JP2019116614A - Thermosetting hard coat agent, laminate film, and decorative molded body - Google Patents

Abstract

To provide a thermosetting hard coat agent, high in general purpose property of a manufacturing method, and excellent in moldability during molding when a decorative molded body is manufactured by using the resulting laminate film, and the laminate film, and further provide a decorative molded body excellent in designability, abrasion resistance, and excellent in chemical resistance (sunscreen cream resistance).SOLUTION: There is provided a thermosetting hard coat agent containing a resin having a diene structure (A) and a curing agent having 2 or more maleimide structures (B), a laminate film having a substrate layer and a hard coat layer formed from the thermosetting hard coat agent, and a decorative molded body having a body to be decorated and the laminate film covering at least a part of the body to be decorated.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermosetting hard coat agent containing a resin having a specific structure and a curing agent, and a laminated film having a hard coat layer formed from the thermosetting hard coat agent. In addition, the present invention relates to a decorated molding having a surface covered with the laminated film.

  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. Moreover, it is calculated | required that it is excellent in abrasion resistance, abrasion resistance, chemical resistance (sun cream resistance etc.) on the surface of the decorated molded article.

  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 a 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.

Patent Document 3 uses an ink composition for hard coat layer having ionizing radiation curing property,
Step (1) A decorative sheet having a hard coat layer forming layer formed by applying at least a release layer and an ink composition having ionizing radiation curing property on one side of a substrate film in an injection molding die in this order Process of arranging
Step (2) An injection step of injecting a molten resin into the cavity, cooling and solidifying, and laminating and integrating the resin molded body and the decorative sheet,
Process (3) A process 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 molded object,
Step (5) A hard coat layer forming step of curing the hard coat layer forming layer provided on the molded body under 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 provided with a hard coat layer containing a resin on a base film, and has an elongation of 10% or more under an atmosphere of 23 ° C. and 50% RH. Certain molding laminated hard coat films are disclosed. 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 base 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).

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

Since a decoration film is used, for example for the interior member of a car, the outstanding design nature is called for. Moreover, while having the outstanding moldability which can be three-dimensionally molded, abrasion resistance, chemical resistance (sun cream resistance etc.) etc. are calculated | required, for example, when using for the interior member of a motor vehicle. Moreover, in order to carry out application development to various uses, the manufacturing method of a decorated molded body with high versatility is calculated | required.
Since it is difficult to uniformly apply ultraviolet light to a molded product having a complicated structure because conventional ultraviolet-curable hard coat layers are cured by irradiation with ultraviolet light after molding, unevenness in the cured state is likely to occur. On the other hand, by molding a decorative film on which a hard coat layer which has already been cured is laminated, it is possible to maintain a cured state uniformly with respect to a molded product of any shape. However, in general, the hard coat layer which has already been cured is inferior in moldability. As described above, the hard coat layer of the decorative film needs to have both moldability and chemical resistance such as sunscreen cream resistance in the cured state.
The above Patent Documents 1 to 8 do not satisfy all of these characteristics.

  This invention is comprised in view of the said background, When manufacturing a decorating molded object using the laminated film obtained, the versatility of a manufacturing method is high and it is excellent in the moldability at the time of shaping | molding, and heat. An object of the present invention is to provide a curable hard coat agent and a laminated film. Furthermore, it aims at providing the decoration molding which is excellent in design nature and abrasion resistance, and excellent in chemical resistance (sun cream resistance etc.).

The present invention solves the above-mentioned problems by incorporating a resin having a diene structure and a curing agent having two or more maleimide structures in a hard coat agent to make the resin thermosetting.
That is, the present invention relates to the following [1] to [9].
[1] A thermosetting hard coat agent comprising a resin (A) having a diene structure and a curing agent (B) having two or more maleimide structures.
[2] The thermosetting hard coat agent according to [1], wherein the diene structure of the resin (A) is a furan structure.
[3] The weight average molecular weight of the resin (A) having a diene structure is in the range of 10,000 to 1,500,000, and the molecular weight of the curing agent (B) having two or more of the maleimide structures is 200 to 1 The thermosetting hard coat agent according to [1] or [2], which is in the range of 1,000.
[4] The diene structure concentration of the resin (A) having a diene structure is 0.05 mmol / g to 6 mmol / g, and the diene structure concentration of the resin (A) having the diene structure and the maleimide structure are two The thermosetting hard-coat agent in any one of [1]-[3] whose molar ratio with the hardening | curing agent (B) which has more than maleimide structure / diene structure is less than one.
[5] The thermosetting hard coat agent according to any one of [1] to [4], further containing an antioxidant.
[6] A laminated film having a base material layer and a hard coat layer formed from the thermosetting hard coat agent according to [1] to [5].
[7] The laminated film according to [6], which has an elongation of 100% or more under a 120 ° C. environment.

[8] The laminated film according to [6] or [7], further comprising at least one of an adhesive layer and a colored layer.
[9] A to-be-decorated body, and a laminated film covering at least a part of the to-be-decorated body, the laminated film being the laminated film according to any one of [6] to [8] There is a decorated molded body.

  ADVANTAGE OF THE INVENTION According to this invention, when manufacturing a decorating molded object using the laminated film obtained, the versatility of a manufacturing method is high and the thermosetting hard-coating agent and laminated film which are excellent in the moldability at the time of shaping | molding are provided. Further, the laminate film can provide a decorative molded body having excellent designability and abrasion resistance, and excellent chemical resistance (such as sunscreen cream resistance).

Typical sectional drawing which shows the structural example of the laminated | multilayer film of this invention. Typical sectional drawing which shows the structural example of the laminated | multilayer film of this invention. Typical sectional drawing which shows the structural example of the laminated | multilayer film of this invention. Typical sectional drawing which shows the structural example of the laminated | multilayer film of this invention. Typical sectional drawing which shows the structural example of the laminated | multilayer film of this invention. Typical sectional drawing which shows the structural example of the laminated | multilayer film of this invention. Typical sectional drawing which shows the structural example of the laminated | multilayer film of this invention. Typical sectional drawing which shows the structural example of the laminated | multilayer film of this invention. Typical sectional drawing which shows the structural example of the laminated | multilayer film of this invention. Reaction schematic which shows Diels-Alder reaction of this invention. The spectral chart of the infrared spectroscopy measurement which shows the presence or absence of the bicyclo [2.2.1] hept- 2-ene structure produced | generated by the Diels-Alder reaction of Example 15, and the reversibility of a structure.

  Hereinafter, an example of an embodiment to which the present invention is applied will be described. In addition, numerical value "AB" specified in this specification shows numerical value A or more and B or less. Also, "(meth) acrylic" means acrylic and methacrylic, and "(meth) acrylate" means acrylate and methacrylate.

<Thermosetting hard coat agent>
The thermosetting hard coating agent of the present invention is a thermosetting hard coating agent containing a resin (A) having a diene structure and a curing agent (B) having two or more maleimide structures.

In general, when a film obtained by thermosetting a thermosetting resin composition is heated and softened to be processed, it is effective to lower the crosslink density in order to impart moldability such as extensibility. However, on the other hand, it is effective to increase the crosslink density in order to impart durability such as chemical resistance (sunproof cream resistance etc.) and surface hardness to the coated film after processing.
By the way, the formability such as extensibility is required only when the temperature of the film is high exactly at the time of forming, and it is required to maintain a certain shape after forming. On the other hand, durability is required after molding. That is, the moldability and the durability do not necessarily have to be compatible at the same time, but the moldability is required at the processing temperature at the time of molding, and the durability in the temperature range centered around room temperature actually used after molding is required. . In consideration of the crosslink density, it is considered suitable that the crosslink density is low at the time of heating during molding and the crosslink density is high after molding.

