JP2019107838A - Decorative film, and decorative formed body - Google Patents

Abstract

To provide a decorative film which is excellent in productivity, excellent in formability when formed as a decorative film, existing on the surface of a decorative formed body after formation, sufficiently tolerable to temperature change in a car, and excellent in abrasion resistance and chemical resistance (such as resistance to a sunscreen cream), and a decorative formed body covered with the decorative film on the surface.SOLUTION: A decorative film 101 comprises a laminate including a hard coat layer HC and a substrate layer 1, in which the hard coat layer HC is a cured product of a photo-curable composition, the hard coat layer HC has an alkylene oxide chain, and the photo-curable composition contains a monomer having a (meth)acryloyl group and a photo-polymerization initiator.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative film carrying a hard coat layer formed from a specific acrylic paint on the surface. In addition, the present invention relates to a decorative molded body, the surface of which is coated with the decorative film, and the hard coat layer is located outside.

  Resin molded products are often used for portable information terminal devices such as smartphones, laptop computers, home appliances, and interior and exterior parts of automobiles. These resin molded products are usually decorated by painting, printing or the like on their surfaces in order to enhance the design after molding a plastic resin. The surface of the decorated molded article is required to be excellent in abrasion resistance, abrasion resistance, and chemical resistance (such as sunscreen cream resistance).

  Conventionally, for the purpose of imparting designability, a colored paint has been applied or printed on the surface of a resin molded product. In addition, in order to protect the surface, hard coat paint has been spray-coated or dip-coated on the surface of the resin molded product. However, it is difficult for such a conventional decoration method to perform decoration with high designability. Moreover, the method of decorating the surface of a resin molding using a decoration film as a method of having replaced with this, for there being a problem in productivity etc. has prevailed. A decorative film is what provided the pattern and the hard-coat layer by printing or application | coating on a base film.

  As a method of using a decoration film, (1) The method of laminating the decoration film on the surface of the resin molded article by setting the resin molded article molded in advance as an object of decoration, (2) Set in a mold There is a method of injecting a resin for injection molding to be decorated into the above-mentioned decorative film, and integrating the resin molded product and the decorative film. In any of the methods (1) and (2), there are a method involving peeling and transfer (transfer) of a part of layers constituting the decorative film and a method not involving the same. A method not involving peeling and transfer (transfer) is suitable for producing a deep-drawn decorative molding as compared with the method involved. In the method (2), the decorative film may be preformed prior to injection of the resin for injection molding. As means for preforming, in addition to vacuum forming, mechanical forming and the like can be mentioned.

  The use of various decorative films is proposed in Patent Documents 1 to 8. Patent Document 1 describes a multilayer body in which a layer made of an acrylic resin (A) and a layer made of an aliphatic polycarbonate resin (B) are laminated. It is described that by using the aliphatic polycarbonate resin (B) having a specific structure, a multilayer body excellent in transparency, heat resistance, impact resistance, UV discoloration resistance, and surface hardness can be obtained.

  In Patent Document 2, a methacrylic resin (with a glass transition temperature of at least one surface of a layer (A) of a polycarbonate resin material) as a resin film which is hard to break, excellent in whitening resistance, high in surface hardness and easy to be molded. Disclosed is a multilayer film formed by laminating a layer (B) of a methacrylic resin material containing 85 to 100 parts by mass of the polycarbonate resin material and 85 to 100 parts by mass of an acrylic rubber particle and 0 to 15 parts by mass of acrylic rubber particles. ing. Moreover, it is also disclosed that the multilayer film is suitably used as a surface decoration film such as an exterior member of a home appliance or an interior member of a car. It is suggested that a polymer of methyl methacrylate is suitable as the methacrylic resin.

In Patent Document 3, using an ink composition for hard coat layer having ionizing radiation curing property,
Step (1) At least a release layer and a hard coat layer forming layer formed by coating an ink composition for hard coat layer having ionizing radiation curability on one side of a substrate film in an injection molding die in this order The process of arranging the decoration sheet which it has.
Step (2) An injection step of injecting a molten resin into the cavity, cooling and solidifying it, and laminating and integrating the resin molded body and the decorative sheet.
Step (3) A step of taking out a molded body in which the resin molded body and the decorative sheet are integrated from the mold.
Process (4) The process of peeling the base film of a decorating sheet from a molding.
Step (5) A hard coat layer forming step of curing the hard coat layer forming layer provided on the molded body in an atmosphere having an oxygen concentration of 2% or less.
The method of manufacturing a decorating molded article through each process of is disclosed.

  Patent Document 4 has a carboxyl group and a hydroxyl group, has a solid content acid value of 15 to 150 mg KOH / g, a solid content hydroxyl value of 2 to 80 mg KOH / g, and a glass transition temperature of 70 to 140 ° C. The vinyl polymer (A) and the polyisocyanate compound (B) are contained, and the content of the polyisocyanate compound is a content that reacts with the solid content hydroxyl value 2 to 80 mg KOH / g of the vinyl polymer (A). A curable resin composition for a film for thermoforming is disclosed.

  Patent Document 5 is a laminated hard coat film for molding, in which a hard coat layer containing a resin is provided on a substrate film, and elongation of the laminated hard coat film under an atmosphere at 23 ° C. and 50% RH. There is disclosed a molding laminated hard coat film having a percentage of 10% or more. The resin contained in the hard coat layer uses an active energy ray curable resin.

  Patent Document 6 shows a topcoat-added decorative sheet having a topcoat layer on one side of the decorative sheet, wherein the topcoat layer has a surface hardness of pencil hardness B or higher at -40 ° C to 130 ° C. The topcoat addition decoration sheet which is 150% or more of a draw ratio in the tension tester in ° C is indicated. It is disclosed that the top coat layer is formed by photocuring the resin composition.

  Patent Document 7 discloses a resin containing a polymer (A) having at least a hydroxyl group and a carboxyl group, a polyisocyanate (B), and a prepolymer (C) having three or more acryloyl groups or methacryloyl groups in one molecule. The transfer film obtained by apply | coating a composition on a peelable gas film is described (Claims 1 and 5). In the second aspect, the polymer (A) includes a polymerizable monomer having a hydroxyl group and an unsaturated double bond, and a polymerizable monomer having a carboxyl group and an unsaturated double bond. The polymer (A) has a hydroxyl value of 5 to 100 mg KOH / g, and a weight average molecular weight of 30, it is described that the polymer (A) has a hydroxyl value of 5 to 100 mg KOH / g. 000 to 300,000, and the glass transition temperature is described to be 60 to 180 ° C.

  Patent Document 8 discloses an integrally formable laminated sheet having a cured resin layer as a top coat layer (claim 1). The hardened resin layer of the top coat layer has a hydroxyl value of 10 to 300 mg KOH / g, a weight average molecular weight of 2,000 to 50,000, and a glass transition temperature (Tg) of 80 ° C. or less. It is described that it is a resin layer obtained by curing a resin composition comprising the hydroxyl group-containing vinyl copolymer (A) and the polyisocyanate compound (B).

Patent document 9 has an acrylic resin, a polyester resin, a polyether resin and a polycarbonate resin having a solubility parameter of less than 20 MPa ^1/2 and having a number average molecular weight of 500 to 20,000 and a hydroxyl value of 50 to 200 mg KOH / g. Disclosed is a coating composition containing, in a specific ratio, a base resin selected from the group consisting of: and a polyisocyanate resin having a solubility parameter of less than 20 MPa ^1/2 and having at least two isocyanate groups at the end. (Claim 1)

JP, 2011-161871, A JP, 2010-125645, A Unexamined-Japanese-Patent No. 2011-161692 JP, 2012-097248, A JP 2012-210755 A JP, 2013-006346, A JP, 2010-126633, A Unexamined-Japanese-Patent No. 2002-347179 JP, 2014-065796, A

  What is specifically disclosed as an acrylic resin (A) in Patent Document 1 is a polymethyl methacrylate resin having a glass transition temperature of 120 ° C. It is thought that the balance between impact resistance and surface hardness is maintained by laminating a flexible aliphatic polycarbonate resin (B) on such a hard resin. However, in the polymethyl methacrylate resin as disclosed in the examples, although it has impact resistance as disclosed in the examples and a sheet having a pencil hardness of 2H is produced, the sheet is inferior in chemical resistance. Poor in sunproof creaminess.

