JP2019119049A - Decorative film and decorative molded body - Google Patents

Abstract

To provide a decorative film excellent in productivity, moldability during molding (160°C elongation), positioned on a surface of the decorative molded body after molding, efficiently tolerable to temperature changes in a vehicle, and further excellent in excoriation resistance, chemical resistance (sunscreen cream resistance or the like), and elongation at 25°C (toughness), and a decorative molded body whose surface is coated by the decorative film.SOLUTION: There is provided a decorative film 101 consisting of a laminate containing a hard coat layer HC on a surface and a substrate layer 1, in which the hard coat layer HC has Tg of 30 to 150°C, and Mw of 55000 to 1000000, and contains a cellulose nanofiber in a heat cured article of an acrylic copolymer (A) having at least one of a hydroxyl group or a carboxyl group, total of a hydroxyl group value and an acid value of 1 to 300 KOH/g, and a curing agent (B) having an isocyanate group, an aziridinyl group, or the like.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative film carrying a hard coat layer formed of a specific acrylic curable composition 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, a colored curable composition has been coated or printed on the surface of a resin molded product for the purpose of imparting design properties. In addition, in order to protect the surface, the hard coat curable composition has been spray-coated or dip-coated on the surface of the resin molded article. 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 may 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. Curable compositions are disclosed which contain 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 2 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 | mold, 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 curable composition disclosed in Patent Document 9 lacks extensibility, and therefore has poor moldability and can not be applied to a decorated 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 (160 ° C. extensibility) at the time of molding as the decorative film, is located on the surface of the decorative molded body after molding, and the temperature in the car It is also resistant to changes, and it is excellent in scratch resistance, chemical resistance (sun cream resistance etc.), and stretchability at 25 ° C. (toughness), and a decorative film and a decorative film coated with a surface. The purpose is to provide a decorative molded body.

The present invention is a decorative film containing a hard coat layer containing cellulose nanofibers in a thermosetting product of an acrylic copolymer (A) having a specific Tg, a specific molecular weight, and a specific functional group and a curing agent (B). The above problem is solved by supporting on the surface of
That is, the present invention relates to the following [1] to [8].

[1] A decorative film comprising a laminate including a hard coat layer and a substrate layer, wherein the hard coat layer comprises an acrylic copolymer (A), a curing agent (B), and a cellulose nanofiber (C). And a thermosetting film of a curable composition containing the above-mentioned components, and satisfying the following conditions (1) to (5).
(1) The glass transition temperature of the said acryl-type copolymer (A) is 30-150 degreeC.
(2) The acrylic copolymer (A) has at least one of a hydroxyl group and a carboxyl group.
(3) The sum of the hydroxyl value and the acid value of the acrylic copolymer (A) is 1 mg KOH / g or more and 300 mg KOH / g or less.
(4) The mass average molecular weight of the acrylic copolymer (A) is 55,000 to 1,000,000.
(5) The curing agent (B) comprises a compound having an isocyanate group or a precursor thereof, a compound having an aziridinyl group, a compound having a carbodiimide group, a metal chelate compound, a metal alcoholate compound and a compound system having an epoxy group It is chosen from the group.

[2] The content of the cellulose nanofibers (C) in the total 100% by mass of the acrylic copolymer (A), the curing agent (B) and the cellulose nanofibers (C) is 0.5 to 20 mass [13] The decorative film according to [1].

[3] The substrate layer is a single layer or a multilayer selected from the group consisting of polyester, polycarbonate, polymethyl methacrylate, polyethylene and polypropylene, [1] or [2]. The decorative film described in.

[4] The decorative film according to any one of [1] to [3], wherein the hard coat layer and the base layer are in contact with each other.

[5] The decorative film according to any one of [1] to [4], further comprising at least one of an adhesive layer and a colored layer.

[6] The decorative film according to [5], wherein the adhesive layer is laminated between the base layer and the hard coat layer.

[7] The decorative film as set forth in [5], wherein the adhesive layer is laminated on the non-facing surface side of the hard coat layer of the base layer.