The hard coat agent of the present invention forms a reversible crosslinked structure utilizing a cycloaddition reaction between a resin (A) having a diene structure and a curing agent (B) having two or more maleimide structures. It is possible to meet such demands.
The cycloaddition reaction is represented by the Diels-Alder reaction, and it is possible to bias the equilibrium between the cyclization reaction and the ring-opening reaction by heat. The equilibrium is biased to the bond dissociation (ring opening) reaction in the higher temperature region.
Therefore, in a laminate film having a hard coat layer formed from the hard coat agent of the present invention incorporating a thermally reversible crosslinking mechanism, partial crosslinking of the cured hard coat layer is unraveled in a high temperature region during molding, The crosslink density decreases and the extensibility develops to improve the moldability. On the other hand, after molding, at around room temperature, the crosslinking is remodeled to increase the crosslinking density, and the resulting decorated molded body exhibits durability.

[Resin (A)]
The resin (A) in the present invention will be described.
In order to construct the cross-linked structure, a chemical structure capable of reversible binding with a curing agent is required, and the resin (A) has a diene structure as a chemical structure capable of reversible binding.

  The diene structure of the present invention is preferably a conjugated diene structure having an unsubstituted or electron donating substituent. Specific examples thereof include a 1,3-butadiene structure, a pyrrole structure, a thiophene structure, a furan structure, an anthracene structure and the like, and in particular, a furan structure is preferable from the viewpoint of the reactivity of the curing agent with the maleimide structure. When the diene structure is a furan structure, both durability such as chemical resistance and surface hardness and moldability are improved.

  The resin (A) is not particularly limited as long as it has a diene structure, and preferred specific examples thereof include poly (meth) acrylates, polyurethanes, polyesters, polyamides and polyimides having the diene structure. Mention may be made of polycarbonates, polyolefins, polystyrenes, polysiloxanes, polyethers, copolymers containing maleic anhydride and epoxy resins, which may be used alone or in mixtures. Among these, acrylic resins can easily introduce a diene structure into the resin (A), and not only can easily control the amount of introduction of the diene structure, but also easily control molecular weight and copolymerization composition, so It is preferable because various physical properties necessary as a coating agent can be compatible.

  The content of the diene structure introduced to the resin (A) in the present invention is preferably 0.05 to 6 mmol / g, more preferably 0.05 to 3 mmol / g, and still more preferably 0.2 to 2 mmol / g. When it exists in the range of 0.05-6 mmol / g, the storage stability over time of resin (A) and transparency may become favorable. As a method of obtaining a resin (A) having a diene structure, 1. A method obtained by copolymerizing "a monomer having a diene structure" and "another monomer", There is a method in which the compound having a diene structure can be reacted with the resin after obtaining a resin capable of reacting with the compound having a diene structure, but from the viewpoint of simplification of the synthesis process, it can be obtained by the former method. Is preferred.

Among the “monomers having a diene structure”, the monomer having a 1,3-butadiene structure as a diene structure is not particularly limited, and, for example, 2,6-hexadiene dicarboxylic acid, 2,6-hexadiene dialdehyde, 2- 6-hexadiene diamine, 2,6-hexadiene dialcohol etc. are mentioned.
The monomer having a pyrrole structure as a diene structure is not particularly limited. For example, vinyl pyrrole, pyrrole styrene, (meth) acrylic acid pyrrole, pyrrole dicarboxylic acid, pyrrole dicarbonyl chloride, pyrrole diamine, pyrrole dialcohol, diformyl pyrrole Etc.

The monomer having a thiophene structure as a diene structure is not particularly limited. For example, vinylthiophene, thienylstyrene, thienyl (meth) acrylate, thiophenedicarboxylic acid, thiophenedicarbonyl chloride, thiophenediamine, thiophenedialcohol, diformylthiophene Etc.
The monomer having a furan structure as a diene structure is not particularly limited. Examples thereof include vinyl furan, furfuryl styrene, furfuryl (meth) acrylate, furan carboxylic acid, furan carbonyl chloride, furan amine, furan alcohol, and diformyl furan. Can be mentioned.

  The monomer having an anthracene structure as a diene structure is not particularly limited. For example, 9-vinylanthracene, 4-anthranylstyrene, (meth) acrylic acid anthracene, diformylanthracene, dihydroxyanthracene, dicarboxyanthracene, dicarbonyl chloride anthracene And diaminoanthracene.

As the "other monomer", for example, a (meth) acrylic acid alkyl ester monomer having 1 to 20 carbon atoms of alkyl group in the ester moiety, a (meth) acrylic acid ester monomer having an ester moiety of alicyclic hydrocarbon group, etc. Can be mentioned.
Examples of (meth) acrylic acid alkyl ester monomers having 1 to 20 carbon atoms of the alkyl group of the ester moiety include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate ( Butyl) butyl acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, decyl (meth) acrylate, Examples include dodecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate.

Examples of (meth) acrylic acid ester monomers having an alicyclic moiety as the ester moiety include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, bornyl ( Examples include meta) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate and the like.
In addition, (meth) acrylic acid ester monomers having an ester moiety of an aromatic group, and ethylenically unsaturated monomers other than acrylic acid esters such as styrene, vinyl ether, vinyl acetate, and acrylonitrile, terephthalic acid, isophthalic acid, orthophthalic acid, Compounds having a dicarboxylic acid such as phthalic acid, compounds having a dialcohol such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-propanediol, tetramethylene diamine, pentamethylene diamine And compounds having a diamine such as 2-methylpentanediamine. These monomers are not limited to such examples, and may be used alone or in combination of two or more types, but one or more types have a (meth) acroyl group from the viewpoint of weather resistance. It is preferred to use a monomer.

The resin (A) of the present invention can be obtained by polymerizing the various monomers exemplified above by a known method using a polymerization initiator. The polymerization can be carried out without solvent, but solution polymerization carried out in an organic solvent is preferred. In emulsion polymerization and suspension polymerization performed in an aqueous system, synthesis is generally carried out by adding an emulsifier or the like, and the durability of the hard coat layer obtained by the presence of the emulsifier is poor.
Examples of solvents that can be used in solution polymerization include acetone, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, toluene, xylene, anisole, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol and the like. However, the present invention is not limited to such exemplifications, and may be used alone or in combination of two or more. Although polymerization temperature can be selected suitably for reaction rate adjustment, it is preferable that it is the range of 50-130 degreeC.

  Examples of the polymerization initiator include azo compounds and organic peroxides. As the azo compounds, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane 1-carbonitrile), 2,2 4'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate), 4 2,4'-azobis (4-cyanovaleric acid) or 2,2'-azobis (2-hydroxymethylpropionitrile), 2,2'-azobis [2- (2-imidazolin-2-yl) propane] Etc. Moreover, as an azo compound, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxy dicarbonate, di-n-propyl peroxy dicarbonate or di (2-ethoxyethyl) peroxy dicarbonate Tert-Butyl peroxy-2-ethylhexanoate, tert-butyl peroxy neodecanoate or tert-butyl peroxy bivalate, (3,5,5-trimethylhexanoyl) peroxide or dipropionyl peroxide, Diacetyl peroxide and the like can be mentioned.

  Obtaining a resin (A) having a diene structure The “compound having a diene structure” used in the method of is not particularly limited, and examples thereof include 2,4-hexadien-1-ol, pyrrole carboxylic acid, formylpyrrole, mercaptothiophene, aminothiophene, formylthiophene and thiophenemethanol. Thiophene carboxylic acid, furfuryl alcohol, furfuryl amine, furfuryl mercaptan, furfural, aminoanthracene, anthracenediol, etc. may be mentioned, and these may be used alone or in combination. A resin (A) having a diene structure can be obtained by reacting these with a resin capable of reacting with a “compound having a diene structure” having a carboxyl group, an epoxy group, an isocyanate group, an acid anhydride group and the like.