  Specifically disclosed as the methacrylic resin (B) in Patent Document 2 is a polymer of 97.8% of methyl methacrylate and 2.2% of methyl acrylate, and has a glass transition temperature of 100 ° C. or higher Resin. Reference 2 also suggests that the multilayer body be applied to an automobile interior material. However, such thermoplastic methacrylic resin (B) is inferior in chemical resistance and inferior in sunscreen cream resistance.

  According to the method described in Patent Document 3, although high hardness and scratch resistance can be obtained, the hard coat layer forming layer coated with the ink composition for hard coat layer having ionizing radiation curability is not cured. In this condition, the strength of the film is weak and it is easily scratched when placed in the mold. In addition, depending on the storage conditions after coating, curing may gradually proceed, and cracking may occur during molding.

  According to the examples, the resin film for thermoforming formed using the curable resin composition described in Patent Document 4 has a solid content hydroxyl value of 40 (mg KOH / g) or more, and a mass average molecular weight of 6000. The vinyl polymer (A) having a glass transition temperature of 76 ° C. or higher is used. Such low molecular weight and high glass transition temperature vinyl polymers are highly crosslinked with high hydroxyl value. When a film for thermoforming using such a resin is vacuum-formed, although it can be molded into a box of 95 mm long, 50 mm wide and 5 mm deep as described in the examples, it is molded after being molded. When used as an interior part, cracks may occur due to temperature changes in the car. Moreover, when it shape | molds in a further deeper type, it can not follow the elongation at the time of shaping | molding.

  The hard coat layer and the top coat layer described in Patent Documents 5 and 6 are all formed by curing with active energy rays, and as shown in Patent Document 3, the uncured state at the time of molding Are easily damaged when placed in the mold. Furthermore, it is difficult to uniformly apply active energy rays to the surface of a three-dimensionally molded product. Also, if the elongation is 10% in an atmosphere at 23 ° C. and 50% RH, deep drawing can not be performed, and even if the draw ratio at 150 ° C. is 150% or more, the change in the temperature inside the vehicle after forming I can not keep up with.

In Patent Document 7, a resin composition is applied onto a peelable substrate film, and after heat curing of a polymer (A) and a polyisocyanate (B), an active energy ray is irradiated to three or more in one molecule. The prepolymer (C) having an acryloyl group or a methacryloyl group is cured to obtain a cured coating.
The cured coating film which used the thermosetting and the curing by active energy ray radiation described in Patent Document 7 in combination has a small strength and is extremely inferior in the abrasion resistance and the sunscreen resistance.

  Since the hydroxyl group-containing vinyl copolymer (A) disclosed in Patent Document 8 has a relatively small weight average molecular weight, the cured coating film obtained has a small strength, and the abrasion resistance and the sunscreen resistance are remarkable. It is inferior.

  The paint composition disclosed in Patent Document 9 lacks extensibility, and therefore has poor formability and can not be applied to a decorative film. The lack of extensibility is presumed to be caused by using a resin having a small number average molecular weight.

  The present invention is a decorative film having excellent productivity, which is excellent in moldability at the time of molding as a decorative film, is positioned on the surface of the decorative molded body after molding, and is sufficiently resistant to temperature changes in the car Further, it is an object of the present invention to provide a decorative film and a decorative molded article having a surface coated with the decorative film, which is excellent in abrasion resistance and chemical resistance (sun cream resistance and the like).

This invention solved the said subject by the hard-coat layer which is a photocured material of the photocurable composition containing the monomer which has a (meth) acryloyl group having an alkylene oxide chain.
That is, the present invention relates to the following [1] to [11].
[1] A decorative film comprising a laminate including a hard coat layer and a substrate layer, wherein the hard coat layer is a photocured product of a photocurable composition,
The hard coat layer has an alkylene oxide chain,
The said photocurable composition contains the monomer which has a (meth) acryloyl group, and a photoinitiator, The decoration film characterized by the above-mentioned.

[2] whether a monomer having a (meth) acryloyl group has an alkylene oxide chain,
Or the photocurable composition further comprises a component (D) having an alkylene oxide chain and having no (meth) acryloyl group,
The decorative film as described in [1].

[3] The monomer according to [1] or [2] according to [1] or [2], which comprises a monomer (A) having an alkylene oxide chain and a monomer (B) having no alkylene oxide chain as the monomer having a (meth) acryloyl group. Decorative film.

[4] A monomer having a (meth) acryloyl group, characterized in that, as a monomer having a (meth) acryloyl group, a monomer (C) having at least one functional group out of a hydroxyl group or a carboxyl group is included [1] The decorating film in any one of-[3].

[5] The decorative film as described in [4], wherein the sum of the hydroxyl value and the acid value of the photocurable composition is 1 to 300 mg KOH / g.

[6] The content of the monomer (A) having an alkylene oxide chain and a (meth) acryloyl group contained in 100% by mass of the photocurable composition is 0.5 to 90% by mass. 5] The decorative film as described in any one.

[7] Any one of [1] to [6], wherein the base material layer is composed of a single layer or a multilayer selected from the group consisting of polyester, polycarbonate, polymethyl methacrylate, polyethylene, and polypropylene. The decorative film described in.

[8] The decorative film according to any one of [1] to [7], wherein the hard coat layer is in contact with the base layer.

[9] The decorative film according to any one of [1] to [8], further comprising at least one of an adhesive layer and a colored layer.

[10] The decorative film according to [9], wherein the adhesive layer is laminated between the base layer and the hard coat layer.

[11] The decorative film according to [9], wherein the adhesive layer is laminated on the side of the base layer not facing the hard coat layer.

[12] The vehicle according to any one of [1] to [11], comprising a body to be decorated and a decoration film covering at least a part of the body to be decorated A decorated molded body.

  The decorative film according to the present invention is excellent in productivity, is excellent in moldability at the time of molding as the decorative film, is positioned on the surface of the decorative molded body after molding, and is sufficiently resistant to temperature change in the vehicle, Furthermore, it is possible to provide a decorative film excellent in abrasion resistance and chemical resistance (such as sunscreen cream resistance), and to provide a decorative molded body whose surface is covered with the decorative film.

Sectional drawing of the structural example of the decoration film of this invention. Sectional drawing of the structural example of the decoration film of this invention. Sectional drawing of the structural example of the decoration film of this invention. Sectional drawing of the structural example of the decoration film of this invention. Sectional drawing of the structural example of the decoration film of this invention. Sectional drawing of the structural example of the decoration film of this invention. Sectional drawing of the structural example of the decoration film of this invention. Cross-sectional view of a structural example of the decorative film of the present invention

  This invention makes a thermoplastic acrylic resin film a hard-coat layer by the hard-coat layer which is a photocuring thing of the photocurable composition containing the monomer which has a (meth) acryloyl group having an alkylene oxide chain. Both moldability and durability which can not be obtained in the case can be achieved.

<Hard coat layer>
The hard coat layer in the present invention is a photocured product of a photocurable composition described later, and the photocurable composition contains a monomer having a (meth) acryloyl group and a photopolymerization initiator.
The hard coat layer has an alkylene oxide chain. When the hard coat layer has an alkylene oxide chain, sunscreen resistance is improved. Sunproof cream resistance is a characteristic which does not produce the appearance defect of a decoration film, after applying and heating a sun protection cream on the hard court layer located on the surface of a decoration film. If it is not resistant, the components in the sunscreen cream corrode the substrate layer constituting the decorative film, resulting in poor appearance. In order to suppress the erosion to the base layer, it is necessary to prevent the sunscreen cream from diffusing in the hard coat layer and reaching the base layer. However, if the crosslink density of the hard coat layer is simply increased, the moldability is degraded. The present inventor noted that the affinity between the component contained in the sunscreen cream which is likely to erode the substrate layer and the alkylene oxide chain is poor, and the hard coat layer contains the alkylene oxide chain, It has been found that the spread and penetration of sunscreen cream can be suppressed.