[8] A vehicle to be decorated, and a decorative film for covering at least a part of the vehicle to be decorated, the decorative film being described in any one of [1] to [7] A decorative molded body which is a decorative film of

  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, the decorative film excellent in abrasion resistance, chemical resistance (sun cream resistance etc.), and crack resistance (toughness) can be provided, and a decorative molded body whose surface is covered with the decorative film can be provided. It became so.

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 Cross-sectional view of a structural example of the decorative film of the present invention

The decorative film of the present invention is a decorative film comprising a laminate including a hard coat layer and a substrate layer, wherein the hard coat layer comprises an acrylic copolymer (A) and a curing agent (B). A decorative film comprising a thermosetting material and a cellulose nanofiber (C) and satisfying the following conditions (1) to (5).
(1) The glass transition temperature of the said acryl-type copolymer (A) is 30-150 degreeC.
(2) The acrylic copolymer (A) has at least one of a hydroxyl group and a carboxyl group.
(3) The sum of the hydroxyl value and the acid value of the acrylic copolymer (A) is 1 mg KOH / g or more and 300 mg KOH / g or less.
(4) The mass average molecular weight of the acrylic copolymer (A) is 55,000 to 1,000,000.
(5) The curing agent (B) comprises a compound having an isocyanate group or a precursor thereof, a compound having an aziridinyl group, a compound having a carbodiimide group, a metal chelate compound, a metal alcoholate compound and a compound system having an epoxy group It is chosen from the group.

  A thermosetting acrylic resin is obtained by using, as a hard coat layer, a layer containing a thermosetting product of an acrylic copolymer (A) having at least one of a hydroxyl group and a carboxyl group and a curing agent (B). The moldability and the surface hardness can be compatible, which can not be obtained when the acrylic resin film which has only been extruded is used as the hard coat layer. Moreover, the light resistance which can not be obtained when making a UV curable acrylic resin film into a hard-coat layer is securable.

<Hard coat layer>
The hard coat layer in the present invention contains a thermosetting product of a curable composition containing an acrylic copolymer (A), a curing agent (B) and a cellulose nanofiber (C) described later.

<Acrylic copolymer (A)>
The acrylic copolymer (A) having a hydroxyl group in the present invention will be described.
The acrylic copolymer (A) in the present invention is obtained by copolymerizing a monomer having at least one of a hydroxyl group and a carboxyl group with another monomer having neither a hydroxyl group nor a carboxyl group. The acrylic copolymer (A) can exhibit high durability after curing by having a hydroxyl group or a carboxyl group which causes a crosslinking reaction with a curing agent (B) described later.

  The acrylic copolymer (A) in the present invention may have only a hydroxyl group or only a carboxyl group, and may further have both a hydroxyl group and a carboxyl group. The hydroxyl group and the carboxyl group can be appropriately selected and used according to the moldability and durability required for the decorative film. In order that the acrylic copolymer (A) does not impair both the moldability and durability of the decorative film, the total of the hydroxyl value and the acid value is preferably 1 mg KOH / g to 300 mg KOH / g, more preferably Is more preferably 3 mg KOH / g or more and 250 mg KOH / g or less, and still more preferably 3 mg KOH / g or more and 150 mg KOH / g or less. When the sum of the hydroxyl value and the acid value is 1 mg KOH / g or more, the crosslink density becomes dense and the durability is improved, and when it is 300 mg KOH / g or less, the extreme increase of the crosslink density is suppressed and the moldability is improved. Do. The sum of the hydroxyl value and the acid value is the sum of the hydroxyl value and the acid value of the acrylic copolymer. 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 acrylic copolymer has no 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) acrylates and products obtained by adding ε-caprolactone to the above hydroxyalkyl (meth) acrylates, with hydroxyalkyl (meth) acrylates being preferred.