  The resin (A) may have other functional groups such as a hydroxyl group and a carboxyl group as long as the effects of the present invention are not impaired. The hard coat agent of the present invention may also contain other curing agent that causes a crosslinking reaction with these functional groups. For example, by giving a hydroxyl group to the resin (A) and blending an isocyanate-based curing agent, strong crosslinking of the hydroxyl group and the isocyanate group occurs to improve the durability.

The weight average molecular weight of the resin (A) is preferably 1,000 to 1,500,000, more preferably 10,000 to 1,500,000, and 100,000 to 1,000,000. Particularly preferred. When the weight average molecular weight is 1,000 or more, the extensibility and durability of the film can be compatible, and when the weight average molecular weight is 1,500,000 or less, the curing agent (B) is blended. It is possible to impart storage stability and excellent coating suitability when used.
The resin (A) having a desired weight average molecular weight can be synthesized by a known method, for example, by appropriately selecting the concentration of the polymerization initiator, the concentration of the monomer in the solvent, and the reaction temperature.

  It is preferable that the glass transition temperature (hereinafter, also referred to as “Tg”) of the resin (A) is 0 to 150 ° C. When the Tg is 0 ° C. or more, the durability of the cured film is improved. When the Tg is 150 ° C. or less, the extensibility of the cured film can be improved, and the viscosity increase of the resin composition can be suppressed.

[Hardener (B)]
The curing agent (B) in the present invention will be described.
The curing agent (B) in the present invention is a curing agent having two or more maleimide structures, and the maleimide structure undergoes cycloaddition reaction with the diene structure of the resin (A).

  Specific examples of the curing agent (B) in the present invention include o-phenylenebismaleimide, m-phenylenebismaleimide, p-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, N, N ′-( Toluene-2,6-diyl) bismaleimide), 4,4'-diphenylmethane bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4,4'-Diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis (3-maleimidophenoxy) benzene, 1,3-bis (4-maleimidophenoxy) benzene, polyphenylmethane maleimide ( CAS NO: 67784-74-1, E (A reaction product of a polymer consisting of mualdehyde and aniline and maleic anhydride), N, N'-ethylenebismaleimide, N, N'-trimethylenebismaleimide, N, N'-propylenebismaleimide, N, N'-tetramethylene Bismaleimide, N, N′-pentamethylene bismaleimide, N, N ′-(1,3-pentanediyl) bis (maleinimide), N, N′-hexamethylene bismaleimide, N, N ′-(1,7 -Heptanediyl) bismaleimide, N, N '-(1,8-octanediyl) bismaleimide, N, N'-(1,9-notanediyl) bismaleimide, N, N '-(1,10-decanediyl) bis Maleimide, N, N '-(1,11-undecanediyl) bismaleimide, N, N'-(1,12-dodecanediyl) bismalei N, N '-[(1,4-phenylene) bismethylene] bismaleimide, N, N'-[(1,2-phenylene) bismethylene] bismaleimide, N, N '-[(1,3-phenylene ) Bismethylene] bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, N, N '-[(methylimino) bis (4,1-phenylene)] bismaleimide, N, N' -(2-hydroxypropane-1,3-diylbisiminobiscarbonylbisethylene) bismaleimide, N, N '-(dithiobisethylene) bismaleimide, N, N'-[hexamethylene bis (iminocarbonylmethylene)] Bismaleimide, N, N'-carbonylbis (1,4-phenylene) bismaleimide, N, N ', N' '-[nitrilotris (ethylene) N, N ′, N ′ ′-[nitrilotris (4,1-phenylene)] trismaleimide, N, N ′-[p-phenylenebis (oxy-p-phenylene)] bismaleimide, N, N '-[methylene bis (oxy) bis (2-methyl-1,4-phenylene)] bismaleimide, N, N'-[methylene bis (oxy-p-phenylene)] bis (maleinimide) N, N '-[ Dimethylsilylene bis [(4,1-phenylene) (1,3,4-oxadiazole-5,2-diyl) (4,1-phenylene)] bismaleimide, N, N ′-[(1,1 3-phenylene) bisoxybis (3,1-phenylene)] bismaleimide, 1,1 ′-[3′-oxospiro [9H-xanthene-9,1 ′ (3′H) -isobenzofuran] -3,6 Diyl] bis (1H-pyrrole-2,5-dione), N, N '-(3,3'-dichlorobiphenyl-4,4'-diyl) bismalemide, N, N'-(3,3'-dimethyl) Biphenyl-4,4′-diyl) bismaleimide, N, N ′-(3,3′-dimethoxybiphenyl-4,4′-diyl) bismaleimide, N, N ′-[methylene bis (2-ethyl-4,4 1-phenylene)] bismaleimide, N, N '-[methylenebis (2,6-diethyl-4,1-phenylene)] bismaleimide, N, N'-[methylenebis (2-bromo-6-ethyl-4, 1-phenylene)] bismaleimide, N, N '-[methylenebis (2-methyl-4,1-phenylene)] bismaleimide, N, N'-[ethylenebis (oxyethylene)] bismaleimide, N, N -[Sulfonylbis (4,1-phenylene) bis (oxy) bis (4,1-phenylene)] bismaleimide, N, N '-[naphthalene-2,7-diylbis (oxy) bis (4,1-phenylene) )] Bismaleimide, N, N ′-[p-phenylenebis (oxy-p-phenylene)] bismaleimide, N, N ′-[(1,3-phenylene) bisoxybis (3,1-phenylene)] bismaleimide N, N '-(3,6,9-trioxaundecane-1,11-diyl) bismaleimide, N, N'-[isopropylidene bis [p-phenyleneoxycarbonyl (m-phenylene)] bismaleimide N, N '-[isopropylidenebis [p-phenyleneoxycarbonyl (p-phenylene)]] bismaleimide, N, N'-[isopropylide Bis [(2,6-dichlorobenzene-4,1-diyl) oxycarbonyl (p-phenylene)] bismaleimide, N, N '-[(phenylimino) bis (4,1-phenylene)] bismaleimide, N, N '-[azobis (4,1-phenylene)] bismaleimide, N, N'-[1,3,4-oxadiazole-2,5-diylbis (4,1-phenylene)] bismaleimide, 2,6-Bis [4- (maleimido-N-yl) phenoxy] benzonitrile, N, N '-[1,3,4-oxadiazole-2,5-diylbis (3,1-phenylene)] Bismaleimide, N, N '-[bis [9-oxo-9H-9-phospha (V) -10-oxaphenanthrene-9-yl] methylene bis (p-phenylene)] bismaleimide, N, N'- Hexafluoroisopropylidenebis [p-phenyleneoxycarbonyl (m-phenylene)]] bismaleimide, N, N '-[carbonylbis [(4,1-phenylene) thio (4,1-phenylene)] bismaleimide, N, N'-carbonylbis (p-phenyleneoxy p-phenylene) bismaleimide, N, N '-[5-tert-butyl-1,3-phenylenebis [(1,3,4-oxadiazole-5) , 2-Diyl) (4, 1-phenylene)]] bismaleimide, N, N '-[Cyclohexylidene bis (4, 1-phenylene)] bismaleimide, N, N'-[methylene bis (oxy) bis ( 2-Methyl-1,4-phenylene)] bismaleimide, N, N '-[5- [2- [5- (dimethylamino) -1-naphthylsulfonylamide] ] Ethylcarbamoyl] -1,3-phenylene] bismaleimide, N, N '-(oxybisethylene) bismaleimide, N, N'-[dithiobis (m-phenylene)] bismaleimide, N, N '-(3) , 6,9-trioxaundecane-1,11-diyl) bismaleimide, N, N '-(ethylenebis-p-phenylene) bismaleimide, BMI-689, BMI-1500, BMI-1700, manufactured by Designer Molecules, Mention may be made of multifunctional maleimides such as BMI-3000, BMI-5000, BMI-9000, ODA-BMI manufactured by JFE Chemical, BAF-BMI, and the like.

