing polyisocyanate of the 2 to 25 wt% of the polycarbonate-based polyurethane (A) (B).
(2) The breaking elongation at 80 ° C. of the skin layer is 250% or more.
(3) The pencil hardness at a load of 500 g measured according to JIS K5400 of the cured layer formed by ultraviolet curing the skin layer is 3B or more.
[2] In the above [1], the non-yellowing polyisocyanate (B) is at least one polyfunctional isocyanate compound selected from the group consisting of an isocyanurate body, a burette body, an adduct body, and a polymer body. The manufacturing method of the decorative molded product of description.
[ 3 ] In the high durability functional molded sheet, the adhesive layer, the skin layer, and the base material sheet are laminated in this order, and adjacent to at least one of the adhesive layer and the skin layer, A design layer is disposed, and at the time of injection molding, a transfer layer composed of the adhesive layer, the skin layer, and the design layer is transferred to a molded product composed of the raw material resin to add design properties. The method for producing a decorative molded product according to [1] or [2] , wherein a decorative molded product is obtained.
[ 4 ] The high durability functional molded sheet is formed by laminating the adhesive layer, the base sheet, and the skin layer in this order, and at least one of the adhesive layer, the base sheet, and the skin layer. The design layer is arranged adjacent to the crucible, and at the time of injection molding, the adhesive layer, the base sheet, the skin layer, and the insert layer composed of the design layer are formed into the molded product composed of the raw material resin. The method for producing a decorative molded product according to [1] or [2] , wherein the decorative molded product to which a design property is imparted is obtained by transferring .
[ 5] The method for producing a decorative molded product according to any one of [1] to [4], wherein the polycarbonate-based polyurethane (A) contains 0.1 to 70% by mass of a structural unit derived from a polycarbonate polyol. .
[6] The additive according to any one of [1] to [5], wherein the polycarbonate-based polyurethane (A) contains 0.1 to 30% by mass of a structural unit derived from polysiloxane having an active hydrogen-containing group. A method for producing decorative molded products.
[7] The method for producing a decorative molded product according to any one of [1] to [6], wherein the polycarbonate-based polyurethane (A) further contains 0.01 to 10% by mass of a photopolymerization initiator.
[8] The method for producing a decorative molded product according to any one of [1] to [7], wherein the design layer is a resin layer or a metal thin film to which a design is applied.
[9] The method for producing a decorative molded product according to any one of [1] to [8], wherein an uneven pattern is formed on the surface of the skin layer.
[10] The decorative molded product according to any one of [1] to [9], wherein the adhesive layer includes at least one selected from the group consisting of a urethane resin, a modified olefin resin, and an acrylic resin. Manufacturing method.

According to the method for producing a decorative molded product of the present invention, a decorative molded product having a complicated surface shape and a surface excellent in scratch resistance can be easily produced .

It is sectional drawing which shows typically the 1st example of the highly durable functional molding sheet used for the manufacturing method of the decorative molded product of this invention. It is sectional drawing which shows typically the 2nd example of the highly durable functional molding sheet used for the manufacturing method of the decorative molded product of this invention.

(Method for manufacturing decorative molded products)
The manufacturing method of the decorative molded product of this invention has an injection molding process and a hardened layer formation process. The injection molding step is a step of injecting the raw material resin into the mold in a state where the highly durable functional molding sheet is disposed in the mold for injection molding. Moreover, a hardened layer formation process is a process of irradiating an ultraviolet-ray and hardening the skin layer of a highly durable functional molding sheet, and forming a hardened layer. And in the manufacturing method of the decorative molded product of this invention, the highly durable functional molding sheet which satisfy | fills the following conditions (1)-(3) is used. Hereinafter, the detail of the manufacturing method of the decorative molded product of this invention is demonstrated.
(1) The skin layer contains a polycarbonate-based polyurethane (A) containing a (meth) acryloyloxy group and 2 to 25% by mass of a non-yellowing polyisocyanate (B) based on the polycarbonate-based polyurethane (A). It consists of a reaction cured product of the resin composition.
(2) The elongation at break of the skin layer at 80 ° C. is 250% or more.
(3) The pencil hardness at a load of 500 g measured according to JIS K5400 of a cured layer formed by ultraviolet curing the skin layer is 3B or more.

  FIG. 1 is a cross-sectional view schematically showing a first example of a highly durable functional molded sheet used in the method for producing a decorative molded product of the present invention. A high durability functional molded sheet (hereinafter, also simply referred to as “functional molded sheet”) 10 shown in FIG. 1 includes an adhesive layer 4, a design layer 3, a skin layer 1, and a base sheet 2 laminated in this order. Yes. The skin layer 1 is a layer having scratch resistance. A separate film 5 may be disposed on the surface of the adhesive layer 4.

  In the injection molding process, the raw material resin is injected into the mold in a state where the functional molding sheet is disposed in the mold for injection molding. When the functional molded sheet 10 having the configuration shown in FIG. 1 is used, the transfer layer 6 composed of the adhesive layer 4, the skin layer 1, and the design layer 3 is transferred to a molded product made of a raw material resin during injection molding. (IMD method). The base sheet 2 is not transferred to the molded product. Even if a long functional molding sheet is intermittently inserted into the mold for the required length, the functional molding sheets that have been cut into the required length are inserted one by one into the mold. May be.

  FIG. 2 is a cross-sectional view schematically showing a second example of a highly durable functional molded sheet used in the method for producing a decorative molded product of the present invention. As for the highly durable functional molding sheet 20 shown in FIG. 2, the contact bonding layer 14, the design layer 13, the base material sheet 12, and the skin layer 11 are laminated | stacked in this order. The skin layer 11 is a layer having scratch resistance. A separate film 15 may be disposed on the surface of the adhesive layer 14 (the surface opposite to the design layer).

  When the functional molded sheet 20 having the configuration shown in FIG. 2 is used in the injection molding process, the insert layer 7 including the adhesive layer 14, the base sheet 12, the skin layer 11, and the design layer 13 is used during the injection molding. Is transferred to a molded product made of a raw material resin, and the molded product and the insert layer 7 are integrated (IML method). Even if a long functional molding sheet is intermittently inserted into the mold for the required length, the functional molding sheets that have been cut into the required length are inserted one by one into the mold. May be.

  In the cured layer forming step, the molded product obtained by transferring the transfer layer or the insert layer obtained by the injection molding step is irradiated with ultraviolet rays. By irradiating with ultraviolet rays, the cured product constituting the skin layer is further crosslinked. For this reason, the hardness of an outer skin layer improves and the decorative molded product (surface layer) excellent in abrasion resistance can be obtained.

(High durability functional molded sheet)
The highly durable functional molded sheet used in the method for producing a decorative molded product of the present invention has a laminated structure including an adhesive layer, a design layer, a skin layer, and a substrate sheet. Details of each layer will be described below.

(Skin layer)
The skin layer constituting the functional molded sheet used in the method for producing a decorative molded product of the present invention has a breaking elongation at 80 ° C. (hereinafter also referred to as “80 ° C. breaking elongation”) of 250% or more, preferably 300. % Or more. In other words, the functional molded sheet used in the present invention has a sufficiently high 80 ° C. breaking elongation of the skin layer, and therefore has a superior three-dimensional formability, such that cracks and the like hardly occur during three-dimensional molding. The upper limit of the 80 ° C. breaking elongation of the skin layer is not particularly limited, but is substantially 1000% or less.