Specific examples of hydroxyalkyl (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4- 4-hydroxypropyl (meth) acrylate Hydroxyalkyl (meth) acrylate having 1 to 4 carbon atoms of alkyl group such as hydroxybutyl (meth) acrylate, 1,1-dihydroxymethyl (meth) acrylate, 1,2-dihydroxyethyl (meth) acrylate, 2,2 -Dihydroxyethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate is mentioned.
Specific examples of the ε-caprolactone adduct to hydroxyalkyl (meth) acrylate include: 1-mole adduct of 2-hydroxyethyl (meth) acrylate with ε-caprolactone, and 2 moles of 2-hydroxyethyl (meth) acrylate with ε-caprolactone The adduct, ε-caprolactone adduct of hydroxyalkyl (meth) acrylate having 1 to 4 carbon atoms such as adduct of 2-hydroxyethyl (meth) acrylate and 3-mol adduct of 2-hydroxyethyl (meth) acrylate, etc. may be mentioned. It is not limited to only this example. 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, carboxyalkyl (meth) acrylate, itaconic acid, fumaric acid, maleic acid, crotonic acid and the like, but the present invention is limited to only such examples. It is not a thing. These monomers having a carboxyl group may be used alone or in combination.

  As the other monomer, any monomer that can be copolymerized with the above-mentioned monomer having a hydroxyl group or a carboxyl group may be used, and vinyl monomers such as styrene and (meth) acrylate can be mentioned. As the alkyl (meth) acrylate, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 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, stearyl (meth) acrylate, Examples include alkyl (meth) acrylates such as tert-butylhexyl (meth) acrylate, 2-acetoacetoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like.

  As a monomer having an alicyclic hydrocarbon group, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cyclododecyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like can be mentioned.

  Examples of monomers having an epoxy group include glycidyl (meth) acrylate, α-methyl glycidyl acrylate, α-methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methyl acrylate, 3,4-epoxycyclohexyl methyl methacrylate and the like.

  Examples of the method for polymerizing the monomer include solution polymerization method, bulk polymerization method, suspension polymerization method, emulsion polymerization method and the like, but the present invention is not limited by such polymerization method. Among these polymerization methods, the solution polymerization method is preferred because the resulting reaction mixture can be used as it is.

  Hereinafter, one embodiment in the case of preparing an acrylic copolymer (A) having a hydroxyl group by solution polymerization of a monomer will be described, but the present invention is not limited to only the embodiment.

  Examples of solvents used for solution polymerization of monomers include aromatic solvents such as toluene and xylene; alcohol solvents such as n-butyl alcohol, propylene glycol monomethyl ether, diacetone alcohol and ethyl cellosolve; ethyl acetate, Ester solvents such as butyl acetate and cellosolve acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and dimethylformamide may be mentioned, but the present invention is not limited to such examples. The amount of the solvent is preferably determined appropriately depending on the concentration of the monomer mixture, the molecular weight of the target acrylic copolymer, and the like.

  As a polymerization initiator, for example, 2,2'-azobis- (2-methylbutyronitrile), tert-butylperoxy-2-ethylhexanoate, 2,2'-azobisisobutyronitrile, benzoyl Peroxide, di-tert-butyl peroxide and the like can be mentioned, but the present invention is not limited to such examples. The amount of the polymerization initiator is usually preferably 0.01 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, per 100 parts by mass of the monomer mixture. When the mass average molecular weight (Mw) is 55,000 or more as in the present invention, the amount of the polymerization initiator is preferably 0.05 to 1 part by mass.

  The polymerization temperature for polymerizing the monomers is usually preferably 40 to 200 ° C., more preferably 40 to 160 ° C. When the mass average molecular weight (Mw) is 55,000 or more as in the present invention, the polymerization temperature is preferably 140 ° C. or less.

  Since the polymerization time of the monomer varies depending on the polymerization temperature, the composition of the monomer mixture, the type and amount of the polymerization initiator and the like and can not be determined indiscriminately, it is preferable to appropriately determine accordingly.

  The glass transition temperature of the acrylic copolymer (A) in the present invention is preferably 30 to 150 ° C., more preferably 50 to 140 ° C., and still more preferably 60 to 130 ° C. When the glass transition temperature is 30 ° C. or more, good abrasion resistance and wear resistance can be obtained, and when the glass transition temperature is 150 ° C. or less, good moldability can be obtained. The glass transition temperature of the acrylic copolymer (A) is determined by the composition ratio of the monomers to be copolymerized.