  Mention may also be made of polyfunctional maleimides obtained by reacting a polyfunctional amine with maleic anhydride. As polyfunctional amines, isophorone diamine, dicyclohexylmethane-4,4'-diamine, manufactured by Huntsman Corporation, Jeffamine D-230 having a terminal aminated polypropylene glycol skeleton, HK-511, D-400, XTJ- 582, D-2000, XTJ-578, XTJ-509, XTJ-510, T-403, T-5000, XTJ-500, XTJ-501, XTJ-502, XTJ-504, with terminal aminated ethylene glycol backbone XTJ-511, XTJ-512, XTJ-542 having XTJ-590 terminal aminated polytetramethylene glycol backbone, XTJ-533, XTJ-536, XTJ-548, XTJ-559 and the like.

  Furthermore, maleimide having a hydroxyl group or a carboxyl group, a poly (meth) acrylate having a carboxyl group, an epoxy group, an isocyanate group, an acid anhydride group or the like, polyurethane, polyester, polyamide, polyimide, polycarbonate, polyolefin, polystyrene, polysiloxane, Mention may also be made of polyfunctional maleimides reacted with polyethers, copolymers containing maleic anhydride, epoxy resins and the like. Preferred are maleimide-added poly (meth) acrylate and maleimide-added polyurethane.

  The molecular weight of the curing agent (B) is preferably 200 to 1,000, and more preferably 200 to 600. When the molecular weight is 1,000 or less, the curing agent (B) is blended to improve the distribution when forming a hard coating agent, and the solution quality stability, storage stability and excellent coating suitability are imparted. It becomes easy to do.

  Although the compounding amount of the curing agent (B) in the thermosetting hard coat agent of the present invention is not particularly limited, the maleimide structure concentration of the curing agent (B) is molar relative to the diene structure concentration of the resin (A). The ratio is preferably 0.1 or more and 1 or less, more preferably 0.1 or more and less than 1, and particularly preferably 0.1 or more and 0.8 or less. Within the above range, when the diene structure concentration present on the resin side is equal to or greater than the maleimide structure concentration, re-crosslinking after heat molding is efficiently performed. Particularly preferably, the diene structure concentration is more than the maleimide structure concentration. The fact that re-crosslinking is performed efficiently indicates that the bicyclo [2.2.1] hept-2-ene structure is abundant in the coating film, resulting in a rigid film derived from the ring structure, and after heat molding Even with high chemical resistance and surface hardness.

  The thermosetting hard coat agent of the present invention may be a so-called two-component mixture type in which the resin (A) and the curing agent (B) are mixed at the time of use, or the resin (A) and the curing agent (B) And may be a one-component type in which is mixed beforehand.

[Organic solvent (C)]
The thermosetting hard coat agent of the present invention preferably contains an organic solvent (C). As the organic solvent (C), known ones may be appropriately selected and used, for example, esters such as ethyl acetate, butyl acetate and cellosolve acetate; acetone, methyl ethyl ketone, isobutyl ketone, methyl isobutyl ketone, acetyl acetone, cyclohexanone etc. Ketones; ethers such as tetrahydrofuran and dioxane; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and ethylene chloride; dimethyl sulfoxide and dimethyl sulfoamide; water, methanol, ethanol and isopropanol And other alcohols. These may be used alone or in any combination of two or more.

  A slip agent can be added to the hard coat agent of the present invention for the purpose of imparting slipperiness to the laminated film described later. The slip agent may, for example, be a fluorine-based slip agent, a silicone-based slip agent or a wax-based slip agent. These slip agents can be used preferably in an amount of 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the solid content of the hard coat agent.

[Antioxidant]
In the hard coat agent of the present invention, a radical reaction caused by a diene structure during storage, coating and aging may occur, and the hard coat agent and the laminated film thereof may turn yellow. In order to prevent yellowing, it is preferable to include various antioxidants as chain terminators.
As the antioxidant, 2,6-di-t-butylparacresol (DBPC), 2,5-di-t-butylparacresol, 4,4 'methylene bis (2,6-di-t-butylphenol), Hindered phenolic antioxidants such as 4,4 'methylene bis (6-t-butyl-o-cresol) or aromatic amine antioxidants such as P, P'-dioctyl diphenylamine, phenyl-α-naphthylamine or phenothiazine And the like, and hindered phenol-based antioxidants that are resistant to discoloration are particularly preferred. Further, it is preferable to use a phosphoric acid ester type antioxidant such as trialkyl phosphite, alkyl allyl phosphite or triaryl phosphite in combination.
The above antioxidant is preferably contained in an amount of 0.001 to 3 parts by mass, particularly preferably 0.05 to 1 parts by mass, in 100 parts by mass of the resin (A) having a diene structure. By making the content particularly preferable, bleed out of the antioxidant to the surface of the hard coat layer is suppressed.
Among the above-mentioned antioxidants, preferred hindered phenolic antioxidants have a molecular weight of 120 to 700 and are low molecular weight antioxidants. By belonging to the range of this molecular weight, the radical scavenging performance in a hard-coat layer improves.

  In addition, when the hard coat layer is formed from the hard coat agent of the present invention, since it is applied so as to be a relatively thick film, there is a general tendency for surface defects to easily occur, but surface defects A surface conditioner may be added to the hard coat agent of the present invention for the purpose of effectively preventing it. As a surface conditioner, BYK company BYK-300, BYK-315, BYK-320 etc. are mentioned. These surface conditioners can be used preferably in an amount of 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass, with respect to 100 parts by mass of the solid content of the hard coat agent.

  The hard coat agent of the present invention may contain other resins other than the resin (A), organic or inorganic fine particles, etc., as long as the object of the present invention is not inhibited. As resin other than the said resin (A), a polyester resin, a urethane resin, an epoxy resin, a thermoplastic acrylic resin, a phenol resin, cellulose ester resin etc. can be mentioned, for example. These resins may have a crosslinkable functional group or may not have a crosslinkable functional group, but preferably have a crosslinkable functional group.

  By containing organic or inorganic fine particles in the hard coating agent of the present invention, the surface of the laminated film is made uneven to impart an antiblocking effect, to give a matte feeling due to the unevenness of the surface, to give strength to the film. It can be given to make it hard to get scratched. It is preferable to contain 0.01-20 mass parts of these microparticles | fine-particles with respect to 100 mass parts of resin (A), and it is more preferable to contain 0.1-10 mass parts. By setting the content to 0.01 parts by mass or more, the above effect can be expected, and by setting the content to 20 parts by mass or less, a strong laminated film 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 addition, if necessary, a curing accelerator may be added to the hard coat agent as long as the effects of the present invention are not impaired. The curing accelerator plays a role as a catalyst which promotes the addition reaction of the diene structure of the resin (A) and the maleimide structure of the curing agent (B). As a Lewis acid to be a catalyst, aluminum chloride, tin tetrachloride, iron trichloride, titanium trichloride, titanium tetrachloride, boron trifluoride, alkylaluminum compounds (such as trimethylaluminum), polyaluminoxane compounds (polymethylaluminoxane, sulfone) Imide-modified polyaluminoxane compounds, sulfonic acid-modified polyaluminoxane compounds, reaction products of polymethylaluminoxane and bistrifluoromethanesulfonimide, etc., scandium compounds (scandium (III) perfluorooctane sulfonate, etc.) The reaction temperature can be lowered.
Furthermore, as a cocatalyst, aliphatic or aromatic esters, chloroacetic esters, ethers, ketones, carbonates and nitro compounds, amines, strong alkali salts of weak acids such as organic carboxylic acids and phosphoric acids Sodium, dibasic hydrogen phosphate, etc., oxides, hydroxides, carbonates, bicarbonates of alkali metals and alkaline earth metals (calcium oxide, magnesium oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, etc.) Etc can be used.

