JP2011183788A - Method for production of molded laminate, and cured coating transfer film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To efficiently and economically form a cured coating film excellent in scratch resistance and weatherability with high productivity using a cured coating transfer film, on a surface of an injection molded body. <P>SOLUTION: A production method for a molded laminate includes: forming, on a base film 2a, a first transfer layer 2b formed by an active energy ray-curable composition for forming the cured coating film, and the first transfer layer 2b of a cured coating transfer film 2 having a second transfer layer 2c for forming a layer of adhesion of the cured coating film with a molded body by contact therewith into a semicured state by irradiation with the active energy rays; arranging the cured coating transfer film 2 in a mold and injection-filling with a thermoplastic resin 3; and curing the first transfer layer 2b by heat of the filled resin. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a method for producing a laminated molded body formed by forming a cured film on the surface of an injection molded body made of a thermoplastic resin, and more specifically, injection molding of a thermoplastic resin using a cured film transfer film. The present invention relates to a method for producing a laminated molded body that simultaneously forms a cured film by transfer, and a laminated molded body produced by this method.
The present invention also relates to a cured film transfer film used in the method for producing the laminated molded body.

  In general, thermoplastic resin molded products such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, vinyl chloride resin, ABS resin, cellulose acetate, and polypropylene are excellent in lightness, easy processability, impact resistance, etc. Used for applications. For example, polycarbonate resin has advantages such as excellent transparency, heat resistance, mechanical strength, and easy processability, so it is widely used in electrical, automotive, medical applications, etc., and in recent years, it is used as a window glass for automobiles. This contributes to improving fuel efficiency by reducing the weight of automobiles.

  However, a thermoplastic resin molded body such as polycarbonate resin has insufficient scratch resistance due to its low surface hardness. In addition, long-term outdoor use has the drawback of yellowing and other deterioration and deterioration problems.

  For the purpose of improving these drawbacks, various surface protective layers such as a cured film (hard coat layer) are formed on the thermoplastic resin molded article to obtain a product.

  Conventionally, as a method for molding a thermoplastic resin, injection molding has been widely adopted because it is excellent in production efficiency and a large-area molded body can be efficiently continuously produced. In this case, there is a method of forming a cured film by applying and curing a coating solution for forming a cured film on the surface of an injection molded molded body. There is a method of forming a cured film simultaneously with injection molding using a cured film transfer film on which a transfer layer for forming a cured film is formed.

  In the cured film transfer film used in this case, a first transfer layer for forming a cured film is generally formed on a base film, and a first adhesive layer between the cured film and the molded body is formed on the first transfer layer. 2 transfer layer is formed, and such a cured film transfer film is placed in a mold for injection molding so that the base film is in contact with the inner surface of the mold, and then in the cavity of the mold. A thermoplastic resin is injected and filled, and injection molding and transfer film formation are simultaneously performed (for example, Patent Documents 1 and 2).

  If the first transfer layer for forming a cured film of such a cured film transfer film is completely cured before transfer, a cured film that follows the surface of the molded body cannot be formed with good adhesion. On the other hand, if the first transfer layer is uncured, it is difficult to form the second transfer layer thereon, so that the first transfer layer is in a semi-cured state, and the curing is completed after the transfer. The method (hereinafter, further curing or completing the curing of the semi-cured transfer layer may be referred to as “follow-up curing”) is employed.

  For example, Patent Document 1 uses a cured film transfer film in which a first transfer layer made of a silicon-based thermosetting composition on a base film is semi-cured and a second transfer layer is formed thereon. A method is proposed in which after injection molding is performed and the transfer layer is transferred to the molded body side, the molded body is removed from the mold, the base film is peeled off, and then heated to further cure the first transfer layer for forming a cured film. Has been.

  Patent Document 2 discloses that after a transfer layer for forming a cured film made of an acrylic active energy ray-curable resin is heated to a semi-cured state, the molded product is taken out from the mold after injection molding and transfer. It describes that the base film is peeled off and further cured by irradiation with active energy rays. This Patent Document 2 describes that setting the first transfer layer in a semi-cured state by irradiating active energy rays makes it difficult to control the irradiation amount of the active energy rays to obtain a desired semi-cured state. Yes.

Japanese Patent No. 3376101 Japanese Patent No. 3233595

As described in Patent Documents 1 and 2, the method of performing post-curing of the transfer layer by heating or irradiation with active energy rays after injection molding and after removing the molded body from the mold has the following problems.
[1] In a process of heating or irradiating active energy rays to a semi-cured cured film-forming transfer layer, the transfer layer that is not fully cured is likely to become dusty or scratched, resulting in a defective product rate. Is expensive.
[2] After injection molding, after the molded body is taken out from the mold, a process for additional curing by heating or irradiation with active energy rays is required, which is disadvantageous in terms of productivity and cost.
[3] Semi-curing by heating or subsequent curing is not energy efficient and requires time for curing.
[4] When additional curing is performed by active energy ray irradiation, uniform curing may not be possible for large areas or complex shapes. In this case, the cured film formed has scratch resistance and weather resistance. It will be inferior.

  The present invention solves the above-mentioned conventional problems, and using a cured film transfer film, a cured film having excellent scratch resistance and weather resistance can be efficiently and economically produced with high productivity. It is an object to provide a technique for forming a surface.

  As a result of intensive investigations to solve the above problems, the present inventors have used a cured film transfer film in which the first transfer layer for forming a cured film is in a semi-cured state by irradiation with active energy rays, By performing additional curing with the heat of the thermoplastic resin injected and filled into the cavity, injection molding and transfer and curing of the transfer layer are performed simultaneously, and heating or irradiation with active energy rays for additional curing after injection molding. By eliminating the need for a process and performing additional curing by heat-curing with an injection filling resin in the mold, the transfer layer for forming the cured film can be uniformly and efficiently cured. The present inventors have found that a cured film having excellent weather resistance can be formed.

  The present invention has been achieved based on such knowledge, and the gist thereof is as follows.

[1] Manufacturing a laminated molded body having a cured film formed on the surface by injection-filling a thermoplastic resin into an injection mold cavity in which a cured film transfer film is arranged and injection-molding the thermoplastic resin In this method, the cured film transfer film comprises a first transfer layer formed of an active energy ray-curable composition for forming the cured film on a base film, and a cured film in contact with the molded body. A second transfer layer having at least two transfer layers including a second transfer layer for forming an adhesive layer with the molded body, and being semi-cured by irradiation with active energy rays. Forming the other transfer layer including the step of obtaining the cured film transfer film, and disposing the cured film transfer film in the mold such that the base film is in contact with the mold; , Thermoplastic in the cavity Fat with injection filling method of the molded laminate, characterized in that a step of performing a curing reaction of the first transfer layer by heat of the filling resin.

[2] In [1], the first transfer layer that is semi-cured by irradiation with active energy rays has a touch-tack property that prevents the first transfer layer-forming material from adhering to the finger by touch and is active. The first transfer layer before irradiation with energy rays and the first transfer after irradiation with active energy rays are measured by a single reflection ATR surface reflection method using an infrared spectrophotometer, and a peak P ₈₁₀ at a wave number of ₈₁₀ cm ⁻¹ is obtained. A method for producing a laminated molded product, wherein a curing rate calculated by the following formula is 0.6 or less from a value of a ratio P ₈₁₀ / P _{1726 to} a peak P ₁₇₂₆ at a wave number of ₁₇₂₆ cm ⁻¹ .
Hardening rate = (active energy ray irradiation before _{P 810 / P 1726 - P 810} / P 1726 after active energy ray irradiation) / active energy ray before irradiation _P 810 _{/ P 1726}

[3] The laminate molding characterized in that, in [1] or [2], the absorbance at a wavelength of 254 nm of the first transfer layer made semi-cured by irradiation with active energy rays is 0.1 or more and 2.0 or less. Body manufacturing method.

[4] In any one of [1] to [3], the active energy ray-curable composition forming the first transfer layer includes the following (A), (B), (C) and (D) ( However, the total of (A) and (B) is 100 parts by weight.)
(A) Polyfunctional (meth) acrylate: 50 to 90 parts by weight (B) Diol (b-1) having alicyclic structure, lactone (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meta ) Urethane (meth) acrylate obtained by reacting acrylate: 10 to 50 parts by weight (C) Curing reaction inhibitor: 0.1 to 20 parts by weight (D) Polymerization initiator: 0.1 to 10 parts by weight

[5] In any one of [1] to [4], the second transfer layer has the following (a-1): 5 to 40% by weight, (a-2): 1 to 70% by weight, -3): A method for producing a laminated molded article comprising a copolymer having a weight average molecular weight of 1,000 to 1,000,000 obtained by copolymerizing 1 to 94% by weight.
(A-1) Unsaturated monomer represented by the following formula (1) CH ₂ = C (R ¹ ) COOR ² (1)
(In Formula (1), R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkyl group which may have a branch having 8 to 30 carbon atoms.)
(A-2) Unsaturated monomer having ultraviolet absorbing group (a-3) Unsaturated monomer copolymerizable with unsaturated monomer of (a-1) and / or (a-2)

[6] The active energy ray-curable composition according to any one of [1] to [5], wherein the surface temperature of the injection-filled thermoplastic resin in contact with the cured film transfer film forms the first transfer layer. A method for producing a laminated molded body, wherein the laminate is held at a temperature equal to or higher than a thermosetting start temperature of an object for 1 second or more.

[7] In any one of [1] to [6], Td is a thermosetting start temperature of the active energy ray-curable composition forming the first transfer layer, and Tr is a resin temperature of the thermoplastic resin to be injected and filled. In such a case, the temperature difference Tr-Td is 50 ° C. or higher and 135 ° C. or lower.

[8] In any one of [1] to [7], the thermal curing start temperature of the active energy ray-curable composition forming the first transfer layer is Td, the resin temperature of the thermoplastic resin to be injected and filled is Tr, When the mold temperature of the injection mold is Tm,
180 ≦ (2 × (Tr−Td)) + Tm ≦ 300
A method for producing a laminated molded body, wherein

[9] A cured film transfer film for transferring and forming a cured film on the surface of a molded body, wherein the film is formed on a base film with an active energy ray-curable composition for forming a cured film. In a cured film transfer film having at least two transfer layers including one transfer layer and a second transfer for forming an adhesive layer between the cured film and the molded body in contact with the molded body, the first transfer layer comprises: The active energy ray-curable composition that is in a semi-cured state by irradiation with active energy rays and that forms the first transfer layer includes the following (A), (B), (C), and (D) ( However, the cured film transfer film is characterized in that the total of (A) and (B) is 100 parts by weight.)
(A) Polyfunctional (meth) acrylate: 50 to 90 parts by weight (B) Diol (b-1) having alicyclic structure, lactone (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meta ) Urethane (meth) acrylate obtained by reacting acrylate: 10 to 50 parts by weight (C) Curing reaction inhibitor: 0.1 to 20 parts by weight (D) Polymerization initiator: 0.1 to 10 parts by weight

[10] In [9], the first transfer layer that has been semi-cured by irradiation with active energy rays has a finger-tack property that prevents the first transfer layer forming material from adhering to the finger by touch and is active. The first transfer layer before irradiation with energy rays and the first transfer after irradiation with active energy rays are measured by a single reflection ATR surface reflection method using an infrared spectrophotometer, and a peak P ₈₁₀ at a wave number of ₈₁₀ cm ⁻¹ is obtained. from the ratio value of _P 810 _{/ P 1726} between the peak _{P 1726} at a wave number 1726 cm ^-1, curing rate calculated by the following formula, the cured film transfer film, characterized in that it is 0.6 or less.
Curing ratio = hardening rate = (active energy ray irradiation before _{P 810 / P 1726 - P 810} / P 1726 after active energy ray irradiation) / active energy ray before irradiation _P 810 _{/ P 1726}

[11] The cured film according to [9] or [10], wherein the first transfer layer semi-cured by irradiation with active energy rays has an absorbance at a wavelength of 254 nm of 0.1 to 2.0. Transfer film.