  In addition, with glass transition temperature said here, it is the glass transition temperature measured by differential scanning calorimetry (DSC) about resin which dried the solution of acrylic type copolymer (A) and made solid content 100%. Indicates For example, the glass transition temperature is predicted by setting an aluminum pan containing a sample weighed about 10 mg of the sample and an aluminum pan not containing the sample in a DSC and using liquid nitrogen in a nitrogen stream. The temperature is cooled to the glass transition temperature minus 50.degree. C., and then the temperature is raised to the predicted glass transition temperature plus 50.degree. C. at a heating rate of 10.degree. C./min, and the DSC curve is plotted. A straight line extending the baseline on the low temperature side of this DSC curve (the DSC curve portion in the temperature range where no transition and reaction occur in the specimen) to the high temperature side, and the slope of the curve of the step change portion of the glass transition is maximized From the intersection with the tangent drawn at such a point, the extrapolated glass transition start temperature (Tg) can be determined, and this can be determined as the glass transition temperature. The glass transition temperature of the present invention is the value measured by the above method.

  The mass average molecular weight (Mw) of the acrylic copolymer (A) constituting the curable composition of the present invention is 55,000 to 1,000,000, and preferably 100,000 to 800,000. . Generally, hard acrylic copolymers are brittle, and acrylic copolymers having good extensibility have low strength. Therefore, as mentioned above, when an acrylic copolymer was used for a decoration film until now, coexistence of a moldability, surface hardness, etc. was not able to be performed. The acrylic copolymer (A) of the present invention can achieve coexistence of moldability and surface hardness by setting the mass average molecular weight to 55,000 or more. By having a mass average molecular weight of 1,000,000 or less, the formation of a gel is prevented, and the generation of a fisheye or the like derived from the gel is suppressed to obtain a hard coat layer having a good surface smoothness. Can. When the number average molecular weight is larger than 20,000, the surface hardness can be further enhanced.

  In addition, said mass mean molecular weight * number average molecular weight is the value of polystyrene conversion by the gel permeation chromatography (GPC) of an acryl-type copolymer (A). For example, the temperature of a column (Showa Denko KF-805LKF-803L, and KF-802) is 40 ° C., THF is used as an eluent, the flow rate is 0.2 ml / min, detection is RI, sample concentration Was 0.2%, and polystyrene was used as a standard sample. The mass average molecular weight of the present invention is the value measured by the above method.

In order to make the mass average molecular weight (Mw) of the acrylic copolymer (A) 55,000 or more,
(1) Reduce the amount of initiator,
(2) lower the reaction temperature,
(3) raise the monomer concentration,
(4) A solvent having a low chain transfer property is used, etc., but one or more of them may be combined.

<Hardener (B)>
The curing agent (B) in the present invention will be described.
The curing agent (B) in the present invention is a compound having a functional group capable of crosslinking with a hydroxyl group or a carboxyl group in the above-mentioned acrylic copolymer (A). By cross-linking the acrylic copolymer (A) and the curing agent (B) to form a cured resin layer, a hard coat layer having high durability can be formed.

  The curing agent (B) is selected from the group consisting of a compound having an isocyanate group or a precursor thereof, a compound having an aziridinyl group, a compound having a carbodiimide group, a metal chelate compound, a metal alcoholate compound and a compound having an epoxy group. It is a compound and has two or more functional groups capable of crosslinking with the hydroxyl group or carboxyl group of the acrylic copolymer (A) in one molecule. The curing agent (B) can be used alone or in combination of two or more.

As a compound which has an isocyanate group, aromatic isocyanate, aliphatic isocyanate, alicyclic isocyanate etc. are mention | raise | lifted, for example. Among them, it is preferable to use an aliphatic isocyanate compound from the viewpoint of yellowing of the molded decorative film. The isocyanate-based curing agent (B) may be used alone or in combination of two or more.
As a compound which has a precursor of an isocyanate group, what blocked the compound which has an isocyanate group by the blocking agent can be mentioned.