  The hard coat agent of the present invention may, if necessary, be a filler, a thixotropy-imparting agent, an anti-aging agent, an antistatic agent, a flame retardant, a thermal conductivity improver, and a plasticizer as long as the effects of the present invention are not impaired. , Various additives such as anti-sagging agent, antifouling agent, antiseptic, disinfectant, antifoaming agent, antifoaming agent, leveling agent, curing agent, thickener, pigment dispersant, silane coupling agent may be further added .

<Laminated film>
Next, the laminated film of the present invention will be described. The laminate film of the present invention has at least a base layer and a hard coat layer formed from the hard coat agent of the present invention, and is suitably used as a decorative film from the viewpoint of achieving both moldability and durability. be able to. When the laminated film is used as a decorative film, an adhesive layer, a colored layer, an ultraviolet absorbing layer, a light reflection preventing layer and the like may be appropriately incorporated in addition to the base material layer. The thickness of the hard coat layer is not particularly limited, but is preferably 1 to 200 μm, and more preferably 5 to 100 μm from the viewpoint of moldability and durability.

  It is preferable that the elongation rate in the 120 degreeC environment of the hard-coat layer of the laminated | multilayer film of this invention is 100% or more. When the laminate film is molded because the elongation rate under an environment of 120 ° C. is 100% or more, molding defects such as cracking and breakage hardly occur. Although the upper limit of the elongation rate is not particularly limited, it is preferably 1000% or less from the viewpoint of coexistence of moldability and durability. In the present invention, when the tensile test is carried out at a tensile speed of 10 mm / min under an environment of 120 ° C. for the hard coat layer of the laminated film, the hard coat layer is stretched without causing appearance defects such as cracking and breakage. It is a rate. In addition, the expansion rate is calculated from “100 × (length after expansion−original length) / (original length)”.

The base material layer which comprises a laminated film plays a role which supports a hard-coat layer, the other colored layer mentioned later, an adhesive bond layer, etc.
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, polyethylene terephthalate film, polycarbonate film, polymethyl methacrylate film, polyamide film, polyimide film, polyvinyl chloride film, polyvinylidene chloride film, polyvinyl alcohol film, polystyrene film, polyacrylonitrile film, etc. A thermoplastic resin film or a film in which chemical crosslinking is further applied to a thermoplastic resin, a metal film such as an aluminum foil, paper, etc. may be mentioned, and one or a plurality of laminated films can be used.
In particular, in terms of transparency and moldability, polyester films, polyethylene terephthalate films, polycarbonate films, and polymethyl methacrylate films 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 polyethylene terephthalate film are laminated with an adhesive.
Polycarbonate films have good moldability, polyethylene terephthalate films have good solvent resistance (for organic solvents, sunscreen creams, etc.), and polymethyl methacrylate films have good hardness. And combinations thereof can be appropriately selected 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 base material layer is not particularly limited, but is preferably 5 to 1000 μm, more preferably 10 to 500 μm, and particularly preferably 10 to 400 μm from the viewpoint of moldability and durability. 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.

  In the laminated film of the present invention, the hard coat agent of the present invention containing the resin (A) and the curing agent (B) is coated on a substrate layer or various cured films, dried and cured to obtain a hard coat layer. It can be manufactured by forming For example, the hard coating agent of the present invention is applied to one side of the substrate layer and immediately put into a drying oven to evaporate the solvent. After the solvent is volatilized, aging is performed if necessary, and the diene structure in the resin (A) and the maleimide structure in the curing agent (B) can be reacted and cured to obtain a laminated film. Moreover, after a colored layer is coated and hardened on a base material layer, a hard coat layer can be further coated on the colored layer to obtain a laminate film.

Alternatively, it can be produced by forming a hard coat layer on a base material layer using an adhesive.
Specifically, first, the hard coating agent of the present invention is coated on a peelable sheet and placed in a drying oven to evaporate the solvent. After the solvent is volatilized, aging is carried out if necessary, and the diene structure in the resin (A) and the maleimide structure in the curing agent (B) are reacted and cured to obtain a cured coating (cast film). Then, an adhesive for lamination is applied to the cast film or / and the substrate layer, and if the adhesive for lamination contains a solvent, the solvent is evaporated and then the cast film and the substrate layer are laminated to form a hard coat. A laminated film having a layer and a substrate layer can be obtained. The peelable sheet is properly peeled before and after lamination.

  As a method for applying the hard coating agent of the present invention, known methods can be used, and specific examples include comma coating, gravure coating, reverse coating, roll coating, lip coating, spray coating and the like. .

  The hard coat agent of the present invention is preferably dried at 50 to 200 ° C., and more preferably at 70 to 180 ° C. 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.

  After drying, the reaction between the diene structure and the maleimide structure is allowed to proceed (aging) usually for about 10 minutes to 5 days in an environment of about room temperature to about 90 ° C. In the case where another curing agent is also contained, it is preferable to additionally age appropriately, separately from the above-mentioned aging. For example, in the case of an isocyanate curing agent or a carbodiimide curing agent, aging of about 1 day to 10 days is preferable in an environment of about room temperature to about 150 ° C., and in the case of an ambient temperature of about room temperature to about 200 ° C. Aging for about 1 minute to 5 days is preferable. The aging temperature and time are not limited to the above conditions, and appropriate conditions may be appropriately selected depending on the amount of functional groups, the ratio of curing agent / functional group, the presence or absence of a curing accelerating catalyst, and the like.

The hard coat layer used for the outermost surface of the laminated film of the present invention is characterized by having a bicyclo [2.2.1] hept-2-ene structure, and the presence or absence of the structure is measured by infrared spectroscopy as follows. Discrimination is possible by the ATR method (total reflection measurement method) in
[1] Resin (A) having a diene structure before reaction, curing agent (B) having two or more maleimide structures, [2] bicyclo [2.2 after reaction and [3] heating (equilibrium state) .1] The state of hept-2-ene structure is shown in FIG.

Also, due to the reaction between the diene structure and the maleimide structure, 650 to 700 cm ^-1 derived from the double bond of the maleimide structure is reduced by the formation of the bicyclo [2.2.1] hept-2-ene structure in the ATR spectral chart. Do. Therefore, in response to heating and cooling of the hard coat layer, it has the property of increasing and decreasing by 650 to 700 cm ⁻¹ . ATR spectrum chart, taking Example 108 as an example, resin (A) having a diene structure as a raw material, and a curing agent having two or more maleimide structures (B), hard coat layer after aging, 150 ° C. immediately after heating The spectra of the hard coat layer and the hard coat layer after re-aging after heating are shown in FIG.

  The solvent may be dried in an oven, and the laminated film taken out may be aged by sheeting, or may be rolled up and aged in a roll. In any case, a tack may remain on the hard coat layer before aging, and a blocking phenomenon may occur when overlapping with the opposite surface of the base 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 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 laminated film of the present invention may further be provided with an adhesive layer and a colored layer as described later. As described above, the adhesive layer is provided between the hard coat layer and the base layer and used to bond the hard coat layer to the base layer, and in the case of using a plurality of base layers, or a colored layer Also used to bond the various layers together.
For example, the first base material layer and the second base material layer can be attached to each other using an adhesive layer. Alternatively, an adhesive layer may be provided on the side opposite to the hard coat layer side of the base material layer, and the laminate film and the object to be decorated such as a resin 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 adhesive agents 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- Vinyl acetate resin, polyvinyl alcohol resin, epoxy resin, silicone resin, phenol resin, styrene-butadiene rubber, nitrile rubber, natural rubber and the like can be mentioned, and one type or two or more types can be used in combination.