That is, by the presence of the alkylene oxide chain in the hard coat layer, the sunscreen cream component is prevented from reaching the base layer, and the sunscreen cream resistance is improved. As a method of incorporating an alkylene oxide chain in the hard coat layer, (i) a method of incorporating a monomer (A) having an alkylene oxide chain and a (meth) acryloyl group in a photocurable composition, (ii) an alkylene oxide chain And (meth) acryloyl group-containing component (D), but from the viewpoint of durability after photocuring, alkylene oxide chains are photocured by the method of (i) It is desirable to incorporate into the internal cross-linked structure. As a method of incorporating an alkylene oxide chain into a crosslinked structure, a compound having a functional group such as a hydroxyl group and an alkylene oxide chain in the photocurable composition, and at least one functional group of hydroxyl group and carboxyl group described later There is also a method in which a monomer (C) having an acryloyl group and a thermosetting agent having a functional group capable of crosslinking with a functional group such as a hydroxyl group are contained and cured by light and heat.
In the present invention, a monomer having at least one functional group of a hydroxyl group and a carboxyl group and having an alkylene oxide chain and a (meth) acryloyl group is a monomer having an alkylene oxide chain and a (meth) acryloyl group ( It shall be included in A).

The case where the photocurable composition contains (i) a monomer (A) having an alkylene oxide chain and a (meth) acryloyl group will be described.
The monomer (A) which has an alkylene oxide chain and a (meth) acryloyl group contains the alkylene oxide chain for providing sunscreen cream resistance, and the (meth) acryloyl group for improving durability by hardening. From the viewpoint of improving the durability, one having a plurality of (meth) acryloyl groups can be used.
Component (D) having an alkylene oxide chain to be described later and having no (meth) acryloyl group
When not using, the content of the monomer (A) having an alkylene oxide chain and a (meth) acryloyl group contained in 100% by mass of the nonvolatile matter of the photocurable composition is 0.5 to 90% by mass Preferably, it is more preferably 1 to 90% by mass. When the content of the monomer (A) having an alkylene oxide chain is 0.5 to 90% by mass, chemical resistance can be improved without deteriorating the moist-heat resistance.

<Monomer (A) Having Alkylene Oxide Chain and (Meth) Acryloyl Group>
Examples of the monomer (A) having an alkylene oxide chain and a (meth) acryloyl group include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polytetraethylene (meth) acrylate, alkoxy polyethylene glycol (meth) acrylate, Alkoxy polypropylene glycol (meth) acrylate, alkoxy poly tetra ethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, phenoxy poly tetra ethylene glycol (meth) acrylate, or multimers thereof Is mentioned,
As a commercial item, for example,
NOF Corporation BLEMMER series (PE-90, PE-200, PE-350, PE-350G, PP-1000, PP-500, PP-800, 50PEP-300, 70PEP-350B, 55PET-800, 10PPB-500B, AE-90U, AE-200, AE-400, AP-200, AP-400, AP-550, AP-800, PME-100, PME-200, PME-400, PME-1000, PME- 4000, 50 POEP-800 B, PLE-200, PLE-1300, PSE-1300, AME-400, ALE-200, 43 PAPE-600 B, ANP-300, 75 ANEP-600, NDMA, PDE-100, PDE-150, PDE- 200, PDE-400, PDE-600, PD -400N, PDP-700, PDT-650, PDBE-200A, PDBE-250, PDBE-450A, PDBE-1300, ADE-200, ADE-300, ADE-400, ADE-600, ADP-400, ADT-250 ),
Osaka Organic Chemical Industry Co., Ltd. biscoat # 192, bis coat # 192, bis coat # 190, bis coat # MTG, 2-MTA, MPE 400A, MPE 550 A, bis coat # 310 HP, bis coat # 335 HP, bis coat # 700 HV, bis coat #, bis coat # 360
Light ester series (BC, 130MA, 041MA, 2EG, 3EG, 4EG, 9EG, 14EG, BP-2EMK) manufactured by Kyoeisha Chemical Co., Ltd., light acrylate series (EC-A, MTG-A, EHDG-AT, 130A, DPM) -A, P2H-A, P-200A, 3EG-A, 4EG-A, 9EG-A, 14EG-A, PTMGA-250, BP-4EAL, BP-4PA,
A-LEN-10, AM-90G, AM-130G, AMP-20GY, M-90G, M-230G, PHE-1G, A-200, A-400, A-600, manufactured by Shin-Nakamura Chemical Co., Ltd. A-1000, A-B 1206 PE, ABE-300, A-BPE-10, A-BPE-20, A-BPE-30, A-BPE-4, A-BPEF, A-BPP-3, APG-100, APG-200, APG-400, APG-700, A-PTMG-65, A-GLY-9E, A-GLY-20E, ATM-35E, 2G, 3G, 4G, 9G, 14G, 23G, BPE-80N, Although BPE-100, BPE-200, BPE-500, BPE-900, BPE-1300N, 1206PE, 9PG, etc. may be mentioned, the present invention is limited to such exemplifications only. Not intended to be. These monomers having an alkylene oxide chain may be used alone or in combination.

<Monomer (B) having no alkylene oxide chain>
In the case of (i), in addition to the monomer (A), it is preferable to use a monomer (B) having no (alkylene) chain and having a (meth) acryloyl group.
The monomer (B) not having an alkylene oxide chain and having a (meth) acryloyl group is a monomer (A) having the above-described alkylene oxide chain and a (meth) acryloyl group, and at least one functional group among hydroxyl group and carboxyl group described later. The monomer which has a (meth) acryloyl group which does not correspond to the monomer which has a (meth) acryloyl group which has a group is meant. By including the monomer (B) having a (meth) acryloyl group, it is possible to adjust the glass transition temperature of the hard coat layer, to impart adhesion with the base material layer, and to adjust the crosslink density.

  Examples of the monomer (B) having a (meth) acryloyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isononyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, Alkyl (meth) acrylates such as stearyl (meth) acrylate, tert-butyl hexyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, cyclopentene (Meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (Meth) acrylate, glycidyl (meth) acrylate, α-methyl glycidyl (meth) acrylate, α-methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) ) Monomer monomer such as acrylate, 1,4-butanediol diacrylate, neopentyl glycol di (meth) acrylate, 3-methyl-1,5 pentanediol di (meth) a Lilate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate Although multimeric monomers such as dipentaerythritol hexa (meth) acrylate and the like can be mentioned, the present invention is not limited to such examples. These monomers may be used alone or in combination.

<Monomer (C)>
The monomer (C) having at least one functional group of a hydroxyl group and a carboxyl group and a photopolymerizable functional group will be described.
The monomer (C) having at least one functional group of a hydroxyl group and a carboxyl group and a photopolymerizable functional group has at least one functional group of a hydroxyl group and a carboxyl group in the molecule, and has an alkylene oxide chain. It is preferable to have a photopolymerizable functional group such as a radically polymerizable (meth) acryloyl group.

  A hydrogen bond is formed by the presence of a hydroxyl group or a carboxyl group in the hard coat layer, but since the hydrogen bond is easily dissociated by heating at the time of molding, the moldability is hardly impaired. On the other hand, the durability of the hard coat layer is improved by hydrogen bonding in a working environment near room temperature where hydrogen bonding is difficult to dissociate.

  When a photocurable composition containing a hydroxyl group and / or a carboxyl group is used, the total of the hydroxyl value and the acid value is preferably 300 mg KOH / g or less in order to form a hard coat layer excellent in water resistance. Preferably, it is 250 mg KOH / g or less, and more preferably 150 mg KOH / g or less. Water resistance can be improved by the sum total of a hydroxyl value and an acid value being 300 mgKOH / g or less. The sum of the hydroxyl value and the acid value is the sum of the hydroxyl value and the acid value of the photocurable composition, for example (1) the hydroxyl value is 5 mg KOH / g, the acid value is 5 mg KOH / g, (2) the hydroxyl group In any case where the value is 0 mg KOH / g (the photocurable composition does not have a hydroxyl group) and the acid value is 10 mg KOH / g, the sum of the hydroxyl value and the acid value is 10 mg KOH / g.