[12] In any one of [9] to [11], the second transfer layer has the following (a-1): 5 to 40% by weight, (a-2): 1 to 70% by weight, (a -3): A cured film transfer film comprising a copolymer having a weight average molecular weight of 1,000 to 1,000,000 obtained by copolymerizing 1 to 94% by weight.
(A-1) Unsaturated monomer represented by the following formula (1) CH ₂ = C (R ¹ ) COOR ² (1)
(In Formula (1), R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkyl group which may have a branch having 8 to 30 carbon atoms.)
(A-2) Unsaturated monomer having ultraviolet absorbing group (a-3) Unsaturated monomer copolymerizable with unsaturated monomer of (a-1) and / or (a-2)

[13] A laminated molded product produced by the method for producing a laminated molded product according to any one of [1] to [8].

[14] The laminate molded article according to [13], wherein a region of 30% or more of the laminate molded article has transparency of a total light transmittance of 10% or more and less than 15% of Haze.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated molded object which has the cured film excellent in the abrasion resistance and the weather resistance on the surface can be efficiently manufactured based on high productivity and economical efficiency.

ADVANTAGE OF THE INVENTION According to this invention, the product excellent in durability can be provided by forming the hardened film excellent in abrasion resistance, a weather resistance, etc. with high adhesiveness on the thermoplastic resin base-material surface.
The laminated molded body of the present invention can be used as a glass substitute for a TV, a liquid crystal monitor, a mobile phone, a glass window, or a similar part thereof, or a panorama roof, sunroof, rear window, front side window, side of a vehicle such as an automobile. Industrially useful as a window material for doors, back doors, sliding doors, hoods, roofs or similar parts.

It is typical sectional drawing which shows the injection molding process in the manufacturing method of the laminated molded body of this invention. In an Example, it is a figure which shows the test piece of the injection-molded shape B (dish type), (b) A figure is a top view, (a) A figure is sectional drawing which follows the AA line of (b) figure, c) The figure is sectional drawing which follows CC line of (b) figure.

  Hereinafter, embodiments of the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of the embodiments of the present invention, and is appropriately modified and implemented without departing from the spirit of the present invention. can do. In the present invention, the description “(meth) acryloyl” means “at least one selected from the group consisting of acryloyl and methacryloyl”, and the description “(meth) acrylate” consists of “acrylate and methacrylate”. Means at least one selected from the group ". Moreover, what added "(poly)" in front of the compound name like "(poly) butanediol" or "(poly) ethylene glycol" means the said compound and either or both of the polymers. To do.

  In the method for producing a laminated molded body of the present invention, a thermoplastic film is injected and filled into a cavity of an injection mold having a cured film transfer film, and the thermoplastic resin is injection-molded. In the method for producing the formed laminated molded body, the cured film transfer film includes a first transfer layer formed of an active energy ray-curable composition for forming the cured film on a base film, A first transfer layer having at least two transfer layers including a cured film and a second transfer layer for forming an adhesive layer between the molded body and being in contact with the molded body, and being semi-cured by irradiation with active energy rays A step of forming another transfer layer including a second transfer layer on the substrate to obtain the cured film transfer film, and the cured film transfer film in a direction in which the base film is in contact with the mold. A step of placing in the mold; The thermoplastic resin together with injecting and filling the said cavity, and having a step of performing a curing reaction of the first transfer layer by heat of the filling resin.

[Thermoplastic resin]
In the present invention, the thermoplastic resin to be injection-molded is not particularly limited, and a generally widely used thermoplastic resin can be used.

  As this thermoplastic resin, for example, acrylic resins such as polycarbonate and polymethyl methacrylate, polyester resins such as polyethylene terephthalate, styrene resins such as vinyl chloride resin and polystyrene, cellulose acetate, and polypropylene can be used. A polymer having a carbonyl group is more preferable from the viewpoint of adhesiveness to the second transfer layer which is an adhesive layer of the cured film transfer film suitable for the present invention. Further, from the viewpoint of preferably satisfying the physical properties as a molded article, polyester, polyarylate, polycarbonate, cellulose acetate and the like are preferable, and polycarbonate resin is more preferable, and aromatic polycarbonate resin is particularly preferable. These thermoplastic resins may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The aromatic polycarbonate resin according to the present invention is a resin obtained by reacting a dihydric alcohol as a dihydric alcohol with a carbonate precursor by an interfacial method or a melting method, and is a mixture of two or more kinds of polycarbonates. There may be. Examples of the carbonate precursor include carbonyl halides such as phosgene, carbonyl esters such as diphenyl carbonate, and haloformates. The aromatic polycarbonate according to the present invention preferably has a polystyrene-reduced weight average molecular weight of about 15,000 to 50,000 by the GPC method.

  The molecular weight of the polycarbonate resin used in the present invention is arbitrary, but is usually 10,000 to 35,000 as the viscosity average molecular weight [Mv] converted from the solution viscosity. By setting the viscosity average molecular weight to 10,000 or more, the mechanical strength is improved and it is suitable for applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is 35,000 or less, the fluidity is lowered and the molding process becomes easy. The viscosity average molecular weight is preferably 18,000 to 35,000, more preferably 20,000 to 30,000. By setting the viscosity average molecular weight to 18,000 or more, it is possible to suppress a decrease in impact strength when a cured film is formed on the surface. Further, two or more kinds of polycarbonate resins having different viscosity average molecular weights may be mixed.

Here, the viscosity average molecular weight [Mv] means that the intrinsic viscosity [η] (unit dl / g) at a temperature of 20 ° C. is obtained with an Ubbelohde viscometer using methylene chloride as a solvent, and the Schnell viscosity formula (η = 1.23 × 10 ⁻⁴ M ^0.83 ).

  The terminal hydroxyl group concentration of the polycarbonate resin used in the present invention is usually 2,000 ppm or less, preferably 1,500 ppm or less, more preferably 1,000 ppm or less. In addition, the lower limit is usually 10 ppm, preferably 30 ppm, more preferably 40 ppm, particularly in the polycarbonate resin produced by the transesterification method.

  By setting the terminal hydroxyl group concentration to 10 ppm or more, a decrease in molecular weight can be suppressed, and the mechanical properties of the resin composition tend to be further improved. Moreover, it exists in the tendency which the residence heat stability and color tone of a resin composition improve more by making terminal group hydroxyl group density | concentration into 2,000 ppm or less. When forming a cured film such as a hard coat, by applying a terminal hydroxyl group concentration of 100 to 2,000 ppm, preferably 200 to 1,000 ppm, and more preferably 300 to 1,000 ppm, with a high terminal hydroxyl group concentration, Its adhesion and durability are improved. The unit of terminal hydroxyl group concentration is the weight of the terminal hydroxyl group expressed in ppm with respect to the weight of the polycarbonate resin, and the measuring method is colorimetric determination (Macromol. Chem. 88 215 (1965) by the titanium tetrachloride / acetic acid method. ).

  For thermoplastic resins such as polycarbonate resins, various additives such as a mold release agent, a heat stabilizer, an ultraviolet absorber, an antistatic agent, a colorant, a whitening agent, a difficulty, and the like within a range not impairing the object of the present invention. A flame retardant may be contained.

As the monomer unit constituting the polymer having a carbonyl group as a thermoplastic resin suitable for an injection molding resin, any known unit can be used, but it is usually used as a monomer unit for polyester, polyarylate, and polycarbonate. It is preferable to use the dihydric alcohol obtained.
Specific examples include the following.

  Hydroquinone, resorcinol, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7- Bifunctional phenolic compounds such as dihydroxynaphthalene;

  4,4′-biphenol, 3,3′-dimethyl-4,4′-dihydroxy-1,1′-biphenyl, 3,3′-di (t-butyl) -4,4′-dihydroxy-1,1 '-Biphenyl, 3,3', 5,5'-tetramethyl-4,4'-dihydroxy-1,1'-biphenyl, 3,3 ', 5,5'-tetra (t-butyl) -4, 4′-dihydroxy-1,1′-biphenyl, 2,2 ′, 3,3 ′, 5,5′-hexamethyl-4,4′-dihydroxy-1,1′-biphenyl, 2,4′-biphenol, 3,3′-dimethyl-2,4′-dihydroxy-1,1′-biphenyl, 3,3′-di (t-butyl) -2,4′-dihydroxy-1,1′-biphenyl, 2,2 '-Biphenol, 3,3'-dimethyl-2,2'-dihydroxy-1,1'-bi Eniru, 3,3' (t-butyl) -2,2'-biphenol compounds such as dihydroxy-1,1'-biphenyl;

  Bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 1, 1-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) pentane, 3,3-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 1,1-bis (4-hydroxyphenyl) hexane, 2,2-bis (4- Hydroxyphenyl) hexane, 3,3-bis (4-hydroxyphenyl) hexane, 2,2-bis (4-hydroxyphenyl) -4-methyl Pentane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) bisphenol compounds having no substituents on the aromatic rings such as cyclohexane;

  Bis (3-phenyl-4-hydroxyphenyl) methane, 1,1-bis (3-phenyl-4-hydroxyphenyl) ethane, 1,1-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2 A bisphenol compound having an aryl group as a substituent on an aromatic ring such as bis (3-phenyl-4-hydroxyphenyl) propane;

  Bis (4-hydroxy-3-methylphenyl) methane, 1,1-bis (4-hydroxy-3-methylphenyl) ethane, 1,1-bis (4-hydroxy-3-methylphenyl) propane, 2,2 -Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, bis (4-hydroxy-3-ethylphenyl) methane, 1,1-bis ( 4-hydroxy-3-ethylphenyl) ethane, 1,1-bis (4-hydroxy-3-ethylphenyl) propane, 2,2-bis (4-hydroxy-3-ethylphenyl) propane, 1,1-bis (4-hydroxy-3-ethylphenyl) cyclohexane, 2,2-bis (4-hydroxy-3-isopropylphenyl) propane, 2,2-bis 4-hydroxy-3- (sec-butyl) phenyl) propane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) ethane, 2 , 2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxy-3,5-dimethylphenyl) cyclohexane, bis (4-hydroxy-3,6-dimethylphenyl) Methane, 1,1-bis (4-hydroxy-3,6-dimethylphenyl) ethane, 2,2-bis (4-hydroxy-3,6-dimethylphenyl) propane, bis (4-hydroxy-2,3, 5-trimethylphenyl) methane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) ethane, 2,2-bis (4-hydroxy-) , 3,5-trimethylphenyl) propane, bis (4-hydroxy-2,3,5-trimethylphenyl) phenylmethane, 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) phenylethane, A bisphenol compound having an alkyl group as a substituent on an aromatic ring such as 1,1-bis (4-hydroxy-2,3,5-trimethylphenyl) cyclohexane;

  Bis (4-hydroxyphenyl) (phenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -1-phenylpropane, bis (4- A bisphenol compound in which a divalent group connecting aromatic rings such as hydroxyphenyl) (diphenyl) methane and bis (4-hydroxyphenyl) (dibenzyl) methane has an aryl group as a substituent;

  Bisphenol compounds in which aromatic rings such as 4,4′-dihydroxydiphenyl ether and 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenyl ether are connected by an ether bond; 4,4′-dihydroxydiphenyl sulfone Bisphenol compounds in which aromatic rings such as 3,3 ′, 5,5′-tetramethyl-4,4′-dihydroxydiphenylsulfone are connected by sulfone bonds; 4,4′-dihydroxydiphenyl sulfide, 3,3 ′, A bisphenol compound in which aromatic rings such as 5,5′-tetramethyl-4,4′-dihydroxydiphenyl sulfide are linked by a sulfide bond;

  Bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, phenolphthalein, etc .:

[Hardened film transfer film]
The cured film transfer film of the present invention includes a base film, a first transfer layer formed on the base film and made of an active energy ray-curable composition for forming a cured film, and a cured film to be formed. It has at least a second transfer layer for forming an adhesive layer between the film and the injection-molded body, and a binder layer and a decorative layer are provided between the first transfer layer and the second transfer layer as necessary. In addition, a transfer layer for other functional layers may be formed.