  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 the hard coat layer and drying it, or by softening the solvent-free adhesive with heat to form a substrate layer or a hard coat (HC A coating method, a cooling method, or an adhesive containing a solvent or not containing solvent is applied on the releasable sheet by the above method to produce an adhesive sheet, and then it is interposed between objects to be adhered. It can be provided by a method of sandwiching the adhesive sheet or the like. 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 laminated film of the present invention may further be provided with a colored layer. A colored layer is laminated in order to give designability when using a laminated film as a decoration film, and it decorates between the hard-coat layer and a base material layer, the hard-coat layer of a base material layer, the other side, etc. When forming a molded body, it 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, a group Examples include a method of printing and drying the material layer, a method of printing on the substrate layer and light irradiation, and a method of vapor-depositing a metal on the substrate layer. Furthermore, when producing a base material layer, it can also be used as a base material layer and a colored layer by coloring using various pigments and dyes. 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 laminated film of the present invention can be produced a decorated molded body by various molding methods such as vacuum molding, pressure molding, TOM molding, injection molding, in-mold molding, press molding, and stamping molding.
A protective film that can be removed from the viewpoints of blocking prevention at the time of laminated film production, scratching prevention, scratching prevention at molding, mold mark prevention, and dirt prevention after the decorated molded body is ready for use after molding It can further be provided on the laminated film.
In addition, when the laminated film is attached to the object to be decorated using the adhesive layer, it is possible to peel off on the adhesive layer provided on the inner side of the laminated film from the viewpoint of blocking prevention. A protective film 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 on the laminated film of the present invention, a method of applying a hard coating agent to a base material layer, drying it, and attaching a protective film when providing a hard coat layer, hard coating on a protective film The agent may be applied, dried, aged if necessary, provided with a hard coat layer, and then bonded to a base material layer. When the hard coat layer is first provided on the protective film, it may be attached using an adhesive as required.

The laminated film of the present invention has various aspects. The specific example of the aspect is demonstrated based on a figure.
FIG. 1 shows the aspect which consists of 2 layer structure of a hard-coat layer (HC) and a base material layer (1).
FIG. 2 shows an embodiment comprising a hard coat layer (HC), a first base layer (1a), and a second base layer (1b). The first substrate layer (1a) and the second substrate layer (1b) can be provided, for example, 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 the non-facing side (hard coat layer (HC) of the hard coat layer (HC) of the substrate layer (1) is provided Shows an embodiment having a colored layer (3) on the opposite side of
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 (HC) 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) on the opposite side to the adhesive layer (2) of a base material layer (1) is shown.
FIG. 7 has a hard coat layer (HC), a first substrate layer (1a), a second substrate layer (1b), a first adhesive layer (2a) and a second adhesive layer (2b) The first adhesive layer (2a) is between the hard coat layer (HC) and the first base layer (1a), and the second adhesive layer (2b) is between the first base layer (1a) and the second base layer The embodiment located between the layer (1 b) is shown.
FIG. 8 has a hard coat layer (HC), a substrate layer (1), a colored layer (3) and an adhesive layer (2), and the non-hard coat layer (HC) of the substrate layer (1) The colored layer (3) is located on the opposite surface side (the side opposite to the side on which the hard coat layer (HC) is provided), and the hard coat layer (HC) and the adhesive layer (2) are located on the surface. Show the aspect of
FIG. 9 has a hard coat layer (HC) and a substrate layer (1), and the non-facing side of the hard coat layer (HC) of the substrate layer (1) (hard coat layer (HC) is provided In the embodiment shown in FIG. 1, an adhesive layer (2) is provided on the side opposite to the

<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 laminated film (decorative film), and the material of the decorative body to be covered (hereinafter referred to as a body to be decorated) is not particularly limited. And known materials can be used.
Examples of materials that can be used as a body to be decorated include wood, paper, metal, plastic, fiber reinforced plastic, rubber, glass, minerals, clay and the like, and one or more kinds may 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 and the like can be mentioned, and one or more kinds can be used in combination.

As a fiber reinforced plastic, a carbon fiber reinforced plastic, a glass fiber reinforced plastic, an aramid fiber reinforced plastic, a polyethylene fiber reinforced plastic etc. are mentioned, for example, It can be used combining 1 type or 2 types or more.
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-aluminized steel, iron-zinc plated steel, aluminized steel, aluminium-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.
The laminated film of the present invention and the body to be decorated can be integrated using a known integration method such as insert molding, in-mold molding, vacuum molding, pressure forming, TOM molding, press molding and the like.

Also, for example, after the laminated film of the present invention is preformed into a desired shape, a plastic or fiber reinforced plastic may be injection-molded so that the laminated film 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 on the surface of the molded body, the hard coating layer side is a preform obtained by preforming the laminate film of the present invention or the laminate film into a desired shape. It can also be attached and obtained so as to be the outermost layer.

  In the decorated molded body of the present invention, the hard coat layer side of the laminated film is positioned as the outermost layer. As described above, the laminated film may be provided with a protective film for preventing appearance defects which may occur in each step such as coating, drying, aging, molding integration, etc. When the decorative molded body is used, the protective film is preferably peeled off.

The decorative molded body manufactured using the laminated film of the present invention as a decorative film is 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. Or, it is used as an exterior part such as an emblem on the front and rear of a car, a center ornament of a tire wheel, and a name plate.
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, "part" indicates "mass part" and "%" indicates mass%.

<Synthesis of Diene Structure-Containing Monomer>
Synthesis Example α Synthesis of “Furfuryl Methacrylate (FFMA)” A four-necked flask equipped with a stirrer, a thermometer, a gas inlet tube, a cooler, and a fractionator equipped with a fractionator of 10 theoretical plates, 650 g (6.6 mol) of furfuryl alcohol, 995 g (9.9 mol) of methyl methacrylate (hereinafter MMA), 91 g (0.6 mol) of diazabicycloundecene as transesterification catalyst (B), and methyl as a polymerization inhibitor After 5.8 g (0.05 mol) of hydroquinone (hereinafter referred to as MEHQ) is charged successively, heating is carried out with a mantle heater so that the internal temperature of the reaction is 120 ° C. to 140 ° C. and the top temperature of the distillation column is 65 ° C. The reaction was carried out while controlling the reflux ratio. After reaching 12 hours from the start of heating, the reaction was stopped and cooled to room temperature. Next, 5 g (0.02 mol) of 2,6-di-tert-butyl-4-methylphenol was added as a polymerization inhibitor, and then the pressure in the system was reduced to 4 mmHg using a high pressure vacuum pump, and the temperature was gradually raised. Distillation was performed. The extract was collected at a distillation temperature of 80 to 100 ° C. to obtain 800 g (4.8 mol) of 2-furfuryl methacrylate (FFMA).

Synthesis Example Synthesis of β “2-thienylmethyl methacrylate (THMA)” Synthesis Example is the same as the synthesis method of Synthesis Example α except that 750 g (6.6 mol) of furfuryl alcohol of Synthesis Example α is used. To give 870 g (4.8 mol) of 2-thienylmethyl methacrylate (THMA).

Synthesis Example of Synthesis of “Methacrylic Acid-9-Anthracenemethyl (ANMA)” Synthesis Method of Synthesis Example α Except that 1370 g (6.6 mol) of 9- (hydroxymethyl) anthracene was used as the furfuryl alcohol of Synthesis Example α The synthesis was carried out in the same manner as in the above to obtain 1320 g (4.8 mol) of methacrylic acid-9-anthracenemethyl (ANMA).

Synthesis Example A-1 “Resin (A) A-1 Solution”
150 parts of methyl ethyl ketone (MEK) was charged into a four-necked flask equipped with a condenser, a stirrer, a thermometer, and a nitrogen introduction pipe, and the temperature was raised while stirring under a nitrogen atmosphere. When the temperature in the flask reaches 78 ° C, this temperature is maintained as the synthesis temperature, and 1.3 parts of 2-anthracene methacrylate, 98.7 parts of methyl methacrylate, and 0.5 parts of azobisisobutyronitrile are mixed. The monomer solution was added dropwise over 2 hours. The reaction was continued every one hour from the end of dropping of the monomer by adding 0.02 part of azobisisobutyronitrile until the unreacted monomer in the solution became 1% or less. When the amount of unreacted monomer is 1% or less, the reaction is terminated by cooling to obtain a resin (A) A-1 solution having a solid content of about 40% and a diene structure concentration of 0.05 mmol / g (solid conversion).
The solid content and the diene structure concentration were measured and calculated by the method described below.