  Examples of the monomer having a hydroxyl group include hydroxyalkyl (meth) acrylate, and specific examples of hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3 -Hydroxyalkyl (meth) acrylate having 1 to 4 carbon atoms in the alkyl group such as -hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 1,1-dihydroxymethyl Although (meth) acrylate, 1,2-dihydroxyethyl (meth) acrylate, 2,2-dihydroxyethyl (meth) acrylate and 2,3-dihydroxypropyl (meth) acrylate can be mentioned, the present invention is described only by such an example. Not intended to be constant. These monomers having a hydroxyl group may be used alone or in combination.

  Examples of the monomer having a carboxyl group include (meth) acrylic acid and carboxyalkyl (meth) acrylate, but the present invention is not limited to such examples. Furthermore, itaconic acid, fumaric acid, maleic acid, crotonic acid and the like can also be used in the present invention. These monomers having a carboxyl group may be used alone or in combination.

  The photocurable composition of the present invention may contain a thermosetting agent having a functional group capable of crosslinking with a functional group such as a hydroxyl group or a carboxyl group. The presence of a thermosetting agent having a functional group capable of crosslinking with a functional group such as a hydroxyl group or a carboxyl group causes a crosslinking reaction between the hydroxyl group or carboxyl group in the monomer and the thermosetting agent to form a more durable hard coat. can do. Examples of the thermosetting agent having a functional group capable of crosslinking with a functional group such as a hydroxyl group or a carboxyl group include, for example, an isocyanate curing agent, an epoxy curing agent, a carbodiimide curing agent, and an aziridine curing agent. It is not limited to the examples.

<Component (D) having an alkylene oxide chain and not having a (meth) acryloyl group>
In the present invention, instead of the monomer (A) having an alkylene oxide chain and a (meth) acryloyl group, the component (D) having an alkylene oxide chain and not having a (meth) acryloyl group is a monomer (B) described above or It can be blended in (C) and used as a photocurable composition for forming a hard coat layer, and it has an alkylene oxide chain in addition to the monomer (A) having an alkylene oxide chain and a (meth) acryloyl group. Component (D) having no (meth) acryloyl group can also be used.
In any case, the content of the component having an alkylene oxide chain is preferably 0.5 to 90% by mass, and more preferably 1 to 90% by mass, in 100% by mass of the nonvolatile matter of the photocurable composition. Is preferred. When the content of the component having an alkylene oxide chain is 0.5 to 90% by mass, chemical resistance can be improved without deteriorating the heat and humidity resistance.

As component (D) which has an alkylene oxide chain and does not have a (meth) acryloyl group, for example, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkylate, polyoxypropylene alkylate, polyethylene glycol Dialkylates, polypropylene glycol dialkylates, polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetraethylene glycol, polyoxyethylene monoalkyl ether, polyoxyethylene dialkyl ether, polyoxypropylene monoalkyl ether, polyoxypropylene dialkyl ether, etc. Listed
As a commercial item, for example,
NONION CO., LTD. Nonionic series (K-204, K-220, K-230, K-2100 W, P-208, P-210, P-213, E-202, E-202 S, E-205, E- -205S, E-212, E-215, E-230, S-207, S-215, S-220, B-250, EH-204, EH-208, ID-203, ID-206, ID-209 , HT-505, HT-507, HT-510, HT-512, HT-518, HT-518, MN-811, L-2, L-4, S-2, S-4, S-6, S -15, S-15K, S-15.4, S-15.4 V, S-40, O-2, O-3, O-4, O-6, DS-60 HN, DO-4, DO-6 ),
Persoft series (NK-60, NK-90C, NK-100, NK-100C),
Dispanol series (TOC, 16, 16A, LS-100),
Pronon series (# 102, # 104, # 201, # 202B, # 204, # 208),
Unilube series (70DP-600B, 70DP-950B, MS-70K, 50DB-22, 50MB-2),
PEG series (# 200T, # 200, # 300, # 400, # 600, # 1000, # 1500, # 1540, # 1540, # 2000, # 4000, # 4000P, # 6000, # 6000P, # 11000, # 20000),
Uniox series (M-400, M-550, M-1000, M-2000, M-2500, M-3000, M-4000, MM-400, G-450, G-750, PKA-5001, PKA- 5006),
Uniol series (D-200, D-250, D-400, D-700, D-1000, D-1200, D-2000, D-4000, TG-330, TG-1000 R, TG-3000, TG- 4000, PB-500, PB-700, PB-2000, PB-4800, DA-400, DA-700, DB-400),
Polyserine series (DC-1100, DC-1800E, 60DC-1800, DC-3000E, DCB-1000, DCB-2000, DCB-4000, TPBC-3030), etc. may be mentioned, but the present invention is only for such illustration. It is not limited.

  The photocurable composition of the present invention contains a photopolymerization initiator. By containing a photoinitiator, when light is irradiated to a photocurable composition, hardening reaction advances and a highly durable hard-coat layer is formed. As the photopolymerization initiator, known ones can be used. For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, diethoxyacetophenone, 4- (2- Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenyl-propane- 1-one, 1-hydroxy-cyclohexyl-phenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, benzyl dimethyl ketal, oligo { 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane}, 4- (2-acryloyl- Acetophenones such as xylethoxy) phenyl-2-hydroxy-2-propyl ketone, benzoins such as benzoin, benzoin isopropyl ether and benzoin isobutyl ether, mixtures of 1-hydroxycyclohexyl-phenyl ketone and benzophenone, 2,4,6- Acylphosphine oxides such as trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, benzyl, methylphenylglyoxy ester, 3,3 ', 4,4'-tetra (T-butylperoxycarbonyl) benzophenone, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophene , 4-Benzoyl-4'-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone Etc., 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, thioxanthone such as 2,4-dichlorothioxanthone, Michler's ketone, aminobenzophenone such as 4,4'-bisdiethylaminobenzophenone 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, 9,10-phenanthrene quinone, camphor quinone, etc., but the present invention is not limited to such examples. These photopolymerization initiators may be used alone or in combination.

  In addition, the photocurable composition of the present invention may contain a photosensitizer. Examples of photosensitizers include triethanolamine, methyldiethanolamine, dimethylethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, benzoic acid Amines such as (2-dimethylamino) ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl and the like can be mentioned.

  In the present invention, the photocurable composition can be used after diluting it with a solvent. The solvent may be appropriately selected and used, and may be appropriately selected, for example, esters such as ethyl acetate, butyl acetate and cellosolve acetate; acetone, methyl ethyl ketone, isobutyl ketone, methyl isobutyl ketone, ketones such as acetylacetone and cyclohexanone; ; Ethers such as dioxane; Aromatic hydrocarbons such as toluene and xylene; Halogenated hydrocarbons such as methylene chloride and ethylene chloride; Dimethyl sulfoxide, dimethyl sulfoamide; Alcohols such as water, methanol, ethanol and isopropanol Can be mentioned. These may be used alone or in any combination of two or more.

  In the present invention, for the purpose of imparting weather resistance to the formed hard coat layer, the photocurable composition can further contain an ultraviolet light absorber, an ultraviolet light stabilizer, and the like. Examples of UV absorbers include organic UV absorbers such as benzotriazole-based UV absorbers, benzophenone-based UV absorbers, triazine-based UV absorbers, indole-based UV absorbers, and inorganic UV absorbers such as zinc oxide UV absorbers such as are raised. As the ultraviolet light stabilizer, ultraviolet light stabilizers such as hindered amine compounds are suitably used. The ultraviolet absorber and the ultraviolet light stabilizer are 0.01 to 25 parts by mass, preferably 0.05 to 20 parts by mass with respect to 100 parts by mass of the solid content of the photocurable composition excluding the ultraviolet absorber and the ultraviolet light stabilizer It is preferred to use.