<Base film>
As a base film, it has heat resistance to the temperature at the time of injection molding of a thermoplastic resin, and has a releasability that can be easily peeled off after the first transfer layer formed thereon is completely cured. There is no particular limitation as long as it is, but a resin film such as polypropylene resin, polyethylene resin, polyamide resin, polyester resin, polyacrylic resin, polyvinyl chloride resin, aluminum foil, copper foil, etc. Cellulose-based sheets such as metal foil, glassine paper, coated paper, cellophane, or a laminate of these films or sheets can be used.

  When the base film has good peelability of the first transfer layer formed thereon, the first transfer layer can be directly formed on the base film.

  When the peelability between the base film and the first transfer layer is not sufficient, the release layer may be formed entirely on the first transfer layer forming surface of the base film. The release layer forming material includes melamine resin release agent, silicone resin release agent, fluororesin release agent, cellulose derivative release agent, urea resin release agent, polyolefin resin release agent , Paraffinic mold release agents and composite mold release agents can be used, and the formation method includes gravure coating method, roll coating method, spray coating method, lip coating method, comma coating method, etc. Printing methods such as gravure printing and screen printing.

Although there is no restriction | limiting in particular, It is preferable that the thickness of a base film is about 10-100 micrometers.
If the thickness of the base film is too thin, the film may break due to insufficient mechanical strength when the transfer layer is formed or handled as a cured film transfer film. In some cases, the material becomes difficult, and it is difficult to follow the mold shape at the time of molding, and transferability may be lowered.

<First transfer layer>
The composition of the active energy ray-curable composition for forming the first transfer layer is not particularly limited, but semi-curing by irradiation with active energy rays and subsequent curing by heat of the injection filling resin at the time of subsequent injection molding are performed satisfactorily. Therefore, it is preferable to contain at least the following components (A), (B), (C) and (D), and further contain the following components (E) to (G) as necessary.
(A) polyfunctional (meth) acrylate (B) diol (b-1) having an alicyclic structure, lactone (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meth) acrylate are reacted. Urethane (meth) acrylate obtained (C) Curing reaction inhibitor (D) Polymerization initiator (E) Hindered amine light stabilizer (F) Colloidal silica (G) Solvent

(A) Polyfunctional (meth) acrylate Examples of the (A) polyfunctional (meth) acrylate used in the active energy ray-curable composition as the coating agent 2 include the following.

1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neo Pentyl glycol adipate di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) Modified bisphenol A di (meth) acrylate, EO-modified phosphoric acid di (meth) acrylate, allylated cyclohexyl di (meth) aurate, isocyanuric acid ethoxy modified di ( ) Acrylate, isocyanuric acid ethoxy modified tri (meth) acrylate, trimethylolpropane di (meth) acrylate and other di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris (acrylic) Roxyethyl) isocyanurate, propionic acid modified dipentaerythritol tetra (meth) acrylate, propionic acid modified dipentaerythritol Penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Kapurorakuron modified dipentaerythritol hexa (meth) acrylate such as trifunctional or more (meth) acrylate;
An adduct of the above-mentioned tri- or higher functional (meth) acrylate and γ-mercaptopropyltrimethoxysilane, colloidal silica and / or silicate hydrolysis condensate;
An adduct of a hydroxyl group-containing acrylate such as glycerin diacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate and isocyanatepropyltriethoxysilane, colloidal silica and / or silicate hydrolysis condensate;

  To alicyclic skeleton isocyanate compounds such as isophorone diisocyanate and hydrogenated diphenylmethane diisocyanate, (poly) butadiene diol, (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) ester diol, (poly) After adding hydroxyl groups of one or more compounds such as caprolactone-modified diol, (poly) carbonate diol, (poly) spiroglycol, etc., 2-hydroxyethyl (meth) acrylate, 2-hydroxy is added to the remaining isocyanate groups. (Meth) acrylate having a hydroxyl group such as propyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl acrylate, pentaerythritol triacrylate Urethane poly (meth) acrylates obtained by response;

  Bisphenol A diglycidyl ether, novolak epoxy resins, trisphenol methane triglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether , Propylene glycol diglycidyl ether, 2,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 2- (3,4-epoxycyclohexyl-5,5- Spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis (2,3-epoxycyclopentyl) ether, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd.) An alicyclic epoxy resin) (meth) epoxy modified with acrylic acid (meth) acrylates such as:

  These polyfunctional (meth) acrylates can be used alone or in combination of two or more.

  In the active energy ray-curable composition for forming the first transfer layer, the content of (A) polyfunctional (meth) acrylate is (A) polyfunctional (meth) acrylate and (B) urethane for reasons of scratch resistance. When the total amount of the (meth) acrylate component is 100 parts by weight, it is preferably 50 to 90 parts by weight, more preferably 60 to 90 parts by weight, still more preferably 60 to 80 parts by weight.

(B) Urethane (meth) acrylate Obtained by reacting diol (b-1) having an alicyclic structure, lactones (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meth) acrylate (B As the urethane (meth) acrylate, for example, those synthesized using the following raw materials can be used.

Examples of the diol (b-1) having an alicyclic structure include compounds in which indene, naphthalene, azulene, anthracene and the like are hydroxyalkylated; bicyclo [5,3,0] decandimethanol, bicyclo [4,4,0 ] decane dimethanol, bicyclo [4,3,0] nonane methanol, norbornanedimethanol, tricyclodecanedimethanol, 1,3-adamantane-diol (1,3-dihydroxy-tricyclo [3,3,1,1 ^{3 , 7} ] decane, 3,9-bis (2-hydroxy-1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, isosorbide, hydrogenated bisphenol A, 1, 4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol And the like.

  Examples of the lactone (b-2) include β-propiolactone, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, α, β, γ-trimethoxy-δ-valerolactone, β -Methyl- [epsilon] -isopropyl- [epsilon] -caprolactone, lactide, glycolide and the like.

  Examples of the polyisocyanate (b-3) include tolylene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, tetramethylxylylene diisocyanate, trimethylhexamethylene. Examples include diisocyanate, 1,5-naphthalene diisocyanate, norbornene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, and lysine diisocyanate.

  As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3 -Phenoxypropyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, etc. are mentioned.

  In order to produce (B) urethane (meth) acrylate according to the present invention, for example, first, tricyclodencan dimethanol is used as the diol (b-1) having an alicyclic structure, and the lactone (b-2) is used. Using ε-caprolactone, an addition reaction is performed by heating to 50 to 220 ° C., preferably 100 to 200 ° C., in the presence of a catalyst to synthesize a caprolactone-modified diol having an alicyclic structure. At this time, the reaction rate is low at low temperatures, and thermal decomposition occurs at high temperatures, which is not preferable. Examples of the catalyst used in this reaction include inorganic salts, inorganic acids, organic alkali metals, tin compounds, titanium compounds, aluminum compounds, zinc compounds, tungsten compounds, molybdenum compounds, and zirconium compounds. After reacting caprolactone-modified diol having an alicyclic structure with diisocyanate (polyisocyanate (b-3)) at 20 to 100 ° C., preferably at 40 to 80 ° C. for 1 to 20 hours, hydroxyl group-containing (meth) acrylate is further added. (B) Urethane (meth) acrylate can be obtained by making it react at 20-100 degreeC for 1 to 20 hours.

  Here, in the reaction of caprolactone-modified diol having an alicyclic structure with diisocyanate, and a reaction product thereof with a hydroxyl group-containing (meth) acrylate, it is preferable to use a catalyst in order to accelerate the reaction. As a catalyst which can be used here, tertiary amine compounds such as organic tin compounds typified by dibutyltin dilaurate, dioctyltin dilaurate and dibutyltin diacetate, and triethylamine can be used.

  In the active energy ray-curable composition for forming the first transfer layer, the content of (B) urethane (meth) acrylate is (A) polyfunctional (meth) acrylate and (B) urethane (for reasons of weather resistance). When the total amount of the (meth) acrylate component is 100 parts by weight, it is preferably 10 to 50 parts by weight, more preferably 10 to 40 parts by weight, and still more preferably 20 to 40 parts by weight.

(C) Curing reaction inhibitor Examples of the (C) curing reaction inhibitor include benzotriazole-based, benzophenone-based, benzoate-based, and cyanoacrylate-based ultraviolet absorbers.

  Specific examples thereof include, for example, 2- (2-hydroxy-5-methyl) benzotriazole, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-5′-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy) -3 ', 5'-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-3', 5'-t-butylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazole-2 -Yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2′-hydroxy-3 ′, 5′-t-pentylbenzotriazol) 2- [2′-hydroxy-5 ′-(1,1,3,3, -tetramethylbutyl)] benzotriazole, 2- (2′-hydroxy-3′-s-butyl-5′-t -Butylbenzotriazole, 2- (2'-hydroxy-3-dodecyl-5'-methylbenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2-methylenebis [4-1,1,3,3-tetramethylbutyl] -6- (2H-benzotriazole-2- Yl) phenol], 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] propionate and polyethylene glycol Benzotriazoles such as 2-hydroxybenzophenone, 5-chloro-2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy Benzophenones such as 2-hydroxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2- ( 4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(methyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl ) -5-[(Ethyl) oxy] -phenol, 2- (4 6-diphenyl-1,3,5-triazin-2-yl-[(propyl) oxy] -phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [ (Butyl) oxy] -phenol, triazines such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, phenyl salicylate, p- Salicylates such as tert-butylphenyl salicylate and p-octylphenyl salicylate 3-hydroxyphenylbenzoate, phenylene-1,3-benzoate, 2-ethylhexyl-2-cyano-3,3′-diphenylacrylate, ethyl-2-cyano -3,3'-diphenyl acrylate, 2- (4,6-diphenyl-1,3,5-triazin-2-yl ) -5-hexyloxyphenol and the like.

  These curing reaction inhibitors such as ultraviolet absorbers can be used alone or in combination of two or more.

In the active energy ray-curable composition for forming the first transfer layer, the content of the (C) curing reaction inhibitor is (A) a polyfunctional (meta) ) When the total amount of acrylate and (B) urethane (meth) acrylate components is 100 parts by weight, it is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, More preferably, it is 0.5-5 weight part.
(C) If there are more curing reaction inhibitors than the above upper limit, semi-curing of the first transfer layer, which will be described later, cannot be sufficiently performed, and there is a possibility that touch tackiness may occur. Curing proceeds too much by irradiation, making it difficult to achieve a good semi-cured state.

(D) Polymerization initiator (D) Examples of the polymerization initiator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2- Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1- (4 Acetophenones such as -morpholinophenyl) -1-butanone; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone; 2,4-dimethyl Thioxanthones such as thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenones such as benzophenone or xanthones; 2-benzyl- Α-amino ketones such as 2-dimethylamino 1-1 (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Osphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H- Examples include photopolymerization initiators such as pyrrol-1-yl) phenyl titanium and η5-cyclopentadienyl-η6-cumenyliron (1 +)-hexafluorophosphate (1-).
These polymerization initiators can be used alone or in combination of two or more.