  Moreover, the pencil hardness in the load 500g measured based on JISK5400 of the hardened layer formed by carrying out the ultraviolet curing of the skin layer of a highly durable functional molding sheet is 3B or more, Preferably it is 2B or more. That is, the functional molded sheet used in the present invention has a sufficiently high cured layer formed by curing the skin layer with ultraviolet rays, so that a decorative molded product having a surface excellent in scratch resistance can be produced. Furthermore, the 80 ° C. breaking elongation of the skin layer before UV curing is sufficiently high as described above. That is, the functional molded sheet used in the present invention is sufficiently cured after ultraviolet irradiation while its skin layer has excellent three-dimensional moldability before ultraviolet irradiation. For this reason, according to the manufacturing method of the decorative molded product of this invention, the decorative molded product which has the surface excellent in abrasion resistance can be manufactured simply, 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 4H or less substantially.

  The skin layer is formed by a reaction cured product of the resin composition. This resin composition contains a polycarbonate-based polyurethane (hereinafter simply referred to as “polycarbonate-based polyurethane” or “polyurethane”) (A) containing a (meth) acryloyloxy group, and a non-yellowing polyisocyanate (B). To do. And the quantity of the non-yellowing polyisocyanate (B) in a resin composition is 2-25 mass% when the quantity of a polyurethane (A) is 100 mass%, Preferably it is 3-15 mass%. is there. When the amount of the non-yellowing polyisocyanate (B) exceeds 25% by mass, the elongation at the time of molding cannot be followed and cracking may occur. On the other hand, when the amount of the non-yellowing polyisocyanate (B) is less than 2% by mass, the skin layer becomes tacky, so that it is necessary to dispose a protective film from the viewpoint of preventing contamination and the like and formed by ultraviolet curing. Scratch resistance and chemical resistance of the cured layer (surface layer) to be formed become insufficient.

The weight average molecular weight of the polyurethane (A) is preferably 1,000 or more, and more preferably 2,000 or more. By using the polyurethane (A) having a weight average molecular weight of 1,000 or more, a three-dimensional moldability can be further improved, and a decorative molded product having an excellent surface due to scratch resistance can be produced. When the weight average molecular weight of the polyurethane (A) is less than 1,000, the surface adhesiveness of the skin layer becomes strong and the operability tends to be lowered. On the other hand, when the weight average molecular weight of the polyurethane (A) exceeds 150,000, the viscosity of the resin composition increases and it tends to be difficult to apply. In addition, it is particularly preferable that the weight average molecular weight of the polyurethane (A) is 3,000 to 100,000 from the viewpoint of more suitably achieving both scratch resistance and three-dimensional moldability. 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: differential refractometer (model number “RI-8020”, manufactured by Tosoh Corporation)
(9) Standard material: TSK standard polystyrene (manufactured by Tosoh Corporation)

  The double bond equivalent of the polyurethane (A) is 160 to 3000 g / eq. It is preferable that it is 180-2500 g / eq. More preferably. When the double bond equivalent of the polyurethane (A) is within the above range, a skin layer having excellent solvent resistance and durability can be provided by ultraviolet curing. In addition, the double bond equivalent of polyurethane (A) is 160 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 (A) is 3000 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.

  Polyurethane (A) is, for example, polycarbonate polyol (V) having a carbonate bond in the polymer main chain, chain extender (low molecular diol) (W), diisocyanate (X), and 1 to 2 terminals or side chains. It can be produced by polymerizing a (meth) acrylate (Y) containing a hydroxy group. Further, if necessary, polysiloxane (Z) having an active hydrogen-containing group such as an amino group or a hydroxy group may be further polymerized.

  The conditions for the polymerization reaction (urethanization reaction) are not particularly limited, and normal urethanization reaction conditions can be applied. For example, the number of functional groups of diisocyanate (X) and the sum of the functional groups of polycarbonate polyol (V), low molecular diol (W), (meth) acrylate (Y), and polysiloxane (Z), which are active hydrogen-containing compounds, The polymerization reaction is carried out at an equivalent ratio of about 1.0. Moreover, you may make it react by any system of a one-shot method and a multistage method. The temperature of the polymerization reaction is usually 20 to 150 ° C, preferably 60 to 110 ° C. And the target polyurethane (A) can be obtained by making it polymerize until there is almost no isocyanate group.

  As the polycarbonate polyol (V), it is preferable to mainly use polycarbonate diol from the viewpoint of urethane synthesis. This is because when a polyfunctional polycarbonate polyol is used, gelation or the like may occur during the polymerization reaction. The proportion of the structural unit derived from the polycarbonate polyol (V) in the polycarbonate-based polyurethane (A) is preferably 0.1 to 70% by mass, and more preferably 10 to 60% by mass. The structural unit derived from each of low molecular diol (W), diisocyanate (X), and (meth) acrylate (Y) as the ratio of the structural unit derived from polycarbonate polyol (V) is less than 0.1 mass%. The content ratio of increases relatively. When the content ratio of these structural units is large, the formed skin layer tends to be brittle. For this reason, when winding up the base material sheet in which the skin layer is formed, the skin layer may be easily broken. Moreover, since the 80 degreeC breaking elongation of the skin layer before ultraviolet curing may be less than 250%, it exists in the tendency for a malfunction to generate | occur | produce at the time of decorative molding.

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

  In addition, when it replaces with polycarbonate polyol (V) and polyester polyol is used, the hydrolysis resistance of the cured layer formed by ultraviolet-curing a skin layer will fall. Moreover, when it replaces with polycarbonate polyol (V) and polyether polyol is used, the heat resistance of the cured layer formed by ultraviolet-curing a skin layer will fall. For the above reasons, it is not preferable to use polyester polyol or polyether polyol.

  The kind of polycarbonate polyol is not particularly limited, and commercially available products and synthesis that are generally available can be used. Specific 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 , Polydecamethylene carbonate diol, and random / 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. In addition, polycarbonate polyol (V) can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the low molecular diol (W) include ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, Aliphatic glycols such as neopentyl glycol and 3-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 diol (W). These low molecular diols (W) can be used alone or in combination of two or more.

  Specific 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′-methylene bis- Mention may be made of alicyclic polyisocyanates such as cyclohexyl diisocyanate. By using these aliphatic polyisocyanates and alicyclic polyisocyanates, a polyurethane (A) that is hardly yellowed by ultraviolet rays or heat can be obtained, so that a more durable skin layer can be formed. . From the viewpoint of reducing the flowability of the resulting resin composition and reducing tack, it is preferable to use at least alicyclic polyisocyanates. These diisocyanate (X) can be used individually by 1 type or in combination of 2 or more types. Trifunctional or higher polyfunctional isocyanates can be used in combination. However, since the resin solution may cause gelation when the amount of the polyfunctional isocyanate used is too large, it is preferable to be careful.