«Measurement of solid content»
Measure the mass of the aluminum plate with lid 55 mm in diameter and 15 mm in depth up to 4 places of decimals. Collect about 1.5 g of the resin solution in an aluminum pan, immediately cover and measure the weight quickly and accurately. With the lid removed, place in a 200 ° C. oven to dry for 10 minutes. After cooling to room temperature, the mass of the aluminum pan and lid is measured, and the solid content is calculated by the following equation.
Solid content (%) = (mass after drying-mass of aluminum pan) / (mass before drying-mass of aluminum pan) x 100

Calculation of diene structure concentration
From the amount charged at the time of synthesis of the monomer having a diene structure, it was calculated from the following formula.
Diene structure concentration = (W _DP / M _DP ) / W _ALL
W _DP : Charge of monomer having diene structure (g)
M _DP : Molecular weight of monomer having diene structure (g / mol)
W _ALL : Total amount of charged monomer (g)

<< Measurement of weight average molecular weight >>
The weight average molecular weight is measured using GPC (gel permeation chromatography) "HPC-8020" manufactured by Tosoh Corporation, using two columns of SHODEX KF-806L, one column of KF-804L, and one column of KF-8021, and using tetrahydrofuran as a solvent. It was. The weight average molecular weight was calculated in terms of standard polystyrene.

<Resin having a diene structure (A)>
* Synthesis Example A-2 to A-13 "Resin (A) A-2 to A-13 Solution"
The reaction was carried out according to the composition of Table 1 to obtain resin (A) A-2 to A-13 solutions. The diene structure equivalent is shown in Table 1. The solid content was all adjusted to be 40%. The weight average molecular weight was adjusted by the amount of initiator added and the concentration of monomers in the solution during polymerization. The symbols in the table are as follows.
FFMA: Furfuryl Methacrylate THMA: Methacrylate-2-thienylmethyl ANMA: Methacrylate-9-anthracenemethyl MMA: Methacrylate HEMA: Methacrylate-2-hydroxyethyl

<Other resin>
* Synthesis Example for Comparative Example AC-1 “Resin AC-1 Solution”
150 parts of methyl ethyl ketone (MEK) was charged into a four-necked flask equipped with a condenser, a stirrer, a thermometer, and a nitrogen introduction pipe, and the temperature was raised while stirring under a nitrogen atmosphere. When the temperature in the flask reached 78 ° C., this temperature was maintained as the synthesis temperature, and a monomer solution in which 100 parts of methyl methacrylate and 0.5 parts of azobisisobutyronitrile were mixed was added dropwise over 2 hours. The reaction was continued every one hour from the end of dropping of the monomer by adding 0.02 part of azobisisobutyronitrile until the unreacted monomer in the solution became 1% or less. When the amount of unreacted monomer is 1% or less, the reaction is terminated by cooling to obtain a solution of resin AC-1 for a comparative example having a solid content of about 40% and a dienophile structure concentration of 0 mmol / g (solid conversion).
The solid content and the diene structure concentration were measured and calculated in the same manner as in Synthesis Example A-1.

* Synthesis Example for Comparative Example AC-2 “Resin AC-2 Solution”
The reaction was carried out according to the composition of Table 1 to obtain a resin AC-2 solution for comparative example. The diene structure equivalent is shown in Table 1. The solid content was adjusted to 40%.

<Hardener having two or more maleimide structures (B)>
B-1: HBMI (N, N'-hexamethylene bismaleimide) maleimide structure concentration: 7.24 mmol / g Molecular weight: 276.29
B-2: Bisphenol A diphenyl ether bismaleimide maleimide structure concentration: 3.51 mmol / g Molecular weight: 570.6
B-3: 4-methyl-1,3-phenylenebismaleimide maleimide structure concentration: 7.09 mmol / g molecular weight: 282.26

<Other curing agent>
BC-1: NCO (hexamethylene diisocyanate)
BC-2: DPGDA (dipropylene glycol diacrylate)

<Antioxidant>
C-1: Adekastab AO-40 manufactured by Adeka Molecular weight: 383
C-2: Adekastab AO-60 manufactured by Adeka Molecular weight: 1178

Example 1
In the resin (A) (A-1) solution obtained in Synthesis Example A-1 containing 100 parts by mass (solid mass) of resin (A) (A-1), “HBMI” (Tokyo) as a curing agent (B) 0.7 parts by mass (solid mass) of N, N'-hexamethylene bismaleimide (manufactured by Kasei Kogyo Co., Ltd.), and then methyl ethyl ketone (MEK) is added and stirred so that the solid content is 30%, and thermosetting A hard coating agent was obtained.

A thermosetting hard coat agent was applied to the release surface of a polymethyl methacrylate (PMMA) film using a doctor blade, and dried in an oven at 100 ° C. for 2 minutes to volatilize solvents. The film thickness after drying was 20 μm. Next, it is left in a temperature-controlled room at 60 ° C. for 4 days to allow the reaction between the resin (A) and the curing agent (B) to proceed (age) to form a cured coating (hard coating layer) on the PMMA film. I got
The results of evaluating the obtained laminated film according to the method described later are shown in Table 3.

<< Gel fraction >>
The obtained laminated film is cut into a size of 2 cm × 5 cm, immersed in 100 mL of methyl ethyl ketone, and placed in an environment of 50 ° C. for 24 hours to measure the mass after sufficient drying, and the mass of laminated film and PMMA film of the same size The gel fraction of the HC layer was determined using the following equation.
When the bicyclo [2.2.1] hept-2-ene structure is sufficiently present in the hard coat layer, the crosslinking strengthens the film so that it does not dissolve in the solvent. Therefore, the gel fraction that functions as a hard coat layer is preferably 60% or more, and more preferably 90% or more.

Gel fraction (%) = [laminated film-laminated film after immersion] / [laminated film-PMMA] x 100

Evaluation of yellowing
Panac Protect HP 50 manufactured by PANAC CO., LTD. Is attached to the obtained laminated film while applying a load of 0.1 MPa with a laminator to block oxygen to the hard coat layer on the surface of the laminated film, at 80 ° C. A test was conducted to evaluate yellowing after standing for 96 hours according to the following criteria. The yellowness (YI) of the laminated film before and after the test is measured using a color difference meter (SZ-Σ90, manufactured by Nippon Denshoku Kogyo Co., Ltd.) to obtain the difference in yellowness. did. When used as a transparent film, the practical level is B or more in the following notation standard.
S: ΔYI is 0 or more and less than 1.5 A: ΔYI is 1.5 or more and less than 3 B: ΔYI is 3 or more and less than 10 C: ΔYI is 10 or more

<< Evaluation of extensibility >>
The laminated film was cut into a width of 10 mm and a length of 20 mm, and a tensile test was performed 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
From the elongation at break (including cracks) of the laminated film, the evaluation was made according to the following criteria. The results are shown in Table 3.
○: Growth rate 200% or more,
Δ: elongation rate 100% or more and less than 200% ×: elongation rate less than 100% When the distance between chucks at the time of rupture of the laminated film is 20 mm, the elongation rate is calculated as 100%. (The laminated film of 10 mm is further stretched by 10 mm.)