  (D) The content of the photopolymerization initiator is the (A) polyfunctional (meth) acrylate and (B) of the active energy ray-curable composition forming the first transfer layer, from the viewpoint of the hardness of the cured film to be formed. When the total amount of the urethane (meth) acrylate component is 100 parts by weight, it is preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight.

(E) Hindered amine light stabilizer (E) As the hindered amine light stabilizer, for example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-hexanoyloxy-2,2,6, 6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetramethylpiperidine, 4-steayloxy-2,2,6,6-tetramethylpiperidine, succinic acid-bis (2,2 , 6,6-tetramethylpiperidine), sebacic acid-bis (2,2,6,6-tetramethylpiperidine), sebacic acid-bis (1,2,2,6,6-pentamethyl-4-piperidine), 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione, N-methyl-3-dodecyl -1-(-2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, N-acetyl-3-dodecyl-1- (2,2,6,6-tetramethyl- 4-piperidine), trimesic acid-tris (2,2,6,6-tetramethyl-4-piperidyl) and the like. These light stabilizers can be used alone or in combination of two or more.

  The blending amount of the light stabilizer is 10% when the total amount of the (A) polyfunctional (meth) acrylate and the (B) urethane (meth) acrylate component is 100 parts by weight from the viewpoint of the hardness of the formed cured film. The amount is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight.

(F) Colloidal silica (F) Examples of colloidal silica include water, methanol, isopropanol, n-butanol, isobutanol, ethylene glycol, ethyl cellosolve, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, and methyl. Silica having an average particle size of 1 to 200 nm is preferable, and silica having an average particle size of 5 to 50 nm is more preferable, using isobutyl ketone, dimethylacetamide, xylene and a mixed solvent thereof as a dispersion medium.

  Here, the average particle diameter of the silica is measured by photographing particles using a scanning electron microscope (JSM-7401F manufactured by JEOL Ltd.), and image analysis software ImageProPlus (manufactured by Media Cybernetics) for 50 particles of this image. Is measured.

  As (F) colloidal silica, in particular, when colloidal silica dispersed in an organic solvent is used, it is preferable because it exhibits high transparency when formed into a coating film. Typically, a solvent having a hydroxyl group or a ketone It is preferable to use an organosilica sol dispersed in a polar solvent having a group. Specific examples of such colloidal silica include “IPA-ST” (IPA-dispersed organosilica sol, manufactured by Nissan Chemical Industries), “MEK-ST” (MEK-dispersed organosilica sol, manufactured by Nissan Chemical Industries), “MIBK”. -ST "(MIBK-dispersed organosilica sol, manufactured by Nissan Chemical Co., Ltd.) or the like, or sols (for example, PGM-dispersed organosilica sol, etc.) obtained by replacing these with a solvent having another hydroxyl group as a raw material.

  (F) The colloidal silica may be either surface-modified or unmodified, but surface-modified colloidal silica is preferably used. For the modification of colloidal silica, a hydrolyzable silicon group or a compound having a silicon group to which a hydroxyl group is bonded can be used. Hydrolyzable silicon groups generate silanol groups by hydrolysis, and these silanol groups react with and bind to silanol groups present on the surface of the colloidal silica to produce surface-modified colloidal silica.

  Examples of silicon group-containing compounds used for the modification of colloidal silica include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, phenyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, β -(Meth) acryloyloxyethyltrimethoxysilane, γ- (meth) acryloyloxypropyltrimethoxysilane, γ- (meth) acryloyloxypropyltriethoxysilane, γ- (meth) acryloyloxypropylmethyldimethoxysilane, vinylorimethoxy Silane, vinyltriethoxysilane, vinylmethyldimethoxysilane, p-vinylphenyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-g Glycidyl trimethoxysilane, .gamma.-aminopropyltrimethoxysilane, p- styryl trimethoxysilane, 3-mercaptopropyl methyl dimethoxy silane, can be mentioned 3-mercaptopropyl trimethoxysilane. A silicon group containing compound can be used individually or in combination of 2 or more types.

  As a surface modification method of colloidal silica, it can be synthesized by reacting colloidal silica with a hydrolyzable silicon group-containing compound, a catalyst, and water at 20 to 100 ° C. for 1 to 40 hours.

  Catalysts used for this reaction include inorganic acids such as hydrochloric acid, hydrofluoric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid; formic acid, acetic acid, oxalic acid, p-toluenesulfonic acid, acrylic acid, methacrylic acid Organic acids such as alkali; acetylacetone aluminum, aluminum 2,2,6,6-tetramethyl-3,5-heptanedionate, aluminum diisopropoxide ethyl acetoacetate, aluminum diisobutoxide ethyl acetoacetate, boric acid Butoxide, dibutyltin dilaurate, dibutyltin dioctate and the like can be used. The amount of these catalysts used is 0.0001 to 5 parts by weight, preferably 0.01 to 1 part by weight, based on 100 parts by weight of the total amount of colloidal silica and hydrolyzable silicon group-containing compound. The amount of water required for hydrolysis is 0.5 to 100 equivalents, preferably 1 to 30 equivalents, relative to the hydrolyzable silicon group.

  As the colloidal silica used in this reaction, colloidal silica in an acidic or basic dispersion form can be used, and acidic colloidal silica is preferred.

  When (F) colloidal silica is blended with the active energy ray-curable composition for forming the first transfer layer, the blending amount is (A) polyfunctional (meth) acrylate and (B) urethane (as solid content). When the total amount of the (meth) acrylate component is 100 parts by weight, it is preferably 50 parts by weight or less, for example, 10 to 40 parts by weight.

(G) Solvent The active energy ray-curable composition for forming the first transfer layer may contain a solvent from the viewpoint of handling the composition. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2 Ethers such as butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- Ether esters such as butoxyethyl acetate and 3-methoxypropyl acetate; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and acetic acid pro Le, esters such as ethyl acetate and butyl acetate; and the like. These solvents can be used alone or in combination of two or more.

  When the active energy ray-curable composition forming the first transfer layer contains a solvent, the active energy ray-curable composition may be prepared as a composition having a solid content concentration of about 5 to 60% by weight. preferable.

<Method for forming first transfer layer>
The method for forming the first transfer layer using the active energy ray-curable composition as described above is not particularly limited, and the active energy ray-curable composition is applied onto a base film according to a conventional method, What is necessary is just to irradiate an active energy ray to the formed coating film and to make it a semi-hardened state.
Examples of the coating method include dipping method, flow coating method, spray method, spin coating method, gravure coating method, roll coating method, blade coating method, air knife coating method, offset method, and bar coating method. Can also be applied. It can also be applied like an image by printing or the like.

  The coating amount is not particularly limited, but the coating is preferably performed so that the film thickness of the first transfer layer semi-cured by irradiation with active energy rays is 1 to 50 μm, preferably 2 to 10 μm.

  When a solvent is used in the active energy ray curable composition as desired, the curable composition is applied to a substrate film and then dried to remove the solvent. The drying conditions in this case vary depending on the boiling point of the solvent, the material of the base film, the coating amount of the curable composition, etc., but in general, the drying is performed at 30 to 120 ° C. for 1 to 30 minutes, preferably Perform at 50-100 ° C. for 1-5 minutes.

  After drying as necessary, the active energy rays used when curing the coating film of the curable composition by irradiating the active energy rays include xenon lamps, low pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halides. Ultraviolet rays emitted from light sources such as lamps, carbon arc lamps, tungsten lamps, etc., and electron beams, α rays, β rays, γ rays, etc., usually taken out from particle accelerators of 20 to 2000 kV can be used.

<Semi-cured state of first transfer layer>
In the present invention, after the active energy ray-curable composition for forming the first transfer layer is applied to the base film, the first transfer layer is brought into a semi-cured state by irradiation with active energy rays.

As the degree of this semi-cured state, when the first transfer layer is touched with a finger, the curable composition that is a material for forming the first transfer layer has a touch-tack property that does not adhere to the finger and is active. The first transfer layer before irradiation with energy rays and the first transfer layer after irradiation with active energy rays are measured by a single reflection ATR surface reflection method using an infrared spectrophotometer, and a peak P ₈₁₀ at a wave number of ₈₁₀ cm ⁻¹ . and the ratio value of _P 810 _{/ P 1726} between the peak _{P 1726} at a wave number 1726 cm ^-1, curing rate calculated by the following formula, 0.6 or less, especially 0.5 or less, especially 0.4 to be the following It is preferable that it is a moderate grade.
Hardening rate = (active energy ray irradiation before _{P 810 / P 1726 - P 810} / P 1726 after active energy ray irradiation) / active energy ray before irradiation _P 810 _{/ P 1726}

  The semi-cured first transfer layer has an absorbance at a wavelength of 254 nm of 0.1 to 2.0, particularly 0.3 to 1.5, particularly 0.5 to 1.3. Is preferred.

  The curing rate and absorbance are indicators for the degree of curing, and if the curing rate is too large, curing has progressed too much and cannot follow the shape of the molded body during injection molding, Defects such as exfoliation and cracking are likely to occur, and if it is too small, it is unpreferable because finger tackiness is exhibited in an uncured state.

  Also, if the absorbance is too small, curing has progressed too much, and it is difficult to follow the shape of the molded body at the time of injection molding, and defects such as peeling of the cured film and occurrence of cracks are likely to occur. It is not preferable because of the finger touch tackiness.

<Second transfer layer>
The constituent material of the second transfer functioning as an adhesive layer between the cured film formed by the first transfer and the injection molded body is not particularly limited, but at least one selected from the group of compounds having a (meth) acryloyl group. It is preferable to contain an acrylic resin obtained by polymerizing a compound. Therefore, the second transfer layer is preferably formed of a composition containing such an acrylic resin.

  Here, the resin obtained by polymerizing at least one compound selected from the group of compounds having a (meth) acryloyl group is a group of compounds having a (meth) acryloyl group in order to adjust the physical properties of the formed adhesive layer. A copolymer of a plurality of types of compounds selected from There are no particular restrictions on the type and copolymerization ratio of the compound having a (meth) acryloyl group used in this case, but if the molecular weight of the compound is too large, it will be difficult to produce a polymer. The number is preferably 50 or less, more preferably 40 or less, and particularly preferably 35 or less.

  As the compound having a (meth) acryloyl group as a polymerization component of an acrylic resin suitable for the second transfer layer, a compound represented by the following formula (1A) is preferably used.

CH ₂ = C (R ¹¹ ) COOR ¹² (1A)

(In Formula (1A), R ¹¹ and R ¹² each independently represents an organic substituent.)

Preferably, R ¹¹ and R ¹² are an alkyl group which may have a substituent, and the alkyl group may have a branched or cyclic structure. R ¹¹ is more preferably an alkyl group having 5 or less carbon atoms, and even more preferably a linear alkyl group having 5 or less carbon atoms.

In order to easily adjust the mechanical strength, adhesiveness, and water absorption of the second transfer layer, R ¹¹ and R ¹² are preferably linear alkyl groups. In particular, R ¹² greatly affects the properties of the adhesive layer to be formed. When adjusting the mechanical strength, adhesiveness, and water absorption of the adhesive layer, the carbon number is preferably 30 or less. Further, for the same reason, R ¹¹ is preferably a linear alkyl group having 5 or less carbon atoms, particularly preferably a hydrogen atom, a methyl group or an ethyl group.