  As the (meth) acrylate (Y), any (meth) acrylate containing 1 to 2 hydroxy groups at the terminal or side chain can be used. The number of (meth) acryloyl groups in these molecules (functional group) is preferably 1 or more, and more preferably 3 or more, from the viewpoint of further improving the scratch resistance of the resulting decorative molded product. Further preferred. These (meth) acrylates (Y) can be used as a chain extender or a terminal terminator for the polyurethane (A). Specific examples of (meth) acrylate (Y) include 2-hydroxylethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate, N-methylol (meth) acrylamide, 2-hydroxy-3-phenoxypropyl (meth). Acrylate, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, glycerol di (meth) acrylate, glycerol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane mono (meth) acrylate, penta Erythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, isocyanuric acid O-modified di (meth) acrylate, 2-hydroxy butyl (meth) acrylate, and the like. These (meth) acrylates (Y) can be used singly or in combination of two or more.

  When polysiloxane (Z) is used as the polymerization monomer, a structural unit derived from polysiloxane (Z) can be introduced into the structure of the resulting polyurethane (A). That is, if polysiloxane (Z) is a both-ends reaction type, the structural unit derived from polysiloxane (Z) will be introduce | transduced into the principal chain of the polyurethane (A) obtained. On the other hand, if the polysiloxane (Z) is a single-end reaction type or a branch reaction type, the structural unit derived from the polysiloxane (Z) is contained in a state branched from the terminal or main chain of the resulting polyurethane (A). The Specific examples of the polysiloxane (Z) include (1) amino-modified polysiloxane and (2) alcohol-modified polysiloxane represented by the following structural formula. Of these, polysiloxane having two hydroxy groups or two amino groups in one molecule is preferable.

(1) Amino-modified polysiloxane

(2) Alcohol-modified polysiloxane

  By using polysiloxane (Z) as a polymerization monomer, it is possible to impart slipping characteristics and slimy feel to a cured layer formed by curing the skin layer with ultraviolet rays. These polysiloxanes (Z) are not simply added to the resin composition, but are contained in the polyurethane (A) as a structural unit (copolymerized), so that the solvent, sunlight, heat Even when it is damaged by moisture, it is retained in the polyurethane (A), and the effect is sustained. The proportion of the structural unit derived from the polysiloxane (Z) in the polyurethane (A) is preferably 0.1 to 30% by mass, and more preferably 0.1 to 10% by mass. When the proportion of the structural unit derived from the polysiloxane (Z) is less than 0.1% by mass, the characteristics of the silicone are hardly expressed. On the other hand, when the proportion of the structural unit derived from polysiloxane (Z) exceeds approximately 30% by mass, the effect of imparting slipping characteristics and slimy feel to the cured layer reaches its peak.

  The resin composition usually contains a solvent. Any solvent can be used as long as it can dissolve the polyurethane (A) and the non-yellowing polyisocyanate (B). 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 And low molecular weight carbonate solvents such as dimethyl carbonate. Among them, a ketone solvent alone, a mixed solvent in which a ketone solvent and another solvent are used in combination, and a mixed solvent in which a ketone solvent and an ester solvent are used together are soluble in polyurethane (A) and dried. It is preferable because of its good properties.

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

  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 resin composition may further contain a photosensitizer such as p-dimethylbenzoate ester, tertiary amines, and thiol sensitizer.

  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 skin 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.

  Moreover, a design can be given to the formed skin layer by mix | blending colorants, extender pigments, etc., such as a silica, an organic bead, a pigment, and dye, with the resin composition for forming a skin layer. That is, the skin layer may exhibit a function as a design layer. In particular, when imparting touch to the skin layer, it is preferable to add organic beads, especially urethane beads, to the resin composition. 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. Examples thereof include 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. Moreover, in order to give not only tactile feeling but also a matte effect, it is preferable to add silica or organic beads. However, when these colorants and the like are excessively blended, ultraviolet curing of the skin layer tends to be inhibited, so that it is preferably used so as not to be excessive. Therefore, it is preferable that the design applied to the skin layer is the minimum necessary, and a full-fledged design is applied to the design layer.

  As the non-yellowing polyisocyanate (B), conventionally known polyfunctional isocyanate compounds having a plurality of isocyanate groups such as isocyanurate, burette, adduct, and polymer can be used. Specific examples of the non-yellowing polyisocyanate (B) include polyfunctional alicyclic isocyanates, polyfunctional aliphatic isocyanates, fatty acid-modified polyfunctional aliphatic isocyanates, block-type polyisocyanates such as blocked polyfunctional aliphatic isocyanates, poly An isocyanate prepolymer etc. can be mentioned.

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

(Design layer)
As a material constituting the design layer, thermoplastic resins and curable resins such as thermosetting and ultraviolet curable can be used. Specific examples of thermoplastic resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated or modified polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins, etc. Can be mentioned. 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 urethane resin, acrylic resin, and epoxy resin. A design layer can be obtained by applying a design to these resins using colorants such as silica, organic beads, pigments, dyes, extender pigments, and the like. 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. Examples thereof include 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. Moreover, it is good also considering the metal thin film provided by carrying out vapor deposition, sputtering, foil transfer, etc. using aluminum, chromium, gold | metal | money, silver, copper etc. as a design layer. The design layer may be provided on the entire surface of the functional molded sheet or may be partially provided depending on the design to be formed.

  The design layer can be provided between the skin layer and the adhesive layer as shown in FIG. 1, or even between the base material sheet and the adhesive layer as shown in FIG. It may be provided. A plurality of design layers may be provided for the purpose of imparting a high degree of design. Furthermore, in order to improve the adhesion between the base sheet and the design layer or between the skin layer and the design layer, a primer layer may be provided between them. Materials constituting the primer layer include thermosetting resins such as two-component curable urethane resins, thermosetting urethane resins, melamine resins, and epoxy resins; thermoplastic resins such as vinyl chloride copolymer resins, etc. Can be mentioned.

(Adhesive layer)
As the constituent material (binder resin) of the adhesive layer, a thermoplastic resin and a curable resin such as thermosetting and ultraviolet curable are used depending on the type of the raw material resin. Specific examples of thermoplastic resins include acrylic resins, acrylic-modified polyolefin resins, chlorinated or modified polyolefin resins, vinyl chloride-vinyl acetate copolymers, thermoplastic urethane resins, thermoplastic polyester resins, polyamide resins, rubber resins, etc. Can be mentioned. 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 and an epoxy resin.

(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.

(Substrate sheet)
The material of the base material sheet is appropriately selected in consideration of suitability for the in-mold molding method (heat resistance, moldability, etc.). Generally, a resin film (sheet) made of a thermoplastic resin is used as a base sheet. Examples of the thermoplastic resin constituting the base sheet include PET, polycarbonate, ABS resin, urethane resin, polyolefin resin, acrylic resin, and alloy resin.

  In addition, about the functional molding sheet | seat used for IMD method, in order to improve the peelability from the base material sheet of a transfer layer, a mold release agent is apply | coated between the base material sheet and the adjacent layer (for example, skin layer). It is preferable to keep it. Examples of the release agent include melamine resin-based, silicone resin-based, fluororesin-based, olefin resin-based, and paraffin-based release agents. Further, by making the surface on the transfer layer side not a flat surface, it is possible to impart a shape (such as an uneven shape) to the skin layer.

  The thickness of the base material sheet constituting the functional molded sheet used in the IML method is preferably a minimum thickness necessary for maintaining strength and shape, and more preferably 20 to 250 μm. If the base sheet is too thin, it may be difficult to ensure strength. On the other hand, if the substrate sheet is too thick, the cost may increase.