<< Production method of decorated moldings >>
Using a TOM forming machine (Fabure Vacuum Co., Ltd., NGF 0406-T), set at the position where the base material side of the laminated film faces the object to be decorated with a rectangular solid so that the hard coat surface is exposed on the surface It shape | molded on condition of the following, and produced the decorating molded body.
Shaped body to be decorated: 5 cm long x 5 cm wide x 1 cm high, made of aluminum Molding temperature: 120 ° C
Heater output: 200% during rapid heating, 80% during normal heating
Rapid heating time: 10 seconds Pressure: 300 kPa
Air pressure: 10 seconds Trace release: 1 second

<< Evaluation of surface hardness >>
The abrasion resistance test by the steel wool shown below was implemented as evaluation of the surface hardness of the obtained lamination film and the decoration molding after the TOM shaping | molding.
The cured coating film surface of the obtained laminated film was rubbed back and forth with 100 g load of steel wool (# 0000) for 10 cycles, and the number of scratches was evaluated based on the following criteria. The results are shown in Table 3.

○: Less than 5 scratches Δ: More than 5 and less than 10 scratches ×: More than 10 scratches

<< Evaluation of chemical resistance >>
0.5 g of a sunscreen cream (Neutrogena UltraSheerDRY-TOUCHSUNSCREEN SPF 55 (manufactured by Johnson & Johnson Co.)) is applied onto the cured coated film surface of the obtained laminated film and its decorated molded body after TOM molding, and the glass Place the board. A further load of 500 g was placed on the glass plate and left at 80 ° C. for 24 hours, leaving the sunscreen cream to spread. After standing, the sunscreen cream was rinsed with water and drained, and then the appearance of a 3 cm diameter circle centered on the portion to which the sunscreen cream was dropped was visually observed and evaluated according to the following criteria. In addition, evaluation was implemented about the location where the film area ratio after TOM shaping | molding is 0.1 times or less compared with TOM shaping | molding front. The results are shown in Table 3.

Good: No appearance defects such as generation of wrinkles and discoloration are observed.
Δ: Discoloration is observed in part.
X: Discoloration is seen overall.

[Examples 2 to 24]
After obtaining a thermosetting hard coat agent adjusted at a ratio shown in Table 2 in the same manner as in Example 1, a cured coating film (hard coat layer) is formed on the film in the same manner as in Example 1 to obtain a laminated film. Obtained. The gel fraction, the presence or absence of yellowing, the extensibility, the surface hardness and the chemical resistance were evaluated in the same manner as in Example 1 for the obtained laminated film. The results are shown in Table 3.

Comparative Examples 1 to 4
After obtaining a thermosetting hard coat agent adjusted at a ratio shown in Table 2 in the same manner as in Example 1, a cured coating film (hard coat layer) is formed on the film in the same manner as in Example 1, and a laminated film is obtained. I got In Comparative Example 2, a curing agent (BC-1) hexamethylene diisocyanate was used as a curing agent.
The gel fraction, the presence or absence of yellowing, the extensibility, the surface hardness and the chemical resistance were evaluated in the same manner as in Example 1 for the obtained laminated film. The results are shown in Table 3.

  As shown in Table 3, the laminated films of Examples 1 to 24 have a hard coat layer composed of a cured product of an appropriate resin (A) and a curing agent (B), and therefore have extensibility, surface hardness and chemical resistance. Excellent. Among them, the laminated films of Examples 8 to 24 are particularly excellent in the surface hardness and the chemical resistance of the hard coat layer of the decorated molded body because the molar ratio: maleimide structure / diene structure is less than 1.

On the other hand, the laminated film of Comparative Example 1 is inferior in durability because the hard coat agent forming the hard coat layer does not contain the resin (A) having a diene structure.
Further, the laminated film of Comparative Example 2 is excellent in durability because the hard coat layer forms an irreversible crosslinked structure of OH-NCO, but the extensibility is largely inferior.
Comparative Examples 3 and 4 are inferior in durability because they do not contain a curing agent having a maleimide structure.

Example 1-1
In the same manner as in Example 1, a hard coat layer was formed on a PMMA substrate to obtain a member 1.
Separately, to 100 parts by mass (solid mass) of resin (A-1), 0.7 parts by mass of N, N'-hexamethylene bismaleimide (solid mass) as a curing agent, 5 parts by mass of MA 100 (carbon black manufactured by Mitsubishi Chemical Corporation) Parts (solid mass), BYK- 9076 (BYK Co., Ltd. dispersant) 0.5 parts by mass (solid mass), methyl ethyl ketone (MEK) is added and stirred so that the solid content is 30%, and color hardening is achieved Resin composition was obtained.

The colored curable resin composition was 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 a 5 μm thick colored layer was provided. .
Next, an adhesive (AD-76G1 manufactured by Toyo Morton Co., Ltd.) was applied onto the colored layer to a dry film thickness of 5 μm to obtain a decorative film having 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% ×: Peeling area 35% or more

[Examples 1-2 to 22]
A decorative film with an adhesive layer and a colored layer is obtained in the same manner as in Example 1-1 except that the adhesive shown in Table 4 is used instead of the adhesive used in Example 1-1. The

Subsequently, with respect to the to-be-decorated body of Table 4, shaping | molding and adhesiveness were evaluated similarly to Example 1-1.
In addition, ABS of a body to be decorated is an acrylonitrile-butadiene-styrene resin, and CFRP is a carbon fiber reinforced resin, and the shape of each of them is the same as the steel member of Example 1-1.

[Example 1-23]
A decorative film having a colored layer was obtained in the same manner as Example 1-1 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.
About the obtained decorating molded object, the adhesiveness of a decorating film and a to-be-decorated body was evaluated by the same method as Example 1-1.

[Example 1-24]
A decorated molded body was produced and evaluated in the same manner as in Example 1-23 except that the injection resin was changed from ABS resin to carbon fiber reinforced resin (CFRP).

(HC): hard coat layer (1), (1a), (1b): substrate layer (2), (2a), (2b): adhesive layer (3): colored layer (101) to (109) : Laminated film

[Examples 2 to 24]
After obtaining a thermosetting hard coat agent adjusted at a ratio shown in Table 2 in the same manner as in Example 1, a cured coating film (hard coat layer) is formed on the film in the same manner as in Example 1 to obtain a laminated film. Obtained. The gel fraction, the presence or absence of yellowing, the extensibility, the surface hardness and the chemical resistance were evaluated in the same manner as in Example 1 for the obtained laminated film. The results are shown in Table 3.
However, Examples 1-8 and 10 are reference examples.

Claims (9)

  A thermosetting hard coat agent comprising a resin (A) having a diene structure and a curing agent (B) having two or more maleimide structures.   The thermosetting hard coat agent according to claim 1, wherein the diene structure of the resin (A) is a furan structure.   The weight average molecular weight of the resin (A) having a diene structure is in the range of 10,000 to 1,500,000, and the molecular weight of a curing agent (B) having two or more of the maleimide structures is 200 to 1,000. The thermosetting hard coat agent according to claim 1 or 2, which is in the range.   The diene structure concentration of the resin (A) having the diene structure is 0.05 mmol / g to 6 mmol / g, and the diene structure concentration of the resin (A) having the diene structure and the curing having two or more of the maleimide structures The thermosetting hard coat agent according to any one of claims 1 to 3, wherein the molar ratio of the agent (B) to the maleimide structure concentration is less than 1 in the maleimide structure / diene structure.   The thermosetting hard coat agent according to any one of claims 1 to 4, further comprising an antioxidant.   A laminated film comprising a base material layer and a hard coat layer formed from the thermosetting hard coat agent according to any one of claims 1 to 5.   7. The laminated film according to claim 6, wherein the elongation at an environment of 120 ° C. is 100% or more.   The laminated film according to claim 6 or 7, further comprising at least one of an adhesive layer and a colored layer. A decorated molded body, comprising: a body to be decorated; and a laminated film covering at least a part of the body to be decorated, wherein the laminated film is the laminated film according to any one of claims 6 to 8. .