From the viewpoint of improving the adhesion of the second transfer layer, the alkyl group represented by R ¹² preferably has 3 or less carbon atoms, and particularly preferably a methyl group.

On the other hand, in order to adjust the water absorption rate of the adhesive layer formed by the second transfer layer, R ¹² is preferably an alkyl group having 8 or more carbon atoms, and the carbon number of the alkyl group is more preferably It has 10 or more carbon atoms, more preferably 12 or more, particularly preferably 16 or more carbon atoms, preferably 30 or less carbon atoms, more preferably 25 or less carbon atoms.

Among them, in the formula (1A), R ¹¹ is preferably a hydrogen atom, a methyl group or an ethyl group, and R ¹² is preferably an alkyl group which may have a branch having 8 to 30 carbon atoms. Accordingly, the compound represented by the formula (1A) is preferably represented by the following formula (1).

Further, from the viewpoint of improving the weather resistance of the laminated molded body, it is preferable that the light transmittance of light having a wavelength of 300 nm is not more than a certain value as a whole of the adhesive layer regardless of the thickness of the formed adhesive layer. In order to adjust the light transmittance, it is preferable that the substituent represented by R ¹² in the formula (1A) is a group that absorbs or blocks light in the vicinity of a wavelength of 300 nm, and more specifically, A compound having a (meth) acryloyl group having a so-called ultraviolet absorbing group derived from a compound used as an ultraviolet absorber is preferred.

Moreover, in order to adjust the light transmittance of the light having a wavelength of 300 nm of the formed adhesive layer, the ultraviolet absorbing group used for the organic substituent represented by R ¹² in the formula (1A) is 2,4- Groups having a benzophenone skeleton such as dihydroxybenzophenone, groups having a triazine skeleton, groups having a benzotriazole skeleton such as 2- (5′-methyl-2′-hydroxyphenyl) benzotriazole, ethyl-2-cyano-3,3 A group having a cyanoacrylate skeleton such as' -diphenyl acrylate, a group having a salicylate skeleton such as phenyl salicylate, or a group having a benzylidene malonate skeleton such as diethyl-p-methoxybenzylidene malonate is preferably used. Among these, a group having a benzophenone skeleton, a group having a triazine skeleton, and a group having a benzotriazole skeleton are preferable, and a group having a benzotriazole skeleton is particularly preferably used.

  Therefore, the second transfer layer has the following (a-1): 5 to 40% by weight, (a-2): 1 to 70% by weight, and (a-3): 1 to 94, in particular. It is preferable to contain an acrylic resin made of a copolymer having a weight average molecular weight of 1,000 or more and 1,000,000 or less, which is obtained by copolymerization with wt%.

(A-1) An unsaturated monomer represented by the following formula (1) (hereinafter sometimes referred to as “unsaturated monomer (a-1)”)
CH ₂ = C (R ¹ ) COOR ² (1)
(In Formula (1), R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkyl group which may have a branch having 8 to 30 carbon atoms.)
(A-2) Unsaturated monomer having ultraviolet absorbing group (hereinafter sometimes referred to as “unsaturated monomer (a-2)”)
(A-3) an unsaturated monomer copolymerizable with the unsaturated monomer (a-1) and / or (a-2) (hereinafter referred to as “unsaturated monomer (a-3)”) There may be cases.)

  More specifically, as the unsaturated monomer (a-1), 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate , Isostearyl (meth) acrylate, cetyl (meth) acrylate, behenyl (meth) acrylate, and the like.

  The unsaturated monomer (a-2) is a compound for adjusting the light transmittance of light having a wavelength of 300 nm of the formed adhesive layer. For example, a benzotriazole skeleton represented by the formula (2) (Hereinafter sometimes referred to as “compound (2)”), a compound having a benzophenone skeleton represented by formula (3) (hereinafter sometimes referred to as “compound (3)”), And a compound having a triazine skeleton as represented by the formula (4) (hereinafter sometimes referred to as “compound (4)”).

(In Formula (2), X represents a hydrogen atom or a chlorine atom, R ³ represents a hydrogen atom, a methyl group, or a tertiary alkyl group having 4 to 8 carbon atoms. R ⁴ is linear or branched. And represents an alkylene group having 2 to 10 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, and n represents 0 or 1.)

(In Formula (3), R ⁵ has the same meaning as in Formula (2). R ⁶ represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ⁷ represents a hydrogen atom or a hydroxyl group. R ⁸ represents a hydrogen atom, a hydroxyl group or an alkoxy group having 1 to 6 carbon atoms.)

(In Formula (4), R ⁵ has the same meaning as in Formula (2). R ⁹ represents a direct bond, —CH ₂ CH ₂ O— or CH ₂ CH (OH) —CH ₂ O—, and n represents R represents an integer of 1 to 5. R ¹⁰ independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group, and p and q each independently represents an integer of 0 to 5.)

  Examples of the unsaturated monomer (a-3) include (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, alkyl vinyl ether, alkyl vinyl ester, styrene, and derivatives thereof. Can be mentioned.

  Among these, specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl. (Meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, ethyl carbitol (meth) Acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, cyanoethyl (meth) acrylate, methoxypolyethylene group Alkoxypolyalkylene glycol (meth) acrylate such as coal (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate Glycidyl ether, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) Acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalate, 2-acryloyloxyethyl phthalate, 2- (meth) acryloyloxyethyl hexa Drophthalate, 2- (meth) acryloylpropyl phthalate, (meth) acryloyloxyethyl succinate, 2-isocyanatoethyl (meth) acrylate, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyl Examples include methyltrimethoxysilane and 3- (meth) acryloyloxypropylmethyltriethoxysilane.

  Specific examples of (meth) acrylonitrile include α-chloroacrylonitrile, α-chloromethylacrylonitrile, α-trifluoromethylacrylonitrile, α-methoxyacrylonitrile, α-ethoxyacrylonitrile, and vinylidene cyanide.

  Specific examples of (meth) acrylamide derivatives include N-methyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N -Methoxy (meth) acrylamide, N, N-dimethoxy (meth) acrylamide, N-ethoxy (meth) acrylamide, N, N-ethoxy (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, N -(2-hydroxyethyl) (meth) acrylamide, N, N-dimethylaminomethyl (meth) acrylamide, N- (2-dimethylamino) ethyl (meth) acrylamide, N, N-methylenebis (meth) acrylamide, N, N-ethylenebis (meth) acrylic Mention may be made of the bromide and the like.

  Specific examples of the alkyl vinyl ether include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, hexyl vinyl ether and the like.

  Specific examples of the alkyl vinyl ester include vinyl formate, vinyl acetate, vinyl acrylate, vinyl butyrate, vinyl caproate, and vinyl stearate.

  Specific examples of the styrene derivative include styrene, p-styryltrimethoxysilane, α-methylstyrene, vinyltoluene, chloromethylstyrene, and the like.

  Furthermore, the resin obtained by polymerizing at least one compound selected from the group of compounds having a (meth) acryloyl group may be a copolymer with another repeating unit having no (meth) acryloyl group. Absent. In this case, the copolymerization ratio of at least one compound selected from the group of compounds having a (meth) acryloyl group and other repeating units is not particularly limited, but in order to obtain the effects of the present invention sufficiently, The ratio of the repeating unit is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, and particularly preferably 10 mol% or less.

  The acrylic resin preferably has a polystyrene-reduced molecular weight weight average molecular weight of 10,000 or more and 1,000,000 or less, particularly 30000 or more and 300,000 or less by gel permeation chromatography (GPC). If the molecular weight of the acrylic resin is too large, the composition for forming the second transfer layer becomes highly viscous and the surface smoothness is impaired, and if it is too small, the adhesion strength is not sufficient.

  The composition for forming the second transfer layer can contain a solvent for the purpose of improving the convenience in obtaining a resin by polymerization and the coating property in forming the second transfer layer.

  Examples of the solvent used include alcohols such as methanol, ethanol, n-propanol, isopropanol, and n-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; 2-methoxyethanol, 2-ethoxyethanol, 2 -Ethers such as butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; 2-methoxyethyl acetate, 2-ethoxyethyl acetate, Ether esters such as 2-methoxypropyl acetate and 2-butoxyethyl acetate; aromatic hydrocarbons such as toluene and xylene; ethyl acetate, proacetate Le, esters such as ethyl acetate and butyl acetate; and the like, may further be a mixture in any proportion of these solvents.

  When the composition for forming the second transfer layer contains a solvent, the acrylic resin content (solid content concentration) of this composition is not particularly limited, but is 1% by weight to 80% by weight, particularly 5% by weight to 50%. It is preferable that it is below wt%.

  The composition for forming the second transfer layer also includes the following stabilizers (for example, hindered amine-based stabilizers), antioxidants (for example, phenol-based, sulfur-based, phosphorus-based antioxidants), anti-blocking agents, Various additives added to this type of composition such as a leveling agent and a silane coupling agent should be added in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the solid content in the composition. Can do.

-Light stabilizer Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-octanoyloxy-2,2,6,6-tetra Methylpiperidine, bis (2,2,6,6-tetramethyl-4-piperidyl) diphenylmethane-p, p'-dicarbamate, bis (2,2,6,6-tetramethyl-4-piperidyl) benzene-1 , 3-disulfonate, hindered amines such as bis (2,2,6,6-tetramethyl-4-piperidyl) phenyl phosphite, nickel bis (octylphenyl ester) Examples include nickel complexes such as fido, nickel complex-3,5-di-t-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, etc. These agents may be used alone or in combination of two or more. May be.

Silane coupling agent As the silane coupling agent, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N -Β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriacetoxysilane, γ-anilino Examples include propyltrimethoxysilane, vinyltrimethoxysilane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-ureidopropyltriethoxysilane, and the like. Can be used. By adding such an agent, an intermediate between the thermoplastic resin injection-molded body, the second transfer layer, the second transfer layer, the first transfer layer (cured film) thereon or a binder layer described later provided as necessary. Adhesion with the transfer layer is maintained for a long time. These agents may be used alone or in combination of two or more.

In order to form the second transfer layer with such a composition, it is usually on a semi-cured first transfer layer formed on a base film or an intermediate transfer layer such as a binder layer described later provided as necessary. The composition is applied. The coating method in this case is not particularly limited, and is a dip coating method, flow coating method, spray method, spin coating method, bar coating method, curtain coating method, die coating method, gravure coating method, roll coating method, blade coating method and It can be applied by any coating method such as an air knife coating method.
The application may be performed in a single step or may be performed in two or more steps. However, it is usually more economical and preferable to perform the application once.

  When the composition for forming the second transfer layer contains a solvent, the composition is applied onto the first transfer layer in a semi-cured state on the base film or an intermediate transfer layer such as a binder layer described later provided as necessary. And then drying to remove the solvent. The drying conditions in this case vary depending on the boiling point of the solvent, the material of the base film, the coating amount, etc., but in general, the drying is performed at 30 to 150 ° C. for 1 to 60 minutes, preferably at 80 to 120 ° C. Perform for 1-10 minutes.

  The thickness of the second transfer layer is usually 1 μm or more, preferably 5 μm or more, more preferably 8 μm or more, and still more preferably as the thickness of the adhesive layer formed on the resulting laminate formed body in order to ensure sufficient adhesion. Is 10 μm or more, and is usually 50 μm or less, preferably 20 μm or less, and more preferably 15 μm or less, because it has excellent drying properties when a composition using a solvent is applied and dried.

<Other layers>
In the cured film transfer film of the present invention, in order to improve the adhesion between the first transfer layer and the second transfer layer, a binder layer may be provided therebetween. The material for forming the binder layer is preferably selected in accordance with the material of the other transfer layer. For example, acrylic resin, vinyl acetate resin, epoxy resin, polyester resin, polycarbonate resin, butyral resin, gelatin , Cellulose resin, polyamide resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer, urethane resin, and other suitable resins are selected, and these resins are dissolved in a solvent as required. Used to form a binder layer as a product.