(Method for producing functional molded sheet (for IMD method))
Hereinafter, an example of a method for producing a functional molded sheet for the IMD method will be described. First, a coating material for the skin layer (resin composition) is applied on the surface of the substrate sheet to form a coating layer. In addition, you may apply | coat a mold release agent to the surface of a base material sheet previously as needed. A skin layer can be formed by drying the formed coating layer. As a method of applying the coating material for the skin layer (coating method), for example, gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, silk screen The usual printing methods such as coating, wire bar coating, flow coating, comma coating, spray coating and the like can be mentioned. The drying temperature of the coating material for the skin layer is usually 60 to 100 ° C, preferably 70 to 90 ° C.

  Subsequently, the resin composition for design layer formation etc. is apply | coated to the upper surface of a skin layer with a normal coating method, and a coating layer is formed. Examples of the method for applying the resin composition for forming the design layer (coating method) include the same method as the method for applying the above-mentioned skin coating material. The drying temperature of the design layer is usually 60 to 100 ° C, preferably 70 to 90 ° C. Moreover, a design layer can also be formed by the inkjet method. In particular, the design layer can be formed by applying UV curable inkjet ink by an inkjet method. As the ink-jet ink, it is a mainstream to use an ink that does not contain water or an organic solvent. When such an ink is used, drying is not particularly required. Similarly, a method for forming a design layer without requiring drying includes a thermal transfer method.

  Moreover, you may transfer the design layer previously formed in the transfer sheet. At this time, in order to improve the adhesion between the design layer and the skin 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 can be formed by applying a resin composition or the like for forming an adhesive layer on the surface of the formed design layer and then drying. Examples of the method for applying the resin composition for forming the adhesive layer (coating method) include the same method as the method for applying the above-mentioned skin coating material. The drying temperature of the paint for the adhesive layer is usually 60 to 100 ° C, preferably 70 to 90 ° C. Alternatively, an adhesive layer previously formed on the transfer sheet may be transferred. The adhesive layer is formed by coating or transferring the entire surface of the portion to be transferred, or partially, if it is partially. In addition, if a skin layer or a design layer has sufficient adhesiveness with respect to a molded article, an adhesive layer can also be abbreviate | omitted.

  The skin layer is aged as necessary to complete the crosslinking reaction between the polyurethane (A) and the non-yellowing polyisocyanate (B). The aging condition is usually about 30 to 60 ° C. for about 1 to 3 days. The aging of the skin layer may be performed before the design layer or the adhesive layer is formed on the base sheet, or may be performed after the design layer or the adhesive layer is formed.

(Production method of functional molded sheet (for IML method))
Next, an example of a method for producing a functional molded sheet for the IML method will be described. First, a coating material for the skin layer (resin composition) is applied on the surface of the substrate sheet to form a coating layer. The method for applying the coating material for the skin layer (coating method) may be the same method as the method for applying the coating material for the skin in the method for producing the functional molded sheet for the IMD method described above. The substrate sheet may be surface-modified by performing primer treatment or corona discharge treatment. These processes may be performed on the back surface as necessary. A skin layer can be formed by drying the formed coating layer.

  Thereafter, the design layer and the adhesive layer may be sequentially formed on the surface of the base sheet opposite to the surface on which the skin layer is formed by the same method as the method for producing the functional molded sheet for the IMD method described above. . In addition, about a skin layer, it aged as needed like the method of producing the functional molding sheet for the above-mentioned IMD method.

(Decorated molding)
The decorative molded product of the present invention is manufactured by the method for manufacturing a decorative molded product of the present invention. That is, the decorative molded product of the present invention has a cured layer formed by ultraviolet curing the above-described skin layer, and thus has excellent scratch resistance.

  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, 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 -80.0 g of butanediol, and 160.0 g of a mixture (hydroxyl value 102.9 mg KOH / g) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were charged. Next, 226 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became uniform, 103.8 g of hexamethylene diisocyanate (HDI) and 161.9 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 80 ° C. using dibutyltin laurate as a catalyst. It was made to react with. 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 solution 1 containing polyurethane 1. The obtained resin solution 1 has a viscosity of 500 dPa · s / 20 ° C., a solid content of 45%, and a double bond equivalent of 588 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 1 measured by GPC was 46,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 1 was about 44%.

(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, 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, 1,3 -80.0 g of butanediol, and 160.0 g of a mixture (hydroxyl value 102.9 mg KOH / g) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were charged. Next, 229 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became uniform, isophorone diisocyanate (IPDI) 274.3 g 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 solution 2 containing polyurethane 2. The obtained resin solution 2 has a viscosity of 400 dPa · s / 20 ° C., a solid content of 45%, and a double bond equivalent of 594 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 2 measured by GPC was 40,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 2 was about 44%.

(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, polyhexamethylene carbonate diol (trade name “Placcel CD220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 360.0 g, 1,3 80.0 g of butanediol, 160.0 g of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g), and a siloxane polyol represented by the following formula (n = integer, terminal) 40.0 g of the number average molecular weight determined by functional group determination = 2,000) was charged.

Next, 229 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became uniform, isophorone diisocyanate (IPDI) 274.3 g 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 solution 3 containing polyurethane 3. The obtained resin solution 3 has a viscosity of 430 dPa · s / 20 ° C., a solid content of 45%, and a double bond equivalent of 594 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 3 measured by GPC was 42,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 3 was about 39%. Moreover, the ratio of the structural unit derived from the siloxane polyol in the polyurethane 3 was about 4.4%.

(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, 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 -80.0 g of butanediol and 160.0 g of glycerin monomethacrylate (trade name “Blenmer GLM”, manufactured by NOF Corporation, hydroxyl value 701.3 mg KOH / g) were charged. Next, 272 g of MEK was charged as a solvent. After the inside of the system became uniform, 175.5 g of hexamethylene diisocyanate (HDI) and 273.6 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 80 ° C. using dibutyltin laurate as a catalyst. It was made to react with. 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 the free isocyanate group disappeared as measured by infrared absorption spectrum analysis. Cyclohexanone was added until the mass ratio of MEK to cyclohexanone was 1: 1 to obtain a resin solution 4 containing polyurethane 4. The resulting resin solution 4 has a viscosity of 550 dPa · s / 20 ° C., a solid content of 30%, and a double bond equivalent of 1089 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 4 measured by GPC was 72,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 4 was about 37%.

(Synthesis Example 5: 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, polyhexamethylene carbonate diol (trade name “Placcel CD220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 360.0 g, 1,4 -80.0 g of butanediol, glycerin monomethacrylate (trade name “Blenmer GLM”, manufactured by NOF Corporation, hydroxyl value 701.3 mg KOH / g) 160.0 g, and siloxane polyol represented by the following formula (n = integer, terminal) 40.0 g of the number average molecular weight determined by functional group determination = 2,000) was charged.

Next, 272 g of methyl ethyl ketone (MEK) was charged as a solvent. After the inside of the system became uniform, 175.5 g of hexamethylene diisocyanate (HDI) and 273.6 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 80 ° C. using dibutyltin laurate as a catalyst. It was made to react with. 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 the free isocyanate group disappeared as measured by infrared absorption spectrum analysis. Cyclohexanone was added until the mass ratio of MEK to cyclohexanone was 1: 1 to obtain a resin solution 5 containing polyurethane 5. The obtained resin solution 5 has a viscosity of 530 dPa · s / 20 ° C., a solid content of 30%, and a double bond equivalent of 1089 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 5 measured by GPC was 71,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 5 was about 33%. Moreover, the ratio of the structural unit derived from the siloxane polyol in the polyurethane 5 was about 3.7%.