  In the present invention, a slip agent can be added to the paint for the purpose of imparting slipperiness to the hard coat layer. Examples of slip agents include fluorine-based slip agents, silicone-based slip agents and wax-based slip agents. These slip agents are preferably used in an amount of 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass, with respect to 100 parts by mass of the solid content of the photocurable composition.

  In the present invention, the paint for forming the hard coat layer may be applied as a relatively thick film, so surface defects may occur in the drying step. A surface conditioner etc. can also be added to a curable composition in order to prevent surface defect. As a surface conditioner, BYK company BYK-300, BYK-315, BYK-320 etc. can be raised. These surface conditioners are preferably used in an amount of 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass, with respect to 100 parts by mass of the solid content of the photocurable composition.

  In the present invention, by containing organic or inorganic fine particles in the coating, the surface of the hard coat layer is made uneven to impart an antiblocking effect, to give a matte feeling due to the surface unevenness, to give strength to the film. Can be made hard to be damaged. It is preferable to contain 0.01-20 mass parts of these microparticles | fine-particles with respect to 100 mass parts of photocurable compositions, and it is preferable to contain 0.1-10 mass parts more preferably. When the content is 0.01 parts by weight or more, the above effect can be expected, and when the content is 20 parts by mass or less, a strong hard coat layer which is excellent in moldability and does not inhibit transparency can be formed.

  Specific examples of the organic fine particles include polytetrafluoroethylene resin, polyethylene resin, polypropylene resin, polymethyl methacrylate resin, polystyrene resin, polyamide resin, melamine resin, guanamine resin, phenol resin, urea resin, silicone resin, methacrylate resin And polymer fine particles such as acrylate resin, or cellulose powder, nitrocellulose powder, wood powder, waste paper powder, shell powder, starch and the like. One type of organic particles may be used, or two or more types may be used in combination.

  Specific examples of the inorganic fine particles include inorganic compounds containing oxides, hydroxides, sulfates, carbonates, silicates, etc. of metals such as magnesium, calcium, barium, zinc, zirconium, molybdenum, silicon, antimony, etc. There are fine particles. Further detailed examples include inorganic materials containing silica, silica gel, aluminum oxide, aluminum hydroxide, calcium hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, aluminosilicate, talc, mica, glass fiber, glass powder, etc. System particles are mentioned. The inorganic particles may be used alone or in combination of two or more.

  In the paint, if necessary, a filler, a thixotropy-imparting agent, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, a thermal conductivity improver, a plasticizer, to the extent that the effects of the present invention are not impaired. Various additives such as anti-sagging agents, antifouling agents, antiseptics, bactericides, antifoaming agents, leveling agents, curing agents, thickeners, pigment dispersants, silane coupling agents may be further added.

  The hard coat layer in the present invention will be described. The hard coat layer of the present invention is formed by photocuring the above-mentioned photocurable composition. The hard coat layer of the present invention may be formed by photocuring the photocurable composition after molding, or may be formed by photocuring the photocurable composition before molding. By photocuring after molding, it is possible to form a hard coat layer that also follows the complicated shape of the molded product, and to improve the storage stability of the decorative film by photocuring before molding. it can. The timing of photocuring the photocurable composition to form a heart coat layer can be appropriately selected depending on the shape of the molded product and the like.

  When the photocurable composition is photocured before molding, the hard coat layer of the present invention preferably has an elongation of 30% or more at the time of molding, for example, at 120 ° C. when broken. When the elongation percentage is 30% or more, it can be easily molded following the mold at the time of molding. Although the upper limit of the elongation is not particularly limited, the elongation is preferably 30 to 1000% from the viewpoint of achieving both moldability and durability. The elongation percentage in the present invention indicates how much the sample is elongated with respect to the original length, and for example, 0% indicates that it does not stretch at all, and 100% indicates that the sample is twice as large as the original. Length (if the original length is 10 mm, it is extended by 10 mm and the entire length is 20 mm).

  In addition, "light" said by this invention means an active energy ray in general, and it is not limited to visible light. The active energy ray includes, for example, ultraviolet light, electron beam, X-ray, ionizing radiation such as α-ray, β-ray and γ-ray, microwave, radio frequency and the like, but if radical active species can be generated Any energy species may be used, such as visible light, infrared light, and laser light. Examples of UV light generating sources include ultra high pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, low pressure mercury lamps, metal halide lamps, xenon lamps, carbon arc lamps, helium / cadmium lasers, YAG lasers, excimer lasers, argon lasers and so on.

  As mentioned above, although a solvent can be contained in a photocurable composition, when it contains a solvent in a photocurable composition, it is preferable to dry a solvent before photocuring.

  When drying a solvent, it is preferable to dry at 50-200 degreeC, and it is more preferable to dry at 70-120 degreeC. Furthermore, the oven is divided into several zones, for example, the oven temperature is inclined from low temperature to high temperature, such as 50 ° C. for the first zone, 70 ° C. for the second zone, 100 ° C. for the third zone, etc. It is preferable to set. The residence time in the oven is usually about 1 to 10 minutes. Several ovens with a fixed temperature may be prepared and then dried for several minutes in ovens of each temperature.

<Decorated film>
Next, the decorative film of the present invention will be described. The decorative film of the present invention comprises a laminate including a hard coat layer obtained by curing a photocurable composition for forming a hard coat layer and a substrate layer.

The base material layer plays a role of supporting the hard coat layer and other colored layers and adhesive layers described later.
The base material layer is not particularly limited as long as it is a film serving as a support, and known materials can be used. For example, polyethylene film, polypropylene film, polyester film, polycarbonate film, polymethyl methacrylate film, polyamide film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polystyrene film, polyacrylonitrile film, aluminum foil, paper And the like, and one or more kinds of layers can be used.
In particular, from the viewpoint of transparency and moldability, polyester films, polycarbonate films, polymethyl methacrylate films, polyethylene, and polypropylene are preferable. Also in these films, it is possible to use one film alone or a laminate of multiple films, for example, a PMMA / PC film in which polymethyl methacrylate (PMMA) is co-extruded on polycarbonate (PC), or polycarbonate It is also possible to use a film in which a film and a polyester film are laminated with an adhesive.
Polycarbonate films have good moldability, polyester films have good solvent resistance (for organic solvents, sunscreen creams, etc.), and polymethyl methacrylate films have good hardness. The combination can be selected appropriately and used.

  A peelable film may be laminated as a protective film on the non-facing side not facing the hard coat layer of the base layer. In particular, since the polycarbonate-based substrate is easily scratched, it is preferable to protect the back side with a protective film until immediately before use.

  The thickness of the substrate layer is not particularly limited, but is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and further 10 to 400 μm from the viewpoint of moldability and durability. preferable. A base material layer may combine two or more types of base materials from which thickness differs, and in that case, it is preferable that the total thickness of each combined base material layer is 5-1000 micrometers.

  The hard coat layer of the present invention will be described. The hard coat layer of the present invention is formed of a photocured product obtained by photocuring the above-described photocurable composition for forming the hard coat layer (hereinafter, also referred to as a paint).

  The method of providing a hard-coat layer on a base material layer is demonstrated. The heart coat layer can be provided by coating the above-mentioned paint on one side of the base layer. If the paint contains a solvent, place it in a drying oven as needed to evaporate the solvent. When the paint contains a thermosetting functional group and a curing agent, it can be further aged as necessary to obtain a hard coat layer.

Alternatively, the hard coat layer can be provided on the base layer using an adhesive.
Specifically, a paint for forming a hard coat layer is applied on a peelable sheet and cured. Apply the adhesive for lamination to the cast film or / and the base layer, and apply the obtained adhesive film (cast film) to the cast film (or the solvent evaporation process and the aging process as required). When the adhesive contains a solvent, after the solvent is evaporated, the cast film and the substrate layer can be laminated to obtain a decorative film having a hard coat layer and a substrate layer. The peelable sheet is properly peeled before and after lamination.