  The thickness of the binder layer is preferably 0.1 to 50 μm, more preferably 1 to 10 μm. When the binder layer is thinner than the above range, the effect of improving the adhesiveness by the binder layer is not sufficient, and when it exceeds the above range, problems such as film breakage occur during transfer molding.

  Examples of the solvent used for forming the binder layer according to the present invention include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and isobutanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone. Ethers such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; 2 Ether ethers such as methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 3-methoxypropyl acetate; Aromatic hydrocarbons such as xylene, ethyl acetate, propyl acetate, esters such as ethyl acetate and butyl acetate; and the like. These may be used alone or in combination of two or more.

  Moreover, in the cured film transfer film of this invention, you may form a pattern layer and / or a metal vapor deposition layer for a decoration between a 1st transfer layer and a 2nd transfer layer.

  The pattern layer is a pattern, pattern, pattern, etc. that is made of ink. The ink used to form the pattern layer is azo pigments, isoinsolin, quinacridone, phthalocyanine blue, aniline black and other organic pigments, cobalt blue, valve Inorganic pigments such as stalks, yellow lead, and titanium oxide, and various organic dyes can be used.

  The metal vapor deposition layer is formed by vacuum deposition of a metal such as aluminum, tin, silver, copper, or chromium.

  Furthermore, in the cured film transfer film of the present invention, a functional layer other than the binder layer and the decorative layer may be formed between the first transfer layer and the second transfer layer.

[Injection molding and transfer]
In the present invention, the cured film transfer film and the thermoplastic resin as described above are used, and after the cured film transfer film is disposed in the injection mold, the thermoplastic resin is injected and filled into the mold cavity. The molding and transfer of the transfer layer are performed, and the semi-cured first transfer layer is additionally cured by the heat of the filling resin to be completely cured.

  Hereinafter, this method will be described with reference to FIG. 1 showing an example of the production process of the method for producing a laminated molded body of the present invention.

In FIG. 1, 1 is a mold composed of a fixed mold 1A and a possible mold 1B, 2 is a cured film transfer film on which a base film 2a, a first transfer layer 2b, and a second transfer layer 2c are formed, and 3 is a heat Plastic resin, 4 is an injection device, 5 is a runner for introducing the thermoplastic resin 3 into the cavity of the mold 1, and 6 is a laminated molded body.
In FIG. 1, the cured film transfer film 2 has only the first transfer layer 2b and the second transfer layer 2c as transfer layers. As described above, the first transfer layer 2b and the second transfer layer 2c Between these, other functional layers such as a binder layer may be formed.

<Arrangement of cured film transfer film>
First, as shown in FIG. 1A, the cured film transfer film 2 is opened with the mold 1 open, and the base film 2a side is the mold surface of the mold (the movable mold 1B in FIG. 1A). Arrange them so that they touch each other.

<Injection filling of thermoplastic resin>
Next, after the mold is clamped, the thermoplastic resin 3 is injected and filled into the cavity of the mold 1 from the injection device 4 through the runner 5 as shown in FIG.

  In injection molding by injection filling of this thermoplastic resin 3, in order to perform effective additional curing and completely cure the first transfer layer, the following conditions (1) to (3) are preferably 1 or more: It is preferable to adopt injection conditions that more preferably satisfy 2 or more, and most preferably satisfy all the conditions (1) to (3).

(1) During injection filling of the thermoplastic resin 3, the surface temperature of the thermoplastic resin 3 on the side in contact with the cured film transfer film 2 is such that the heat of the active energy ray curable composition forming the first transfer layer 2b. It is held for 1 second or more, more preferably 1 to 5 seconds at a temperature equal to or higher than the curing start temperature Td (hereinafter, this holding time may be referred to as “Td or higher holding time”).
Here, the surface temperature of the thermoplastic resin that is in contact with the cured film transfer film that has been injected and filled can be measured by a temperature sensor disposed in the mold cavity. At this time, even if the temperature sensor is not in direct contact with the molten resin, the thickness of the cured coated transfer film is thin so as not to affect the temperature measurement. The fact that the surface temperature was maintained at a temperature equal to or higher than the thermal curing start temperature Td of the active energy ray-curable composition of the first transfer layer for 1 second or more is confirmed by checking the transition of the measured temperature in time series. Can be sought.
Conventionally, even if a thermoplastic resin that has been heated and melted is injection-filled, the thermoplastic resin is instantaneously cooled in the mold, and thus, on the side in contact with the cured film transfer film of the thermoplastic resin. In order to maintain the surface temperature at a temperature equal to or higher than the thermal curing start temperature of the active energy ray curable composition of the first transfer layer for 1 second or longer, it is necessary to adjust the resin temperature or mold temperature of the thermoplastic resin. is there.

(2) When the thermosetting start temperature of the active energy ray-curable composition forming the first transfer layer 2b is Td and the resin temperature of the thermoplastic resin 3 to be injected and filled is Tr, the temperature difference Tr-Td is 50 to 135 ° C, preferably 50 to 120 ° C, more preferably 50 to 100 ° C.

(3) Td is the thermosetting start temperature of the active energy ray-curable composition forming the first transfer layer 2b, Tr is the resin temperature of the thermoplastic resin 3 to be injected and filled, and the mold temperature of the injection mold 1 Is Tm,
Preferably, 180 ≦ (2 × (Tr−Td)) + Tm ≦ 300,
More preferably, 180 ≦ (2 × (Tr−Td)) + Tm ≦ 250,
Particularly preferably, 200 ≦ (2 × (Tr−Td)) + Tm ≦ 250
And

When the holding time equal to or greater than Td in (1) is too short, Tr−Td in (2) is too small, or (2 × (Tr−Td)) + Tm in (3) is too small, There is a case where the first transfer layer cannot be completely cured due to insufficient curing by additional curing.
On the other hand, when the holding time of (1) is too long, Tr-Td of (2) is too large, or (2 × (Tr-Td)) + Tm of (3) is too large, curing is performed. The film transfer film 2 may be wrinkled or melted due to heat.
In addition, the thermosetting start temperature Td of the active energy ray-curable composition for forming the first transfer layer is usually about 150 to 250 ° C. in the above-described preferable active energy ray-curable composition blend.

The injection molding conditions in the present invention are not particularly limited as long as the conditions (1) to (3) are satisfied. For example, the following conditions are adopted.
Resin temperature of thermoplastic resin: Any resin temperature suitable for injection molding of the selected molding material may be used. For example, it is 260 to 320 ° C. for polycarbonate resin.
Mold temperature: about 30 to 130 ° C. Resin filling rate: 10 to 250 cm ³ / sec
Holding pressure: 25 to 60% of resin filling pressure for 2 to 30 seconds Cooling time: 5 to 30 seconds

<Demolding of laminated molded body>
After performing the transfer and additional curing together with the injection molding, as shown in FIG. 1C, the mold is opened and the laminated molded body 6 is taken out. In the laminated molded body 6, the first transfer layer 2b and the second transfer layer 2c of the cured film transfer film 2 are transferred to the surface of the injection molded body, and the first transfer layer 2b is completely cured by additional curing. The resulting cured film is formed with good adhesion by the adhesive layer of the second transfer layer.

[Laminated molded product]
There is no restriction | limiting in particular about the form of the laminated molded object of this invention manufactured in this way, It may be any forms, such as a plate-shaped, sheet-shaped, film-shaped, various-shaped molded object. Moreover, the cured film forming surface may be planar, or partially or entirely curved.

In addition, there is no particular limitation on the thickness and size of the injection-molded body made of the thermoplastic resin of the laminated molded body. For example, in a window material application, it is used as a plate having a thickness of about 2 to 10 mm. The area is preferably about 400 cm ^{2 to 2} m ² . Further, the design surface of the product is such that the radius of curvature R [m] in the long side direction is 5000R to 20000R, particularly about 10000R to 20000R, and the short side R is about 1000R to 15000R, particularly about 5000R to 10,000R. You may curve so that the surface which comprises the side may become convex.

In the laminated molded body of the present invention, the surface hardness (Martens hardness) of the cured film on the surface is preferably 160 N / mm ² or more. When the surface hardness is less than 160 N / mm ² , sufficient scratch resistance cannot be obtained, and the use as a product is limited. In particular, the surface hardness is preferably 200 N / mm ² or more. The higher the surface hardness, the better.

  Moreover, when using the laminated molding of this invention as a window member use, the area | region of 30% or more, Preferably 35% or more, More preferably, 40 to 100%, total light transmittance is 10% or more, Haze is It preferably has a transparency of less than 15%.

When the total light transmittance of the laminated molded body is less than 10% or the haze is 15% or more, it becomes difficult to apply to applications requiring transparency.
The total light transmittance of the laminated molded body is preferably 15% or more, more preferably 20% or more. Moreover, Haze is preferably 4% or less, more preferably 2% or less.
The larger the total light transmittance of the laminated molded body, the better. However, the upper limit is usually 99%.
Moreover, although the haze of a laminated molded body is so preferable that it is small, the normal minimum is 0.1%.

  In addition, the total light transmittance, the Haze value, and the like of the laminated molded body of the present invention are values measured by the method described in the Examples section described later.

  Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples.

[Production Example 1]
In a flask equipped with a thermometer, a stirrer and a reflux condenser, 200 g of propylene glycol monomethyl ether, 100 g of toluene, 150 g of methyl methacrylate, 40 g of stearyl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) phenyl] -2H-benzotriazole (RUTSUA 93 manufactured by Otsuka Chemical Co., Ltd.) 10 g and 2,2′-azobis (2,4-dimethylvaleronitrile) 2 g were added, reacted at 65 ° C. for 3 hours, and further 2,2′-azobis ( 2,4-dimethylvaleronitrile) 1 g was added and reacted for 3 hours to obtain an acrylic resin 1 containing a copolymer having a nonvolatile content (resin content) of 40% by weight and a polystyrene equivalent weight average molecular weight of 180,000 by GPC. .

[Production Example 2]
In a flask equipped with a thermometer, stirrer and reflux condenser, 200 g of propylene glycol monomethyl ether, 100 g of methyl isobutyl ketone, 148 g of methyl methacrylate, 40 g of stearyl methacrylate, (2, [2′-hydroxy-5 ′-(methacryloxyethyl) 10 g of phenyl] -2H-benzotriazole (RUVA93 manufactured by Otsuka Chemical Co., Ltd.), 2 g of 2-methacryloyloxyethyl phosphate, and 2 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were added and reacted at 65 ° C. for 3 hours. Further, 1 g of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and reacted for 3 hours to obtain a non-volatile content (resin content) of 40% by weight and a polystyrene equivalent weight average molecular weight of 150,000 by GPC. An acrylic resin 2 containing a polymer was obtained.

[Production Example 3]
Add 39.3 g of tricyclodecane dimethanol, 46.6 g of ε-caprolactone, and 0.1 g of tetraoctyltin to a flask equipped with a thermometer, stirrer and reflux condenser, and heat at 180 ° C. for 15 hours under a nitrogen stream. After stirring, 88.9 g of isophorone diisocyanate, 46.5 g of 2-hydroxyethyl acrylate, 55.3 g of phenoxydiethylene glycol acrylate, 0.2 g of dibutyltin laurate and 0.1 g of hydroquinone monomethyl ether were added, and the mixture was stirred at 80 ° C. under an air stream. The mixture was heated and stirred for a time to obtain urethane acrylate.