(Comparative Synthesis Example 1: 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, polycaprolactone diol (trade name “Placcel 220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 400.0 g, 1,4-butane Diol 80.0 g and dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate mixture (hydroxyl value 102.9 mg KOH / g) 160.0 g were charged. Next, 226 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became uniform, 103.8 g of hexamethylene diisocyanate (HDI) and 161.9 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 80 ° C. using dibutyltin laurate as a catalyst. It was made to react with. 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 solution 6 containing polyurethane 6. The obtained resin solution 6 had a viscosity of 550 dPa · s / 20 ° C., a solid content of 45%, and a double bond equivalent of 588 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 6 measured by GPC was 50,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 6 was about 0%.

(Comparative Synthesis Example 2: 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, polycaprolactone diol (trade name “Placcel 220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 400.0 g, 1,4-butane Diol 80.0 g and glycerin monomethacrylate (trade name “Blenmer GLM”, manufactured by NOF Corporation, hydroxyl value 701.3 mg KOH / g) 160.0 g were charged. Next, 272 g of MEK was charged as a solvent. After the inside of the system became uniform, 175.5 g of hexamethylene diisocyanate (HDI) and 273.6 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 80 ° C. using dibutyltin laurate as a catalyst. It was made to react with. 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 the free isocyanate group disappeared as measured by infrared absorption spectrum analysis. Cyclohexanone was added until the mass ratio of MEK to cyclohexanone was 1: 1 to obtain a resin solution 7 containing polyurethane 7. The obtained resin solution 7 had a viscosity of 560 dPa · s / 20 ° C., a solid content of 30%, and a double bond equivalent of 1089 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 7 measured by GPC was 73,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 7 was about 0%.

(Comparative Synthesis Example 3: 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 polytetramethylene glycol (trade name “PTMG2000”, manufactured by Mitsubishi Chemical Corporation, number average molecular weight by terminal functional group determination = 2,000), 1,4-butanediol 80.0 g and glycerol monomethacrylate (trade name “Blenmer GLM”, manufactured by NOF Corporation, hydroxyl value 701.3 mgKOH / g) were charged. Next, 272 g of MEK was charged as a solvent. After the inside of the system became uniform, 175.5 g of hexamethylene diisocyanate (HDI) and 273.6 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 80 ° C. using dibutyltin laurate as a catalyst. It was made to react with. 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 the free isocyanate group disappeared as measured by infrared absorption spectrum analysis. Cyclohexanone was added until the mass ratio of MEK to cyclohexanone was 1: 1 to obtain a resin solution 8 containing polyurethane 8. The obtained resin solution 8 has a viscosity of 505 dPa · s / 20 ° C., a solid content of 30%, and a double bond equivalent of 1089 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 8 measured by GPC was 72,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 8 was 0%.

(Comparative Synthesis Example 4: Synthesis of polyurethane 9)
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, polycaprolactone diol (trade name “Placcel 220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 360.0 g, 1,4-butane Diol 80.0 g, a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (hydroxyl value 102.9 mg KOH / g) 160.0 g, and a siloxane polyol represented by the following formula (n = integer, terminal functional group) 40.0 g of the number average molecular weight by quantitative determination = 2,000) was charged.

Next, 229 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became uniform, isophorone diisocyanate (IPDI) 274.3 g 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 solution 9 containing polyurethane 9. The obtained resin solution 9 has a viscosity of 420 dPa · s / 20 ° C., a solid content of 45%, and a double bond equivalent of 594 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 9 measured by GPC was 43,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 9 was 0%. Moreover, the ratio of the structural unit derived from the siloxane polyol in the polyurethane 9 was about 4.4%.

(Comparative Synthesis Example 5: Synthesis of polyurethane 10)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, polyhexamethylene carbonate diol (trade name “Placcel CD220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 400.0 g, 1,4 -80.0 g of butanediol and 20.0 g of a mixture (hydroxyl value: 102.9 mg KOH / g) of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate were charged. Next, 185 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became uniform, 93.0 g of hexamethylene diisocyanate (HDI) and 145.1 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C. and 80 ° C. using dibutyltin laurate as a catalyst. It was made to react with. 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 solution 10 containing polyurethane 10. The obtained resin solution 10 has a viscosity of 600 dPa · s / 20 ° C., a solid content of 45%, and a double bond equivalent of 3838 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 10 measured by GPC was 53,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 10 was about 54%.

(Comparative Synthesis Example 6: Synthesis of polyurethane 11)
A reaction vessel equipped with a stirrer, a reflux condenser, a thermometer, an air blowing tube, and a manhole was prepared. While replacing the inside of the reaction vessel with air, polyhexamethylene carbonate diol (trade name “Placcel CD220”, manufactured by Daicel Chemical Industries, Ltd., number average molecular weight by terminal functional group determination = 2,000) 360.0 g, 1,4 -80.0 g of butanediol, 40.0 g of glycerin monomethacrylate (trade name “Blenmer GLM”, manufactured by NOF Corporation, hydroxyl value 701.3 mg KOH / g), and a siloxane polyol represented by the following formula (n = integer, 40.0 g of number average molecular weight by terminal functional group quantification = 2,000) was charged.

Next, 202 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became uniform, 112.4 g of hexamethylene diisocyanate (HDI) and 175.3 g of 4,4′-methylenebis-cyclohexyl diisocyanate were charged at 50 ° C., and 80 ° C. using dibutyltin laurate as a catalyst. It was made to react with. 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 the free isocyanate group disappeared as measured by infrared absorption spectrum analysis. Cyclohexanone was added until the mass ratio of MEK to cyclohexanone was 1: 1 to obtain a resin solution 11 containing polyurethane 11. The obtained resin solution 11 has a viscosity of 550 dPa · s / 20 ° C., a solid content of 30%, and a double bond equivalent of 3231 g / eq. Met. Moreover, the weight average molecular weight of the polyurethane 10 measured by GPC was 75,000, and the ratio of the structural unit derived from the polycarbonate polyol in the polyurethane 11 was 45%. Moreover, the ratio of the structural unit derived from the siloxane polyol in the polyurethane 11 was about 5.0%.

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

(Skin layer paint 2)
2. 100 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) and a filler for design (trade name “Silicia 420”, Fuji Silysia Chemical Co., Ltd.) with respect to 100 g of the resin solution 1 obtained in Synthesis Example 1. Manufactured, wet method silica, average particle system 3.1 μm) 13.5 g was added, and MEK and cyclohexanone were blended at a mass ratio of 1: 1 to obtain a mixed solution of 30% solid content. A paint shaker was used to disperse the resulting mixture using glass beads as media. Then, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone were blended at a mass ratio of 1: 1. Thus, a skin layer coating material 2 having a solid content of 28% was obtained.

(Skin layer coating 3)
2.25 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was added to 100 g of the resin solution 2 obtained in Synthesis Example 2. Furthermore, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and 23.1% isocyanate), MEK and cyclohexanone are blended at a mass ratio of 1: 1. Thus, a skin layer coating material 3 having a solid content of 30% was obtained.

(Skin layer coating 4)
2.25 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was added to 100 g of the resin solution 3 obtained in Synthesis Example 3. Furthermore, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and 23.1% isocyanate), MEK and cyclohexanone are blended at a mass ratio of 1: 1. Thus, a skin layer coating material 4 having a solid content of 30% was obtained.