  As aromatic isocyanate, 1,3-phenylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate Isocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanatobenzene, dianisidine diisocyanate, 4,4'-diphenylether diisocyanate, 4,4 ', 4 "- Triphenylmethane triisocyanate etc. can be raised.

  Examples of aliphatic isocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate etc. can be raised.

  As an alicyclic isocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentadiisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2 2,4-Cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis (cyclohexylisocyanate), 1,4-bis (isocyanatomethyl) cyclohexane etc. can be raised

  These isocyanate-based curing agents (B) further include adducts of the above-mentioned isocyanate and a polyol compound such as trimethylolpropane, buret bodies and isocyanurate bodies of the above-mentioned isocyanate, and furthermore, above-mentioned isocyanates and known polyether polyols and polyester polyols. It is preferable to use as an adduct with acrylic polyol, polybutadiene polyol, polyisoprene polyol and the like.

  Among these isocyanate-based curing agents (B), low yellowing type aliphatic or alicyclic isocyanates are preferable from the viewpoint of designability, and from the viewpoint of the film strength of the cured film, a nurate body and an adduct body are preferable. . More specifically, a nurate or adduct of hexamethylene diisocyanate (HDI), and a nurate or adduct of 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI) are preferable. Moreover, these mixtures are also used suitably.

  In the present invention, a blocked isocyanate curing agent may be used as a compound having a precursor of an isocyanate group from the viewpoint of storage stability of the curable composition for forming a hard coat layer. As the blocked isocyanate curing agent, one obtained by blocking the above unblocked isocyanate curing agent with various blocking agents is used, and as the blocking agent, one which dissociates at a relatively low temperature of about 80 ° C. to 120 ° C. preferable. When using a non-blocking isocyanate-based curing agent, the acrylic copolymer (A) and the curing agent (B) are packaged separately and mixed before use. It is preferably used.

  Examples of the compound having an aziridinyl group include 2,2′-bishydroxymethylbutanol tris [3- (1-aziridinyl) propionate], 4,4′-bis (ethyleneiminocarbonylamino) diphenylmethane and the like. It is not limited only to such examples, and these can be used alone or in combination of two or more.

  As a compound having a carbodiimide group, for example, N, N'-di-o-toluylcarbodiimide, N, N'-diphenylcarbodiimide, N, N'-di-2,6-dimethylphenylcarbodiimide, N, N'- Bis (2,6-diisopropylphenyl) carbodiimide, N, N'-dioctyldecylcarbodiimide, N-triyl-N'-cyclohexylcarbodiimide, N, N'-di-2,2-di-tert. -Butylphenyl carbodiimide, N-triyl-N'-phenyl carbodiimide, N, N'-di-p-nitrophenyl carbodiimide, N, N'-di-p-aminophenyl carbodiimide, N, N'-di-p- Hydroxyphenyl carbodiimide, N, N'-di-cyclohexyl carbodiimide, and N, N'- di-p- toluyl carbodiimide etc. are mentioned. Examples of such carbodiimides include Carbodilite series manufactured by Nisshinbo Co., Ltd. However, the carbodiimides are not limited to such exemplifications, and these can be used alone or in combination of two or more.

Examples of the metal constituting the metal chelate compound and the metal alcoholate compound include, for example, aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, zirconium, etc. It is not limited and may be used alone or in combination of two or more. Among them, aluminum, zinc, zirconium and titanium are preferable.
If it illustrates more specifically,
Examples of metal chelate compounds include aluminum ethyl acetoacetate / diisopropylate, alkyl acetoacetate aluminum diisopropiolate, aluminum tris ethyl acetoacetate, aluminum monoacetyl acetate bis ethyl acetoacetate, aluminum tris acetyl acetonate, aluminum monoisopropoxy Aluminum compound of mono- oreoxyethyl acetoacetate;
Zirconium compounds such as zirconium tetraacetyl acetate, zirconium tributoxy monoacetyl acetate, zirconium monobutoxy acetyl acetate bisethyl acetoacetate, zirconium dibutoxy bis ethyl acetoacetate;
Titanium compounds such as titanium diisopropoxy bis acetyl acetate, titanium tetra acetyl acetate, titanium dioctyloxy bis octylene glycolate, titanium diisopropoxy bis ethyl acetoacetate, polyhydroxy titanium stearate, etc.
Ethoxy acetylacetonato zinc, zinc bisacetylacetonato zinc, propoxy acetylacetonato zinc, butoxy acetylacetonato zinc, ethoxy ethyl acetoacetate zinc, bis ethyl acetoacetate zinc, propoxy ethyl acetoacetate zinc, butoxy ethyl Zinc compounds such as acetoacetate zinc can be mentioned.