  As the method of applying the paint, known methods can be used, and specific examples thereof include comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating and the like.

  The laminate obtained by applying the paint may remain tacky in the coating before photocuring, and may cause a blocking phenomenon when it overlaps with the opposite surface of the substrate layer. In order to prevent such a blocking phenomenon, a separator for blocking prevention can be laminated on the coating film when stacking in sheets or when winding in a roll. As the separator, a PET film subjected to release treatment, an unstretched propylene film, a polyethylene film or the like is suitably used.

  The paint for forming the hard coat layer is preferably defoamed before being applied to the base material layer or the releasable sheet. When the foam contained in the paint, when it was applied to the base material layer or the releasable sheet, the foam was mixed into the film being formed, and the foam was broken on the surface of the coated film after drying or curing There may be marks left. As a method of degassing, it may be waited until the foam disappears after stirring, or it may be forcibly defoamed by a vacuum defoamer or the like.

The decorative film of the present invention may further be provided with an adhesive layer and a colored layer as described later. As shown in FIG. 6, the adhesive layer (2) can be provided between the hard coat layer (HC) and the base layer (1) and used to bond the hard coat layer to the base layer. . Alternatively, as shown in FIG. 7, it is also used to bond various layers when using a plurality of base material layers (1a) and (1b) or when using a colored layer.
An adhesive layer may be provided on the side opposite to the hard coat layer side of the base material layer, and the decorative film and the object to be decorated such as a molded body may be bonded to each other.

The adhesive constituting the adhesive layer is not particularly limited, and any known adhesive can be used, and examples thereof include a thermosetting adhesive, a pressure sensitive adhesive, a hot melt adhesive and the like, and one or two types are used. The above can be used in combination.
The component which comprises these adhesives is not specifically limited, For example, polyester resin, poly (meth) acrylate resin, polyurethane resin, polyether resin, polyamide resin, polyimide resin, polyethylene resin, polystyrene resin, polypropylene resin, ethylene-acetic acid A vinyl resin, a polyvinyl alcohol resin, an epoxy resin, a silicone resin, a phenol resin, a styrene-butadiene rubber, a nitrile rubber, a natural rubber, etc. are mentioned, It can be used 1 type or in combination of 2 or more types.

  A method of providing an adhesive layer will be described. The adhesive layer is formed by applying a solvent-containing adhesive directly to the substrate layer or hard coat layer and drying it, or by softening the solvent-free adhesive with heat to coat the substrate layer or hard coat. An adhesive sheet containing an adhesive containing a solvent, with or without a solvent, is applied by the above method to the adhesive sheet, and the adhesive sheet is then provided between the objects to be adhered. Can be provided by a method of sandwiching After the adhesive layer is provided, an aging treatment may be further performed. Further, the thickness of the adhesive layer is not particularly limited, and the thickness can be arbitrarily set so as to secure the adhesive strength, but it is in the range of 1 to 200 μm from the balance of the adhesive strength and the durability. Is preferred.

  As the method of applying the adhesive, known methods can be used, and specific examples thereof include comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating and the like.

  The decorative film of the present invention may further be provided with a colored layer. A colored layer is laminated in order to give design to a decorative film, and when it is made into a decorative molded body, such as a hard-coat layer and the other side of a base material layer, between a hard-coat layer and a base material layer. The position can be freely provided as long as it does not become the outermost layer. In addition, coloring in the present invention is meant to include various decorations such as pictures, designs, metallic tones, characters, patterns, etc. in addition to a single color, and a plurality of different colored layers may be laminated.

  The method of obtaining a colored layer is demonstrated. The colored layer is obtained by applying a colored paint to a substrate layer and drying it, applying to a substrate layer, drying, aging, applying it to a substrate layer and irradiating it with light, substrate A method of printing and drying the layer, a method of printing on the substrate layer and light irradiation, and a method of vapor-depositing a metal on the substrate layer may be mentioned. The thickness of the colored layer is not particularly limited as long as the intended color, pattern and the like can be recognized, but from the viewpoint of moldability, the thickness is preferably 500 μm or less.

  As a method of providing the colored layer on the substrate, known methods can be used, and specifically, comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating, silk screen printing, offset Printing, gravure printing, inkjet printing, vapor deposition etc. can be mentioned.

The decorative film of the present invention can be produced a decorative molded body by various molding methods such as vacuum molding, pressure molding, TOM molding, injection molding, in-mold molding, press molding, and stamping molding.
It is on acrylic film from the point of prevention of blocking at the time of decorative film production, prevention of damage, prevention of damage at molding, prevention of mold marks, and prevention of stain after molding until the decorative molded body is put to use. A peelable protective film can further be provided on the acrylic film.
In addition, when the decorative film is attached to the object to be decorated using the adhesive layer, it can be peeled off on the adhesive layer provided on the inside of the decorative film from the viewpoint of blocking prevention. Can also be provided.

  The protective film which can be used by this invention is not specifically limited, A well-known plastic film and a paper film can be selected suitably, and can be used. As a film which can be used as a protective film, for example, polyethylene film, polypropylene film, polyester film, polycarbonate film, polymethyl methacrylate film, polyamide film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polystyrene Although a film, a polyacrylonitrile film, aluminum foil, paper etc. are mentioned, it is not limited and what 1 type or multiple types laminated | stacked can be used. Further, the protective film may be subjected to peeling treatment or adhesion treatment on the above-mentioned plastic film.

  As a method of providing a protective film to the decoration film of the present invention, a coating liquid is applied to a base material layer, it is made to dry, when a hard coat layer or an adhesive layer is provided, a protective film is pasted together, protection After a coating liquid is apply | coated on a film, it dries as needed, aging is performed, a hard-coat layer and an adhesive bond layer are provided, and the method of bonding together with a base material layer or a decoration film etc. are mentioned. When the hard coat layer is first provided on the protective film, it may be attached using an adhesive as required.

The decorative film of the present invention has various aspects. The specific example of the aspect is demonstrated based on a figure.
FIG. 1 shows an embodiment having only the hard coat layer (HC) and the substrate layer (1).
FIG. 2 shows an embodiment having a hard coat layer (HC), a substrate layer (1a) and a substrate layer (1b). The first substrate layer (1a) and the second substrate layer (1b) can be provided by coextrusion.
FIG. 3 shows an embodiment in which the adhesive layer (2) is located between the hard coat layer (HC) and the substrate layer (1).
FIG. 4 has a hard coat layer (HC) and a substrate layer (1), and is on the opposite side of the substrate layer (1) (the side opposite to the side on which the hard coat layer (HC) is provided) The aspect which has a colored layer (3) is shown.
FIG. 5 has a hard coat layer (HC), a substrate layer (1) and a colored layer (3), and a colored layer (3) between the hard coat layer (2) and the substrate layer (1) Shows the mode in which is located.
FIG. 6 has a hard coat layer (HC), a substrate layer (1), an adhesive layer (2) and a colored layer (3), and between the hard coat layer (HC) and the substrate layer (1) The adhesive layer (2) is located in and the aspect which has a colored layer (3) in the other side (opposite to the adhesive layer (2) being provided) of a base material layer (1) is shown.
FIG. 7 shows the hard coat layer (HC), the first base layer (1a), the second base layer (1b), the first adhesive layer (2a) and the second adhesive layer (2b) And the first adhesive layer (2a) is between the hardcoat layer (HC) and the first substrate layer (1a), and the second adhesive layer (2b) is the first group. The aspect located in a material layer (1a) and a 2nd base material layer (1b) is shown.
FIG. 8 has a hard coat layer (HC), a base layer (1), a colored layer (3) and an adhesive layer (2), and the opposite side of the base layer (1) (hard coat layer (HC) The colored layer (3) is located on the side opposite to the side provided with), and the hard coat layer (HC) and the adhesive layer (2) are located on the surface, respectively.