(Skin layer coating 5)
2. 100 g of the resin solution 3 obtained in Synthesis Example 3, 2.25 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) and a filler for design (trade name “DIMIC BEADS UCN-5070D”, Daiichi Seika Kogyo Co., Ltd., urethane organic beads, average particle size 7 μm) 13.5 g was added, and MEK and cyclohexanone were blended at a mass ratio of 1: 1 to obtain a mixed solution with a solid content of 30%. . A paint shaker was used to disperse the resulting mixture using glass beads as media. Then, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone were blended at a mass ratio of 1: 1. Thus, the skin layer coating material 5 having a solid content of 28% was obtained.

(Skin layer coating 6)
To 100 g of the resin solution 4 obtained in Synthesis Example 4, 1.5 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was blended. Furthermore, 1.5 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone are blended in a mass ratio of 1: 1. Thus, a skin layer coating material 6 having a solid content of 28% was obtained.

(Skin layer coating 7)
For 100 g of the resin solution 4 obtained in Synthesis Example 4, 1.5 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) and a filler for design (trade name “DIMIC BEADS UCN-5070D”, 9.0 g (urethane organic beads manufactured by Dainichi Seika Kogyo Co., Ltd., average particle size: 7 μm) was added, and MEK and cyclohexanone were blended at a mass ratio of 1: 1 to obtain a mixed solution having a solid content of 28%. A paint shaker was used to disperse the resulting mixture using glass beads as media. Then, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone were blended at a mass ratio of 1: 1. Thus, a skin layer coating material 7 having a solid content of 25% was obtained.

(Skin layer paint 8)
To 100 g of the resin solution 5 obtained in Synthesis Example 5, 1.5 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was blended. Furthermore, 1.5 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone are blended in a mass ratio of 1: 1. Thus, a skin layer coating 8 having a solid content of 28% was obtained.

(Skin layer paint 9)
For 100 g of the resin solution 5 obtained in Synthesis Example 5, 1.5 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) and a filler for design (trade name “DIMIC BEADS UCN-5150D”, 9.0 g (urethane organic beads, average particle size: 15 μm, manufactured by Dainichi Seika Kogyo Co., Ltd.) was added, and MEK and cyclohexanone were blended at a mass ratio of 1: 1 to obtain a mixed solution having a solid content of 28%. . A paint shaker was used to disperse the resulting mixture using glass beads as media. Then, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone were blended at a mass ratio of 1: 1. Thus, a skin layer coating material 9 having a solid content of 25% was obtained.

(Comparative skin coating 1)
2.25 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was added to 100 g of the resin solution 6 obtained in Comparative Synthesis Example 1. Furthermore, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and 23.1% isocyanate), MEK and cyclohexanone are blended at a mass ratio of 1: 1. Thus, a comparative skin layer coating material 1 having a solid content of 30% was obtained.

(Comparative skin coating 2)
To 100 g of the resin solution 7 obtained in Comparative Synthesis Example 2, 1.5 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was blended. Furthermore, 1.5 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone are blended in a mass ratio of 1: 1. Thus, a comparative skin layer coating material 2 having a solid content of 28% was obtained.

(Comparative skin coating 3)
To 100 g of the resin solution 8 obtained in Comparative Synthesis Example 3, 1.5 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was blended. Furthermore, 1.5 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone are blended in a mass ratio of 1: 1. Thus, a comparative skin layer coating material 3 having a solid content of 28% was obtained.

(Comparative skin coating 4)
2.25 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was added to 100 g of the resin solution 9 obtained in Comparative Synthesis Example 4. Furthermore, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and 23.1% isocyanate), MEK and cyclohexanone are blended at a mass ratio of 1: 1. Thus, a comparative skin layer coating 4 having a solid content of 30% was obtained.

(Comparative skin coating 5)
2.25 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was added to 100 g of the resin solution 10 obtained in Comparative Synthesis Example 5. Furthermore, 2.25 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and 23.1% isocyanate), MEK and cyclohexanone are blended at a mass ratio of 1: 1. Thus, a comparative skin layer coating 5 having a solid content of 30% was obtained.

(Comparative skin coating 6)
To 100 g of the resin solution 11 obtained in Comparative Synthesis Example 6, 1.5 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was blended. Furthermore, 1.5 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone are blended in a mass ratio of 1: 1. Thus, a comparative skin layer coating 6 having a solid content of 28% was obtained.

(Comparative skin layer coating 7)
2.25 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was added to 100 g of the resin solution 1 obtained in Synthesis Example 1. Furthermore, 0.5 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone are blended in a mass ratio of 1: 1. Thus, a comparative skin layer coating material 7 having a solid content of 30% was obtained.

(Comparative skin coating 8)
2.25 g of a photopolymerization initiator (trade name “Irgacure 184”, manufactured by BASF) was added to 100 g of the resin solution 1 obtained in Synthesis Example 1. Furthermore, 13.5 g of non-yellowing polyisocyanate (trade name “Duranate TPA-100”, manufactured by Asahi Kasei Co., Ltd., containing 100% solids and containing 23.1% isocyanate), MEK and cyclohexanone are blended at a mass ratio of 1: 1. Thus, a comparative skin layer coating material 8 having a solid content of 30% was obtained.

<Preparation of composition for design layer>
(Composition 1 for design layers)
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 -40.0 g of butanediol was charged. Next, 146 g of methyl ethyl ketone (MEK) was charged as a solvent. After the system became uniform, 143.0 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 solution 1 for a design layer containing polyurethane. The viscosity was 420 dPa · s / 20 ° C., the solid content was 40%, and the weight average molecular weight 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 with respect to 100.0 g of the obtained resin solution 1 for design layer, and mass ratio of MEK and cyclohexanone as a solvent The composition 1 for a design layer having a solid content of 30% was obtained by blending at a ratio of 1: 1.

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

(Composition 3 for design layer)
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.

(Design layer composition 4)
100 g of resin solution 1 for design layer 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) MEK and cyclohexanone as a solvent were blended at a mass ratio of 1: 1 to obtain a design layer composition 4 having a solid content of 30%.

<Preparation of resin composition for adhesive layer>
The resin composition for adhesive layers shown below can be used not only as a material for forming the adhesive layer but also as a primer for improving the adhesion between the design layer and the substrate sheet.

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

(Adhesive layer resin composition 2)
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 2 for an adhesive layer containing polyurethane. The obtained adhesive layer resin composition 2 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 2 for adhesive layers was 21,000.

(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. 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 3 for contact bonding layers which consists of an acrylic polymer was obtained. The obtained adhesive layer resin composition 3 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 3 for adhesive layers was 35,000.

<Production of functional molded sheet: for IMD method>
Example 1
A PET film having a thickness of 200 μm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the design layer composition 4 was applied to the surface of the skin layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 3 was applied to the surface of the formed design layer with a bar coater and dried at 80 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. Thereafter, 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).

(Examples 2-9 and Comparative Examples 1-8)
A functional molded sheet (Examples 2 to 2) was prepared in the same manner as in Example 1 except that the skin layer was formed using the types of skin layer paints or comparative skin layer paints shown in Tables 1 and 2. 9 and Comparative Examples 1 to 8) were obtained.