[Preparation of coating agent for transfer layer formation]
Each material was mixed with the formulation shown in Table 1 to prepare each coating agent for forming a transfer layer.
Details of each material described in Table 1 are as follows.

Acrylic resin 1: Acrylic resin 1 produced in Production Example 1
Acrylic resin 2: Acrylic resin 2 produced in Production Example 2
Binder resin: Vinyl chloride / vinyl acetate manufactured by Union Carbide
/ Hydroxyl-modified acrylic resin (trade name: VAGF)
Multifunctional acrylate 1: Dipentalysitol hexaacrylate manufactured by Nippon Kayaku Co., Ltd.
(Product name: Kayalad DPHA)
Multifunctional acrylate 2: Pentaerythritol triacrylate manufactured by Osaka Organic Chemical Co., Ltd.
(Product name: Biscote 300)
Multifunctional acrylate 3: Isocyanuric acid EO-modified acrylate manufactured by Toagosei Co., Ltd.
(Product name: Aronix M313)
Urethane acrylate: Urethane acrylate produced in Production Example 3 Curing reaction inhibitor 1: Triazine UV absorber manufactured by Ciba Specialty Chemicals
(Product name: TINUVIN400)
Curing reaction inhibitor 2: Benzotriazole ultraviolet rays manufactured by Ciba Specialty Chemicals
Absorbent (trade name: TINUVIN213)
HALS1: Hindered amine light stabilizer manufactured by Ciba Specialty Chemicals
(Product name: TINUVIN123)
HALS2: Sankyo Co., Ltd. hindered amine light stabilizer (trade name: Sanol LS765)
PGM: Propylene glycol monomethyl ether Photopolymerization initiator 1: Ciba Specialty Chemicals
(Product name: Irgacure 184)

[Manufacture of cured film transfer film]
On a base sheet using a 38 μm thick polyester resin film as a base film,
A melamine resin release agent is applied by a gravure coating method to form a release layer having a thickness of 1 μm, and then a coating agent for forming the first transfer layer (coating agent T1, T2 or T3) is used with a bar coater. And dried by heating at 80 ° C. for 2 minutes. Next, the coating film was irradiated with a predetermined amount of ultraviolet rays shown in Tables 2 and 3 using a 120 W / cm ² high-pressure mercury lamp. Next, a coating agent for forming a second transfer layer (coating agent P1 or P2) was applied using a bar coater, and heated and dried at 120 ° C. for 5 minutes to produce a cured film transfer film (Examples 1 to 3, 7-11, Comparative Examples 1-3).

  When a binder layer is formed between the first transfer layer and the second transfer layer (Examples 4 to 6), the first transfer layer is formed in the same manner as described above, and then the binder layer forming coating agent is formed. (Binder) was applied using a bar coater, and then a second transfer layer was formed in the same manner as described above to produce a transfer film.

The first transfer layer, the binder layer, and the second transfer layer were formed so that the thicknesses of the obtained laminated molded bodies were as follows.
First transfer layer: 6 μm
Binder layer: 5 μm
Second transfer layer: 7 μm

[Thermoplastic resin]
The following two types of thermoplastic resins were used for injection molding.
PC: Aromatic polycarbonate resin pellet “Iupilon (registered trademark) S-3000UR” manufactured by Mitsubishi Engineering Plastics Co., Ltd. (This resin pellet was dried in hot air at 120 ° C. for 5 hours before injection molding.)
PMMA: “Product name Acripet VH” manufactured by Mitsubishi Rayon Co., Ltd. (This resin pellet was dried with hot air at 100 ° C. for 5 hours before injection molding.)

[injection molding]
<Injection molding of shape A (flat plate)>
Using a molding resin shown in Tables 2 and 3 and the following injection molding machine, a cured film transfer film was placed in a mold to produce a test piece of 150 mm × 100 mm × thickness 3 mm under the following molding conditions. As the gate, a film gate (150 mm width, 2 mm thickness) was used. In the mold cavity, a temperature sensor was installed on the cavity surface (150 mm × 100 mm surface) 10 mm in the molten resin flow direction from the gate tip, and a cured film transfer film was disposed on the surface with the sensor. And the temperature state of filling resin was measured with the said sensor over a cured film transfer film.
Injection molding machine: “J150EP-2M” manufactured by Nippon Steel Works (clamping force 150t)
Molding conditions: Molding resin temperature: listed in Tables 2 and 3
Mold temperature: listed in Tables 2 and 3
Filling time: 1.8 seconds
Holding time of Td or more: listed in Tables 2 and 3
Holding pressure: 50% of the peak pressure during injection for 15 seconds
Cooling time: 20 seconds

<Injection molding of shape B (dish mold)>
Using the molding resin shown in Tables 2 and 3 and the following injection molding machine, a cured film transfer film is placed in the mold, and the shape shown in FIG. 2 is 100 mm × 100 mm × 3 mm thickness × 10 mm aperture H under the following molding conditions. The test piece was manufactured. A side gate (10 mm width, 2 mm thickness) was used as the gate. In the mold cavity, a temperature sensor was installed on the cavity surface (150 mm × 100 mm surface) 10 mm in the molten resin flow direction from the gate tip, and a cured film transfer film was disposed on the surface with the sensor. And the temperature state of filling resin was measured with the said sensor over a cured film transfer film.
Injection molding machine: “J150EP-2M” manufactured by Nippon Steel Works (clamping force 150t)
Molding conditions: Molding resin temperature: listed in Tables 2 and 3
Mold temperature: listed in Tables 2 and 3
Filling time: 1.2 seconds
Holding time of Td or more: listed in Tables 2 and 3
Holding pressure: 50% of the peak pressure during injection for 15 seconds
Cooling time: 20 seconds

  When the shape A is molded, the cured film transfer film is inserted into the stationary mold side of the injection mold so as to avoid the molding resin gate, and when the shape B is molded, an injection living mold as shown in FIG. Inserted on the movable side. Subsequently, in any case, molding was performed in the order of mold clamping → resin filling → holding pressure → cooling → mold opening → product removal (extrusion). At the time of taking out the obtained laminated molded body, the cured film was transferred to the molded body side, and the base film of the cured film transfer film remained in the mold.

[Examples 1 to 11 and Comparative Examples 1 to 3]
The laminated molded bodies obtained under the conditions shown in Tables 2 and 3 were evaluated as follows, and the results are shown in Tables 2 and 3.
In addition, evaluation about a laminated molded object was performed about the test piece of the shape A (flat plate) except evaluation of a moldability.

<Absorbance>
Apply the coating agent for forming the first transfer layer on the quartz plate under the same conditions as when forming the first transfer layer of the cured film transfer film so that the film thickness is the same as that of the first transfer layer of the cured film transfer film. A cured sample was prepared, and the absorbance at a wavelength of 254 nm was measured for this sample using an ultraviolet-visible spectrophotometer (V570 manufactured by JASCO Corporation).

<Curing rate>
For the above absorbance measurement sample, it was measured by single reflection ATR surface reflection method using an infrared spectrophotometer (Thermo Co. Magna550), the peak at the peak _{P 810} and the wave number 1726 cm ^-1 at a wave number 810 cm ^-1 _{P 1726} From the value of the ratio P ₈₁₀ / P ₁₇₂₆ , the following formula was used.
Hardening rate = (active energy ray irradiation before _{P 810 / P 1726 - P 810} / P 1726 after active energy ray irradiation) / active energy ray before irradiation _P 810 _{/ P 1726}

<Tactile touch>
During the production of the cured film transfer film, the first transfer layer was applied to the base film and cured, and then the state of the coating film surface was confirmed by finger touch and evaluated according to the following criteria.
○: The component of the film does not adhere to the finger.
X: The component of the film adheres to the finger.

<Moldability>
The test piece of each laminated molded body was visually observed and evaluated according to the following criteria.
◯: There are no defects such as peeling of the cured film and occurrence of cracks, which is good.
X: The cured film has defects such as wrinkles and peeling cracks and cannot be practically used.

<Haze>
About the test piece of the laminated molded object, haze value (H%) was calculated | required according to JISK-7136.

<Adhesion (initial adhesion)>
In accordance with JIS K5600, 100 squares are made at intervals of 2 mm on the surface of the cured film of the laminate molded specimen, and cellophane tape (24 mm made by Nichiban) is pressed and peeled upward. It was evaluated with.
○: None of the 100 squares peeled off the cured film.
X: There exists peeling of a cured film.

<Abrasion resistance>
The test specimen of the laminated molded body is subjected to a Taber abrasion test in accordance with JIS K7204 under the conditions of a wear wheel CS-10F, a load of 500 g, and a rotation speed of 100 cycles, and a difference ΔH (%) in haze value before and after the test is calculated. It was measured. The smaller this value, the better the scratch resistance.

<Abrasion resistance after additional UV irradiation>
The cured film surface after the substrate film of the test piece of the molded laminate is peeled off, after irradiation with ultraviolet rays of 3000 mJ / cm ² using a high pressure mercury lamp of 120 W / cm ² at an ultraviolet irradiation apparatus, the JIS K7204 In conformity, a Taber abrasion test was performed under the conditions of wear wheel CS-10F, a load of 500 g, and a rotation speed of 100 cycles, and a haze value difference ΔH (%) before and after the test was measured.

<Dust adhesion>
The surface of the cured film of the test piece of the laminated molded body was visually observed and evaluated according to the following criteria.
○: Dust does not adhere.
X: Dust adheres.

<Total light transmittance / Haze>
About the test piece of a laminated molded object, the total light transmittance was calculated | required according to JIS K-7361-1, and the haze value (%) was calculated | required according to JIS K-7136.

<Moisture and heat resistant adhesion>
The specimen of the laminated molded body was allowed to stand for 2 weeks under the conditions of 50 ° C. and 95% Rh, and then evaluated by the following two methods (1) and (2). Evaluation was made according to the criteria.
(1) It observed visually and confirmed the presence or absence of peeling of a cured film, and the occurrence of defects, such as a crack.
(2) A cross-cut tape peeling evaluation based on JIS D0202-1988 was performed.
That is, 10 × 10 squares (total of 100 squares) are cut into the cured film, and a cellophane tape (“CT24” manufactured by Nichiban Co., Ltd.) is stuck on the finger pad, and then the tape is peeled off. The presence or absence of peeling was confirmed visually.
○: No peeling or defect in both (1) and (2).
Δ: Peeling and cracks were observed in (1), but no peeling was observed in (2).
X: Peeling, cracks, etc. are not observed in (1), but peeling occurs in (2).
XX: Defects such as peeling and cracking are observed in both (1) and (2).

<Weather resistant adhesion>
Using a xenon arc type weather resistance promotion evaluation tester, a weather resistance promotion test is performed on a test piece of a laminated molded body under the conditions of a black panel temperature of 70 ° C., a water spray for 18 minutes in a 120-minute cycle, and an integrated ultraviolet ray irradiation amount of 500 mJ / m ^2. After the test, the same evaluation criteria were evaluated by the two methods (1) and (2) in the same manner as in the evaluation of the moisture and heat resistance adhesion.

[Reference Example 1]
Except for not using a cured film transfer film, injection molding of shape A (flat plate) was performed using PC in the same manner as described above, and coating agent P1 was applied to the surface of the obtained injection molded body using a bar coater. After heating and drying at 120 ° C. for 5 minutes, the coating agent T1 was applied using a bar coater, heated and dried at 80 ° C. for 2 minutes, and then an ultraviolet ray having an amount shown in Table 2 using a 120 W / cm ² high-pressure mercury lamp. Was cured by irradiation to form a cured film.