<Decorated molded body>
Next, the decorated molded body of the present invention will be described.
The decorative molded body of the present invention is a molded body whose surface is covered with the above-mentioned decorative film, and the material of the molded body to be covered (hereinafter referred to as a body to be decorated) is not particularly limited. It can be used.
Wood, paper, metal, plastic, fiber reinforced plastic, rubber, glass, mineral, clay etc. can be mentioned as an example of the material which can be used as a body to be decorated, and one or two or more kinds can be used in combination Can.
Examples of the plastic include polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyurethane, epoxy resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, poly (meth) acrylate, polycarbonate, polyamide, polyimide Polyphenylene ether, polyphenylene sulfide, polyester, polytetrafluoroethylene, etc. may be mentioned, and one type or two or more types can be used in combination.
Examples of the fiber reinforced plastic include carbon fiber reinforced plastic, glass fiber reinforced plastic, aramid fiber reinforced plastic, polyethylene fiber reinforced plastic and the like, and one or more types can be used in combination.
As the metal, for example, hot rolled steel, cold rolled steel, galvanized steel, electrogalvanized steel, galvanized steel, alloyed galvanized steel, zinc alloy plated steel, copper plated steel, zinc-nickel plated steel, Zinc-aluminium-plated steel, iron-zinc plated steel, aluminum-plated steel, aluminum-zinc plated steel, tin-plated steel, etc., aluminum, stainless steel, copper, aluminum alloy, electromagnetic steel, etc., one or more kinds It can be used in combination. In addition, a metal-repellent layer may be provided on the surface of the metal.

  There is no limitation in particular in the method to integrate with the decoration film of this invention, and the said to-be-decided body, It can be integrated by a well-known integration method. As an integration method, for example, insert molding, in-mold molding, vacuum molding, pressure forming, TOM molding, press molding and the like can be used.

For example, after the decorative film of the present invention is preformed into a desired shape, a plastic or fiber reinforced plastic may be injection-molded so that the hard coat layer side is the outermost layer, to obtain a decorated molded body.
Alternatively, a molded body is obtained from plastic, fiber reinforced plastic, or metal, and a hard coat is applied to the surface of the molded body according to the decorative film of the present invention or a preformed body having a decorative film desired shape. It can also be obtained by sticking so that the layer side is the outermost layer.

  In the decorated molded body of the present invention, the hard coat layer side of the decorated film is positioned as the outermost layer. As described above, the hard coat layer of the decorative film may be provided with a protective film for protecting appearance defects which may occur in each step such as coating, drying, aging, and molding integration. It is preferable that the said protective film is peeled in the scene where the decorated molded object is used.

The decorative molded body thus obtained can be used as an interior part of a car such as a metal or piano black tone instrument panel decoration panel, shift gate panel, door trim, air conditioner operation panel, car navigation, etc. Used as exterior parts such as emblems, center ornaments of tire wheels, and name plates.
In addition to exterior components such as home appliances, smart keys, smartphones and mobile phones, and notebook computers, in addition to automotive interior and exterior components, exterior materials such as helmets and suitcases, and LCD screens such as car navigation systems and LCD TVs are protected. It can be suitably used for protective sheets, exterior materials such as electricity storage devices, sports goods such as tennis rackets and golf shafts, doors and partitions for houses, construction materials such as wall materials, and the like.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples. In the examples, "parts" means "parts by mass" and "%" means "mass%" (excluding "% in elongation percentage").

Preparation of Photocurable Composition "A-1"
0.5 part of AM-90G (Methoxy polyethylene glycol # 400 acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name "AM-90G"), 95.5 parts of HDDA (1,6-hexanediol diacrylate), Irgacure 184 (1 Four parts of -hydroxy-cyclohexyl-phenyl-ketone (manufactured by BSAF, product name "IRGACURE 184") was placed in a light shielding bottle and stirred well to obtain a photocurable composition A-1. The content of the component having an alkylene oxide chain was 0.5% by mass.

Preparation of Photocurable Composition “A-2 to 17”
Preparation of Comparative Photocurable Composition "B-1"
In the same manner as for the photocurable composition A-1, each component is compounded at the compounding ratio shown in Table 1 and stirred to form photocurable compositions A-2 to 17 and a photocurable composition B-1 for comparison. The contents of the components having an alkylene oxide chain and the sum of the hydroxyl value and the acid value are shown in Table 1.
The acid value and the hydroxyl value were measured by the following method.

<< Measurement of acid number (AV) >>
Approximately 1 g of the resin solution is accurately weighed into a stoppered Erlenmeyer flask, and dissolved by adding 50 ml of a mixed solution of toluene / ethanol (volume ratio: toluene / ethanol = 2/1). To this, add phenolphthalein TS as an indicator and hold for 30 seconds. Then, it titrates with 0.1 mol / L alcoholic potassium hydroxide solution until the solution becomes pinkish. The acid value was determined by the following equation. The acid value is a numerical value of the dry state of the resin.
Acid value (mg KOH / g) = (a × F × 56.1 × 0.1) / SS: collection amount of sample × (solid content of sample / 100) (g)
a: Titration of 0.1 mol / L alcoholic potassium hydroxide solution (ml)
F: titer of 0.1 mol / L alcoholic potassium hydroxide solution

<< Measurement of hydroxyl value (OHV) >>
Approximately 1 g of the resin solution is accurately weighed into a stoppered Erlenmeyer flask, and dissolved by adding 50 ml of a mixed solution of toluene / ethanol (volume ratio: toluene / ethanol = 2/1). Furthermore, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride is dissolved in pyridine to a volume of 100 ml) is added, and the mixture is heated to 100 ° C. and stirred for about 1 hour. To this, add phenolphthalein test solution as an indicator and hold for 30 seconds. Then, titrate with 0.5 mol / L alcoholic potassium hydroxide solution until the solution becomes pinkish. Separately, as a blank test, an acetylating agent is added only to a toluene / ethanol mixed solution, and a solution heated at 100 ° C. for 1 hour is titrated with a 0.5 mol / L alcoholic potassium hydroxide solution. The hydroxyl value was determined by the following formula. The hydroxyl value is a numerical value of the dry state of the resin.
Hydroxyl value (mg KOH / g) = {(b-a) x F x 56.1 x 0.5} / S + D
S: amount of sample collected × (solid content of sample / 100) (g)
a: 0.5 mol / L Titration of alcoholic potassium hydroxide solution (ml)
b: Titration of 0.5 mol / L alcoholic potassium hydroxide solution in blank experiment (ml)
F: titer of 0.5 mol / L alcoholic potassium hydroxide solution D: acid value (mg KOH / g)

Example 1
After applying photocurable composition A-1 to a polymethyl methacrylate (PMMA) film with a thickness of 100 μm using a doctor blade, it was irradiated with a high pressure mercury lamp (accumulated light quantity: 1000 mJ / cm ² ) for hard coating A decorative film having a layer thickness of about 10 μm was obtained.
About the obtained decorative film, according to the method mentioned later, evaluation of moldability, abrasion resistance, and chemical resistance was performed. The results are shown in Table 2.

<Evaluation of extensibility>
The obtained decorative film was stretched by 200% under the following conditions.
Tensile tester: "Table-top precision universal testing machine AGS-X" (manufactured by Shimadzu Corporation)
Heating furnace: "Temperature chamber TCE-N300" (manufactured by Shimadzu Corporation)
Sample width: 10 mm
Temperature: 120 ° C
Tension speed: 1 mm / min
Chuck distance: 10 mm
The surface of the hard coat layer after 50% elongation was observed and evaluated according to the following criteria.
:: no cracks were found △: one or more cracks were found × Hard coat layer is completely broken

«Evaluation of chemical resistance»
Apply 0.5 g of sunscreen cream (Neutrogena Ultra Sheer DRY-TOUCH SUNSCREEN SPF 55 (manufactured by Johnson & Johnson Co., Ltd.)) to the hard coat layer of the obtained decorative film, and mount a glass plate from above . A load of 500 g was further placed on the glass plate and left at 80 ° C. for 24 hours. After standing, the sunscreen cream was rinsed with water and drained, and then the appearance of the decorative film was visually observed from the hard coat layer side and evaluated according to the following criteria.
◎: appearance defects such as generation of wrinkles and discoloration were not observed in both the hard coat layer and the base material layer.
○: A part of the hard coat layer floats from the substrate layer.
Δ: Discoloration of the substrate layer is observed in part.
X: Discoloration of the substrate layer is observed overall.