(Example 10)
A PET film having a thickness of 200 μm was prepared as a base sheet. Processing (concave / convex processing) was performed using an embossed roll with a crucible heated to 250 ° C. to form a concave / convex pattern on the surface of the base sheet. Apply the coating material 1 for the skin layer with a bar coater on the surface of the substrate sheet on which the concave and convex pattern is formed, and dry it at 90 ° C. for 2 minutes to form a skin layer with a thickness of 15 μm. It was. Next, the design layer composition 4 was applied to the surface of the skin layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 3 was applied to the surface of the formed design layer with a bar coater and dried at 80 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. Thereafter, 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 10).

(Example 11)
A PET film having a thickness of 200 μm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the design layer composition 1 was applied to the surface of the skin layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 3 was applied to the surface of the formed design layer with a bar coater and dried at 80 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. Thereafter, 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 11).

(Example 12)
A PET film having a thickness of 200 μm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the adhesive layer resin composition 3 was applied to the surface of the skin layer with a bar coater and dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. Aluminum which is the composition 2 for design layers was vapor-deposited on the surface of the formed primer layer to form a design layer. The adhesive layer resin composition 3 was applied to the surface of the formed design layer with a bar coater. Thereafter, it was dried at 80 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. Thereafter, 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 12).

(Example 13)
A PET film having a thickness of 200 μm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the design layer composition 3 was applied to the surface of the skin layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 3 was applied to the surface of the formed design layer with a bar coater and dried at 80 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. Thereafter, 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 13).

(Example 14)
A PET film having a thickness of 200 μm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the design layer composition 4 was applied to the surface of the skin layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 1 was applied to the surface of the formed design layer with a bar coater and dried at 80 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. Thereafter, 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 14).

(Example 15)
A PET film having a thickness of 200 μm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the design layer composition 4 was applied to the surface of the skin layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 2 was applied to the surface of the formed design layer with a bar coater and dried at 80 ° C. for 2 minutes to form an adhesive layer having a thickness of 20 μm. Thereafter, 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 15).

<Manufacture of decorative molded products: IMD method>
While using acrylonitrile-butadiene-styrene copolymer (ABS resin) as a raw material resin, the functional molded sheets of Examples 1 to 13 and Comparative Examples 1 to 8 were used, respectively, and injection molding was performed by the IMD method. . The injection molding conditions were a resin temperature of 230 ° C., a mold temperature of 70 ° C., and a resin pressure of 300 kg / cm ² , and the transfer layer (adhesive layer, skin layer, and design layer) was transferred to a molded product made of the raw material resin. . Then, using an ultraviolet irradiation machine (trade name “UNICURE UVC-02512S1AA01”, manufactured by USHIO INC.), The transferred transfer layer is irradiated with UV light so that the accumulated light amount is 2000 mJ / cm ^2, and the skin layer is cured. The cured layer was formed to obtain a decorative molded product. Moreover, while using polypropylene and a polycarbonate as raw material resin, respectively, except having used the functional molding sheet | seat of Example 14 and 15, respectively, the decorative molded product was obtained like the above.

<Production of functional molded sheet: for IML method>
(Example 16)
An ABS sheet having a thickness of 0.2 mm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the adhesive layer resin 3 is applied to the back surface of the base sheet (the surface opposite to the surface on which the skin layer is formed) with a bar coater and dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. did. The design layer composition 4 was applied to the surface of the formed primer layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 3 was applied to the surface of the formed design layer with a bar coater and 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 stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 16).

(Examples 17-24 and Comparative Examples 9-16)
A functional molded sheet (Examples 17 to 17) was formed in the same manner as in Example 16 except that the skin layer was formed using the types of skin layer paints or comparative skin layer paints shown in Tables 3 and 4. 24 and Comparative Examples 9 to 16).

(Example 25)
An ABS sheet having a thickness of 0.2 mm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the adhesive layer resin 3 is applied to the back surface of the base sheet (the surface opposite to the surface on which the skin layer is formed) with a bar coater and dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. did. The design layer composition 4 was applied to the surface of the formed primer layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. Processing (unevenness processing) was carried out using an embossed roll containing creasing heated to 100 ° C., and an uneven pattern was formed on the surface of the skin layer. Next, the adhesive layer resin composition 3 was applied to the surface of the design layer with a bar coater and 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 stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 25).

(Example 26)
An ABS sheet having a thickness of 0.2 mm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the adhesive layer resin 3 is applied to the back surface of the base sheet (the surface opposite to the surface on which the skin layer is formed) with a bar coater and dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. did. The design layer composition 1 was applied to the surface of the formed primer layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 3 was applied to the surface of the formed design layer with a bar coater and 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 stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 26).

(Example 27)
An ABS sheet having a thickness of 0.2 mm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the adhesive layer resin 3 is applied to the back surface of the base sheet (the surface opposite to the surface on which the skin layer is formed) with a bar coater and dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. did. Aluminum which is the composition 2 for design layers was vapor-deposited on the surface of the formed primer layer to form a design layer. The adhesive layer resin composition 3 was applied to the surface of the formed design layer with a bar coater and 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 stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 27).

(Example 28)
An ABS sheet having a thickness of 0.2 mm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the adhesive layer resin 3 is applied to the back surface of the base sheet (the surface opposite to the surface on which the skin layer is formed) with a bar coater and dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. did. The design layer composition 3 was applied to the surface of the formed primer layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 3 was applied to the surface of the formed design layer with a bar coater and 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 stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 28).

(Example 29)
A 0.2 mm thick polypropylene (PP) sheet (surface energy 30 mN / m) was prepared. Corona discharge treatment was performed on both the front and back surfaces of this PP sheet to obtain a base material sheet having a surface energy of 37 mN / m. The coating material 1 for the skin layer was applied to the surface of the obtained base sheet with a bar coater, 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. Next, the adhesive layer resin 1 is applied to the back surface of the base sheet (the surface opposite to the surface on which the skin layer is formed) with a bar coater and dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. did. The design layer composition 4 was applied to the surface of the formed primer layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 1 was applied to the surface of the formed design layer with a bar coater and 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 stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 29).

(Example 30)
A polycarbonate (PC) sheet having a thickness of 0.2 mm was prepared as a base sheet. The coating material 1 for the skin layer was applied to the surface of this base sheet with a bar coater, 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. Next, the adhesive layer resin 2 is applied to the back surface of the base sheet (the surface opposite to the surface on which the skin layer is formed) with a bar coater and dried at 90 ° C. for 2 minutes to form a primer layer having a thickness of 5 μm. did. The design layer composition 4 was applied to the surface of the formed primer layer with a bar coater and dried at 90 ° C. for 2 minutes to form a design layer having a thickness of 20 μm. The adhesive layer resin composition 2 was applied to the surface of the formed design layer with a bar coater and 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 stuck on the surface of the formed adhesive layer to obtain a functional molded sheet (Example 30).