  The thickness of the adhesive layer by the coating agent P1 and the thickness of the cured film by the coating agent T1 were the same as in Example 1.

  About the test piece of this laminated molded body, the total light transmittance, Haze, adhesion, scratch resistance, dust adhesion, wet heat resistance, and weather resistance were evaluated in the same manner as in Example 1, and the results are shown in Table 3. It was shown to.

  From the above results, the following can be understood.

  In Comparative Example 1, since the UV irradiation amount to the first transfer layer during production of the cured film transfer film was large and the cured film was in a completely cured state, cracks occurred in the cured film during injection molding, particularly in a dish-shaped test piece. It is impractical.

  In Comparative Example 2, the UV irradiation amount to the first transfer layer at the time of production of the cured film transfer film is small, but the coating agent for forming the first transfer layer does not contain the curing reaction inhibitor, so the UV irradiation amount is small. Since curing proceeds and almost complete curing occurs, as in Comparative Example 1, cracks occur in the cured film during injection molding.

  In Comparative Example 3, since the first transfer layer of the cured film transfer film was formed only by drying and was not cured by UV irradiation, there was a touch-tack property, and the transfer layer flow and transfer unevenness occurred during injection molding, which was not practical. Is possible.

On the other hand, after the first transfer layer of the cured film transfer film was semi-cured by UV irradiation, the first transfer layer was further cured by the heat of the filling resin at the time of injection molding to form a cured film. In Examples 1 to 11, laminated molded articles having excellent scratch resistance and weather resistance can be obtained.
In these examples, almost the same results were obtained with the scratch resistance and the additional UV irradiation scratch resistance, and the first transfer layer was completely cured by additional curing in the mold during injection molding. I understand that.

  In Examples 7 to 9, since the value of Tr−Td and / or (2 × (Tr−Td)) + Tm is small and the additional curing is slightly insufficient, these conditions are within the preferred range of the present invention. Scratch resistance is inferior compared with Examples 1-6, 10, and 11 which satisfy | fill.

Example 10 is an example in which the UV irradiation amount to the first transfer layer at the time of manufacturing the cured film transfer film is relatively small, and the curing rate in the semi-cured state of the first transfer layer is small compared to the other examples. However, a laminated molded article excellent in scratch resistance and weather resistance was obtained without any problem.
On the other hand, in Example 11, the UV irradiation amount to the first transfer layer at the time of manufacturing the cured film transfer film was relatively large, and the curing rate of the first transfer layer in the semi-cured state was higher than that of the other examples. Although it was a large example, a laminated molded article having excellent scratch resistance and weather resistance was obtained without any problem.

Reference Example 1 is an example in which a cured film is formed by an application method to an injection molded body, not a cured film transfer film. In this method, after injection molding, coating and drying are performed for forming a cured film. Further, the curing process is required, the process is complicated, and the scratch resistance of the formed cured film is inferior to that of the cured films formed in Examples 1 to 6 and Examples 10 and 11, and dust is also generated. It is attached.
This is because, as in the present invention, when the first transfer layer semi-cured by irradiation with active energy rays is completely cured by additional curing with heat of the filling resin in the mold, it is uniformly distributed over the entire first transfer layer. When heat is applied and sufficient curing is performed, when all curing is performed with active energy rays, such uniform and sufficient curing cannot be performed, and the formed cured film has a slight scratch resistance. This is presumably due to being inferior.

  The laminated molded body of the present invention has a cured film excellent in scratch resistance and weather resistance on the surface of a thermoplastic resin molded body, and is used for headlamp covers, vehicle window materials, vehicle roof materials, and buildings. It is useful for window materials, exterior wall materials for buildings, soundproof walls for roads, display face plates, mobile phone members, and the like. Furthermore, since it can be a laminated molded body having high scratch resistance, abrasion resistance, and weather resistance while maintaining high transparency, it is used as a resin window material, particularly outdoors, for a long period of time. It is suitable as a window material for automobiles exposed to temperature change, humidity change, ultraviolet irradiation, infrared irradiation, and wind and rain.

DESCRIPTION OF SYMBOLS 1 Metal mold | die 1A Fixed mold | type 1B Movable type | mold 2 Cured film transfer film 2a Base film 2b 1st transfer layer 2c 2nd transfer layer 3 Thermoplastic resin 4 Injection apparatus 5 Runner 6 Laminated molding 10 Dish type test piece

Claims (14)

In a method for producing a laminated molded body having a cured film formed on a surface by injection-filling a thermoplastic resin into a cavity of an injection mold having a cured film transfer film and injection-molding the thermoplastic resin ,
The cured film transfer film comprises a first transfer layer formed of an active energy ray-curable composition for forming the cured film on a substrate film, and the cured film and the molded body in contact with the molded body. Having at least two transfer layers including a second transfer layer for forming an adhesive layer;
A step of forming another transfer layer including a second transfer layer on the first transfer layer that has been semi-cured by irradiation with active energy rays to obtain the cured film transfer film;
Disposing the cured film transfer film in the mold such that the base film is in a direction in contact with the mold;
A method for producing a laminated molded body comprising: injecting and filling a thermoplastic resin into the cavity, and performing a curing reaction of the first transfer layer by an amount of heat of the filled resin. 2. The first transfer layer in a semi-cured state by active energy ray irradiation according to claim 1, has a touch-tack property that prevents the first transfer layer forming material from adhering to the finger by finger touch, and active energy ray irradiation. The first transfer layer after the previous first transfer layer and the first transfer after irradiation with active energy rays are measured by a single reflection ATR surface reflection method using an infrared spectrophotometer, and a peak P ₈₁₀ at a wave number of ₈₁₀ cm ⁻¹ and a wave number of 1726 cm ^{− A} method for producing a laminated molded article, wherein the curing rate calculated by the following formula from the value of the ratio P ₈₁₀ / P _{1726 to} the peak P ₁₇₂₆ in ¹ is 0.6 or less.
Hardening rate = (active energy ray irradiation before _{P 810 / P 1726 - P 810} / P 1726 after active energy ray irradiation) / active energy ray before irradiation _P 810 _{/ P 1726}   3. The method for producing a laminated molded article according to claim 1, wherein the absorbance at a wavelength of 254 nm of the first transfer layer made semi-cured by irradiation with active energy rays is 0.1 or more and 2.0 or less. The active energy ray-curable composition for forming the first transfer layer according to any one of claims 1 to 3 includes the following (A), (B), (C), and (D) (provided that (A) And (B) is 100 parts by weight in total).
(A) Polyfunctional (meth) acrylate: 50 to 90 parts by weight (B) Diol (b-1) having alicyclic structure, lactone (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meta ) Urethane (meth) acrylate obtained by reacting acrylate: 10 to 50 parts by weight (C) Curing reaction inhibitor: 0.1 to 20 parts by weight (D) Polymerization initiator: 0.1 to 10 parts by weight 5. The second transfer layer according to claim 1, wherein the second transfer layer has the following (a-1): 5 to 40 wt%, (a-2): 1 to 70 wt%, and (a-3): 1. A method for producing a laminated molded article, comprising a copolymer having a weight average molecular weight of 1,000 or more and 1,000,000 or less, obtained by copolymerizing ˜94% by weight.
(A-1) Unsaturated monomer represented by the following formula (1) CH ₂ = C (R ¹ ) COOR ² (1)
(In Formula (1), R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkyl group which may have a branch having 8 to 30 carbon atoms.)
(A-2) Unsaturated monomer having ultraviolet absorbing group (a-3) Unsaturated monomer copolymerizable with unsaturated monomer of (a-1) and / or (a-2)   6. The thermosetting of the active energy ray-curable composition according to claim 1, wherein the surface temperature of the injection-filled thermoplastic resin that is in contact with the cured film transfer film is the first active layer. A method for producing a laminated molded body, wherein the laminate molded body is held at a temperature equal to or higher than a temperature for 1 second or longer.   In any one of Claim 1 to 6, when the thermal curing start temperature of the active energy ray-curable composition forming the first transfer layer is Td, and the resin temperature of the thermoplastic resin to be injected and filled is Tr, the temperature Difference Tr-Td is 50 degreeC or more and 135 degrees C or less, The manufacturing method of the laminated molded object characterized by the above-mentioned. 8. The injection molding die according to claim 1, wherein Td is a thermosetting start temperature of the active energy ray-curable composition forming the first transfer layer, Tr is a resin temperature of the thermoplastic resin to be injected and filled, and When the mold temperature is Tm,
180 ≦ (2 × (Tr−Td)) + Tm ≦ 300
A method for producing a laminated molded body, wherein A cured film transfer film for transferring and forming a cured film on the surface of a molded body, the first transfer layer being formed on a base film with an active energy ray-curable composition for forming a cured film And a cured film transfer film having at least two transfer layers including a second transfer for forming an adhesive layer between the cured film and the molded body in contact with the molded body,
The first transfer layer is in a semi-cured state by irradiation with active energy rays, and the active energy ray curable composition for forming the first transfer layer has the following (A), (B), (C) and A cured film transfer film comprising (D) (however, the total of (A) and (B) is 100 parts by weight).
(A) Polyfunctional (meth) acrylate: 50 to 90 parts by weight (B) Diol (b-1) having alicyclic structure, lactone (b-2), polyisocyanate (b-3) and hydroxyl group-containing (meta ) Urethane (meth) acrylate obtained by reacting acrylate: 10 to 50 parts by weight (C) Curing reaction inhibitor: 0.1 to 20 parts by weight (D) Polymerization initiator: 0.1 to 10 parts by weight In Claim 9, the 1st transfer layer made into the semi-hardened state by active energy ray irradiation has a touch tuck property in which this 1st transfer layer formation material does not adhere to a finger by finger touch, and active energy ray irradiation The first transfer layer after the previous first transfer layer and the first transfer after irradiation with active energy rays are measured by a single reflection ATR surface reflection method using an infrared spectrophotometer, and a peak P ₈₁₀ at a wave number of ₈₁₀ cm ⁻¹ and a wave number of 1726 cm ⁻ A cured film transfer film, wherein the curing rate calculated by the following formula from the value of the ratio P ₈₁₀ / P _{1726 to} the peak P ₁₇₂₆ in ¹ is 0.6 or less.
Curing ratio = hardening rate = (active energy ray irradiation before _{P 810 / P 1726 - P 810} / P 1726 after active energy ray irradiation) / active energy ray before irradiation _P 810 _{/ P 1726}   The cured film transfer film according to claim 9 or 10, wherein the absorbance at a wavelength of 254 nm of the first transfer layer which has been semi-cured by irradiation with active energy rays is 0.1 or more and 2.0 or less. The second transfer layer according to any one of claims 9 to 11, wherein the second transfer layer has the following (a-1): 5 to 40% by weight, (a-2): 1 to 70% by weight, and (a-3): 1. A cured film transfer film comprising a copolymer having a weight average molecular weight of 1,000 or more and 1,000,000 or less, obtained by copolymerization of ˜94% by weight.
(A-1) Unsaturated monomer represented by the following formula (1) CH ₂ = C (R ¹ ) COOR ² (1)
(In Formula (1), R ¹ represents a hydrogen atom, a methyl group or an ethyl group, and R ² represents an alkyl group which may have a branch having 8 to 30 carbon atoms.)
(A-2) Unsaturated monomer having ultraviolet absorbing group (a-3) Unsaturated monomer copolymerizable with unsaturated monomer of (a-1) and / or (a-2)   A laminated molded product produced by the method for producing a laminated molded product according to any one of claims 1 to 8.   14. The laminated molded product according to claim 13, wherein a region of 30% or more of the laminated molded product has transparency with a total light transmittance of 10% or more and less than 15% of Haze.

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