«Evaluation of abrasion resistance»
The hard coat layer of the obtained decorative film was rubbed with steel wool (# 0000) for 10 cycles with a load of 100 g, and the number of scratches was evaluated based on the following criteria.
:: 4 or less scratches ○: 5 to 19 scratches Δ: 20 to 49 scratches ×: 50 or more scratches

[Examples 2 to 17], [Comparative Example 1]
In the same manner as in Example 1, the photocurable compositions A-2 to A-17 described in Table 1 and the photocurable composition B-1 for comparison were coated on a PMMA film and photocured to obtain a decorative film. .
The evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

  As shown in Table 2, in Examples 1 to 17, the decorative film having a hard coat layer which is a cured product of a suitable photocurable composition is excellent in stretchability, chemical resistance, and abrasion resistance.

  On the other hand, as shown in Table 2, Comparative Example 1 does not contain the component having an alkylene oxide chain in the photocurable composition, so the components of the hard coat layer and the sunscreen cream are in affinity, and the chemical resistance is poor. .

[Example 18]
A hard coat layer was formed on a polycarbonate substrate having a thickness of 100 μm instead of the PMMA substrate used in Example 1 to obtain a decorative film, and the same evaluation as in Example 1 was performed. The results are shown in Table 3.

[Examples 19 to 22]
A decorative film was obtained using the base material (each thickness 100 μm) shown in Table 3 instead of the polycarbonate base material used in Example 18, and the same evaluation as in Example 17 was performed. The results are shown in Table 3.
In Example 19, a hard coat layer was formed on the polymethacrylic side of the two-layered film of polymethacrylic and polycarbonate.

[Example 23]
In the same manner as in Example 1, a hard coat layer was formed on a PMMA substrate to obtain a member 1.
Separately, photocurable composition “A-1” 100 parts by mass (solid mass) MA 100 (carbon black manufactured by Mitsubishi Chemical Corp.) 5 parts by mass (solid mass), BYK- 9076 (dispersant manufactured by BYK) 0.5 mass A part (solid mass) was added, and methyl ethyl ketone (MEK) was further added to a solid content of 30% and stirred to obtain a colored curable resin composition.

The colored curable resin composition is applied to the PMMA side of the member 1 using a bar coater, dried in an oven at 100 ° C. for 1 minute to volatilize the solvent, and then irradiated with a high pressure mercury lamp (accumulated light amount: 1000 mJ / cm ² ) and a 5 μm thick colored layer was provided.
Next, an adhesive (AD-76G1 manufactured by Toyo Moreton Co., Ltd.) was applied onto the colored layer to a dry film thickness of 5 μm to obtain a decorative film with an adhesive layer and a colored layer. .

In accordance with the following procedure, a decorative molded body is obtained, in which the decorative film is carried on the surface of the convex side of a rectangular steel member (a body to be decorated) having the following shape.
<Procedure>
A square steel member was installed in a molding machine, and the adhesive layer of the decorative film was disposed above the steel member so as to face the steel member without coming into contact with the steel member.
Next, while the decorative film is heated to about 120 ° C., it is vacuum molded on the surface of the steel member with a vacuum suction force of about 1.5 atmospheric pressure to cure the adhesive layer and the colored layer, and the steel member is made The decorative molded body which the decorative film carry | supports on the surface of the convex side of was obtained.
<Square steel member>
A steel plate is formed into a square 90 mm long × 90 mm wide × 5 mm deep, with a corner R of about 10.

«Evaluation of adhesion»
A grid-like scratch is made to reach deep from the hard coat layer side of the convex part surface (surface of 90 mm by 90 mm) of the decorative molded body to the interface between the decorative film and the object to be decorated, JIS The test was performed by the cellophane tape peeling method according to K-5400. The number of squares not peeled off in 100 squares was counted, and the adhesion between the decorative film and the object to be decorated was evaluated according to the following criteria.
○: Peeling area 0%
:: Peeling area greater than 0%, less than 35% x: Peeling area 35% or more

[Examples 24 to 44]
A decorative film having an adhesive layer and a colored layer was obtained in the same manner as in Example 23, except that the adhesive shown in Table 4 was used instead of the adhesive used in Example 23.

Subsequently, molding and adhesion were evaluated on the objects to be decorated described in Table 4 in the same manner as in Example 23.
The ABS of the body to be decorated is an acrylonitrile-butadiene-styrene resin, and the CFRP is a carbon fiber reinforced resin, and the shape of each is the same as that of the steel member of Example 22.

[Example 45]
A decorative film having a colored layer was obtained in the same manner as in Example 23 except that the adhesive layer was not provided.
The obtained decorative film is inserted into the cavity of an injection molding mold, vacuum suction is performed under the condition of about 1.5 atmospheric pressure while heating to about 120 ° C., and a square (90 mm long × 90 mm wide × depth It was preformed into a square of 5 mm, with a corner R of about 10).
Next, an ABS resin was injection-molded to a thickness of about 3 mm on the colored layer side of the preform at a molding temperature of 220 to 240 ° C. and a mold temperature of 30 to 50 ° C. to obtain a decorated molded body.
The adhesion between the decorative film and the object to be decorated was evaluated in the same manner as in Example 23 for the obtained decorative molded body.

[Example 46]
A decorated molded body was produced in the same manner as in Example 45 except that the injection resin was changed from ABS resin to carbon fiber reinforced resin (CFRP), and the same evaluation was performed.

(HC): hard coat layer (1), (1a), (1b): substrate layer (2), (2a), (2b): adhesive layer (3): colored layer (101) to (108) : Decorative film

Claims (12)

A decorative film comprising a laminate including a hard coat layer and a substrate layer, wherein the hard coat layer is a photocured product of a photocurable composition,
The hard coat layer has an alkylene oxide chain,
The said photocurable composition contains the monomer which has a (meth) acryloyl group, and a photoinitiator, The decoration film characterized by the above-mentioned. Whether the monomer having a (meth) acryloyl group has an alkylene oxide chain,
Or the photocurable composition further comprises a component (D) having an alkylene oxide chain and having no (meth) acryloyl group,
The decorative film according to claim 1.   The decorative film according to claim 1 or 2, characterized in that the monomer (A) having an alkylene oxide chain and the monomer (B) not having an alkylene oxide chain are contained as the monomer having a (meth) acryloyl group.   The monomer (C) having at least one functional group of a hydroxyl group or a carboxyl group and a photopolymerizable functional group is contained as the monomer having a (meth) acryloyl group. The decorative film described in the item.   The sum total of the hydroxyl value of the said photocurable composition and an acid value is 1-300 mgKOH / g, The decoration film of Claim 4 characterized by the above-mentioned.   The content of the monomer (A) having an alkylene oxide chain and a (meth) acryloyl group contained in 100% by mass of the photocurable composition is 0.5 to 90% by mass. The decorative film described in.   The said base material layer consists of a single layer or multiple layers selected from the group consisting of polyester, polycarbonate, polymethyl methacrylate, polyethylene, and polypropylene, The any one of Claims 1-6 characterized by the above-mentioned. Decorative film.   The decorative film according to any one of claims 1 to 7, wherein the hard coat layer and the base material layer are in contact with each other.   The decorative film according to any one of claims 1 to 8, further comprising at least one of an adhesive layer and a colored layer.   The decorative film according to claim 9, wherein the adhesive layer is laminated between the base layer and the hard coat layer.   The decorative film according to claim 9, wherein the adhesive layer is laminated on the non-facing surface side of the hard coat layer of the base layer. It has a to-be-decorated body and the decorating film which coat | covers at least one part of the said to-be-decorated body, The said decorating film is a decorating film of any one of Claims 1-11, Decorative molded body.