<Manufacture of decorative molded products: IML method>
The functional molded sheets of Examples 16 to 28 and Comparative Examples 9 to 16 are inserted into the molds so that their adhesive layers are on the molded product side, and heated to 150 ° C. to mold the functional molded sheets. Then, it was adapted to the inner shape of the mold. The mold was closed, and injection molding was performed by the IMD method using acrylonitrile-butadiene-styrene copolymer (ABS resin) as a raw material resin. The injection molding conditions were a resin temperature of 230 ° C., a mold temperature of 70 ° C., a resin pressure of 300 kg / cm ² , and an insert layer (adhesive layer, skin layer, base material layer, and design layer) made of a raw material resin. I transferred it to the product. Then, using an ultraviolet irradiation machine (trade name “UNICURE UVC-02512S1AA01”, manufactured by USHIO INC.), The transferred insert layer is irradiated with UV so that the integrated light quantity is 2000 mJ / cm ^2, and the skin layer is cured. The cured layer was formed to obtain a decorative molded product. Moreover, while using polypropylene and a polycarbonate as raw material resin, respectively, except having used the functional molding sheet | seat of Example 29 and 30, respectively, the decorative molded product was obtained like the above.

<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 Tables 1-4.
A: No cracking or whitening of the coating layer was observed in the skin layer and the design layer, and the shape of the mold was followed well.
○: 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 skin layer and the design layer could not follow the shape of the mold, and cracking of the coating film or whitening was observed.

(2) Elongation at 80 ° C. The coating material for the skin layer and the coating material for the comparative skin layer were each coated on release paper so that the dry film thickness was about 30 μm, and then aged at 45 ° C. for 1 day. Formed. After aging, using an infrared spectrophotometer, it was confirmed that absorption derived from 2,270 cm ⁻¹ isocyanate group (non-yellowing polyisocyanate) had disappeared, and the coating film was 15 mm wide × long A test piece was prepared by cutting to a size of 60 mm. About the produced test piece, an autograph (trade name “AGS-J 500N”, manufactured by Shimadzu Corporation) and a constant temperature test apparatus (trade name “TCR1-200”, manufactured by Shimadzu Corporation) were used at a temperature of 80 ° C. The elongation at break at 80 ° C. was measured under the conditions of a distance between chucks of 20 mm and a pulling speed of 200 mm / min. The results are shown in Tables 1-4.

(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 Tables 1-4.

(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 Tables 1-4.
○: No significant change was observed in the cured layer.
X: Swelling or peeling of the cured layer was observed.

(5) Light resistance Based on JASO M346-1993, the acceleration test was implemented using the xenon weatherometer on the conditions shown below.
Irradiance: 48 to 162 W / m ²
Wavelength: 300-400nm
Black panel temperature: 89 ± 3 ℃
Irradiation time: 8 weeks Heat quantity: 2000kJ
Light was irradiated to the surface of the decorative molded product (ultraviolet-cured cured layer) produced under the above conditions. The appearance of the cured layer after the test was observed, and light resistance was evaluated according to the evaluation criteria shown below. The results are shown in Tables 1-4.
○: Discoloration, choking, cracking, cracking, etc. did not occur in the cured layer.
X: Discoloration, choking, cracking, cracking, etc. occurred 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 Tables 1-4.
○: 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 article (ultraviolet-cured) was subjected to a jungle test that was held at a temperature of 70 ° C. and a relative humidity of 95% for 8 weeks. The external appearance of the hardened layer after a test is observed, and the result of having evaluated hydrolysis resistance according to the evaluation criteria shown below is shown to Tables 1-4.
○: Whitening, choking, cracking, cracking, etc. did not occur in the cured layer.
X: Whitening, choking, cracking, cracking, etc. occurred in the cured layer.

  As is clear from the results shown in Tables 1 to 4, the functional molded sheets of Examples 1 to 30 had good three-dimensional moldability without causing cracks or cracks. Furthermore, it is confirmed that the decorative molded products obtained using the functional molded sheets of Examples 1 to 30 are excellent in scratch resistance, solvent resistance, light resistance, heat resistance, and hydrolysis resistance. It was done.

  According to the method of manufacturing a decorative molded product of the present invention, for example, an interior material or exterior material of a vehicle such as an automobile; a housing of a home appliance such as a television, a personal computer, or a mobile phone; a building such as a wall, floor, or ceiling It is possible to easily produce decorative molded products such as containers.

1, 11: skin layer 2, 12: base sheet 3, 13: design layer 4, 14: adhesive layer 5, 15: separate film 6: transfer layer 7: insert layer 10, 20: highly durable functional molded sheet

Claims (10)

Injection molding in which a raw resin is injected into the mold in a state in which a highly durable functional molded sheet having a laminated structure including an adhesive layer, a design layer, a skin layer, and a base sheet is placed in the mold for injection molding Process,
A cured layer forming step of curing the skin layer by irradiating ultraviolet rays to form a cured layer, and
A method for producing a decorative molded product, which uses a material satisfying the following conditions (1) to (3) as the highly durable functional molded sheet.
(1) The skin layer has a double bond equivalent containing a (meth) acryloyloxy group of 160 to 3000 g / eq. Polycarbonate-based polyurethane (A), and comprises a reaction cured product of the resin composition containing a non-yellowing polyisocyanate of the 2 to 25 wt% of the polycarbonate-based polyurethane (A) (B).
(2) The breaking elongation at 80 ° C. of the skin layer is 250% or more.
(3) The pencil hardness at a load of 500 g measured according to JIS K5400 of the cured layer formed by ultraviolet curing the skin layer is 3B or more. The decoration according to claim 1, wherein the non-yellowing polyisocyanate (B) is at least one polyfunctional isocyanate compound selected from the group consisting of an isocyanurate body, a burette body, an adduct body, and a polymer body. Manufacturing method of molded products. The high-durability functional molded sheet has the adhesive layer, the skin layer, and the base sheet laminated in this order, and the design layer is adjacent to at least one of the adhesive layer and the skin layer. Has been placed,
2. A decorative molded product to which a design property is imparted is obtained by transferring a transfer layer composed of the adhesive layer, the skin layer, and the design layer to a molded product composed of the raw material resin during injection molding. Or the manufacturing method of the decorative molded product of 2 . The highly durable functional molded sheet has the adhesive layer, the base sheet, and the skin layer laminated in this order, and is adjacent to at least one of the adhesive layer, the base sheet, and the skin layer. And the design layer is arranged,
At the time of injection molding, a decorative molded product to which design properties are imparted by transferring an insert layer composed of the adhesive layer, the base sheet, the skin layer, and the design layer to a molded product composed of the raw material resin. The manufacturing method of the decorative molded product of Claim 1 or 2 which obtains.   The manufacturing method of the decorative molded product as described in any one of Claims 1-4 in which the said polycarbonate-type polyurethane (A) contains 0.1-70 mass% of structural units derived from a polycarbonate polyol.   The decorative polyurethane molded product according to any one of claims 1 to 5, wherein the polycarbonate-based polyurethane (A) contains 0.1 to 30% by mass of a structural unit derived from polysiloxane having an active hydrogen-containing group. Production method.   The method for producing a decorative molded product according to any one of claims 1 to 6, wherein the polycarbonate-based polyurethane (A) further contains 0.01 to 10% by mass of a photopolymerization initiator.   The method for producing a decorative molded product according to any one of claims 1 to 7, wherein the design layer is a resin layer or a metal thin film to which a design is applied.   The method for producing a decorative molded product according to any one of claims 1 to 8, wherein an uneven pattern is formed on a surface of the skin layer.   The method for producing a decorative molded product according to any one of claims 1 to 9, wherein the adhesive layer includes at least one selected from the group consisting of a urethane resin, a modified olefin resin, and an acrylic resin.

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