As metal alcoholate compounds, for example, aluminum ethylate, aluminum propylate, aluminum isopropylate, aluminum diisopropylate monosec butyrate, aluminum monoisopropylate disec butyrate, aluminum compound of aluminum sec butyrate; diethoxy zinc, dipropoxy zinc, Zinc compounds such as dibutoxy zinc; titanium compounds such as titanium ethylate, titanium propylate, titanium isopropylate, titanium butyrate, etc.
Zirconium ethylate, zirconium propylate, zirconium isopropylate, zirconium butyrate, zirconium monopropyl tristearate, zirconium dipropyl distearate, zirconium tripropyl monostearate, zirconium monobutoxy tristearate, zirconium dibutoxy distearate And zirconium compounds such as zirconium tributoxy monostearate.
Moreover, although the condensation product of the metal alcoholate includes cyclic aluminum oxide isopropylate, cyclic aluminum oxide octylate, and cyclic aluminum oxide stearate, the present invention is not limited to such an example, and these may be used alone or in combination. More than species can be used in combination.

  As a compound having an epoxy group, for example, 1,6-hexanediol, neopentyl glycol, diglycidyl ether of aliphatic diol such as polyalkylene glycol, sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol , Polyglycidyl ethers of aliphatic polyols such as trimethylolpropane, polyglycidyl ethers of alicyclic polyols such as cyclohexanedimethanol, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, sebacic acid and the like Ester, polyglycidyl ester of polyvalent aromatic carboxylic acid, resorcinol, bis- (p-hydroxyphenyl) methane, 2,2-bis- (p-hydroxy) Diglycidyl ether or polyglycidyl ether of polyhydric phenol such as phenyl) propane, tris- (p-hydroxyphenyl) methane, 1,1,2,2-tetrakis (p-hydroxyphenyl) ethane, N, N-diglycidyl N-glycidyl derivatives of amines such as aniline, N, N-diglycidyl toluidine, N, N, N ', N'-tetraglycidyl-bis- (p-aminophenyl) methane, triglycidyl derivatives of aminophor, tris Although glycidyl tris (2- hydroxyethyl) isocyanurate, triglycidyl isocyanurate, ortho cresol type epoxy, phenol novolac type epoxy are mentioned, it is not limited only to this illustration, these are used alone or in combination of 2 or more types Can be used .

  In addition to the curing agent, it is also possible to further use a compound capable of chemically bonding with the functional group contained in the acrylic copolymer (A), for example, an oxazoline compound. Monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, 2,4-diphenyl-2-oxazoline etc. as an oxazoline compound 2,2 '-(1,3-phenylene) -bis (2-oxazoline), 2,2'-(1,2-ethylene) -bis (2-oxazoline), 2,2 '-(1,4- (1,4-ethylene) Examples include dioxazoline compounds such as butylene) -bis (2-oxazoline) and 2,2 '-(1,4-phenylene) -bis (2-oxazoline), but are not limited to such examples. These can be used alone or in combination of two or more.

A curable composition for forming a hard coat layer (hereinafter sometimes simply referred to as "curable composition") may be an acrylic copolymer (A), a curing agent (B) and, if necessary, an alkylene. It is possible to obtain a curable composition for forming a hard coat layer by measuring and blending predetermined amounts of a component having an oxide chain and a solvent (an organic solvent is preferable) and additives described later and sufficiently stirring with a stirrer. .
Alternatively, it may be a so-called two-liquid mixing type in which the curing agent (B) is mixed with other components at the time of use.

  The curing agent (B) can be appropriately blended in any amount, but in particular, curing equivalent to the hydroxyl group / carboxyl group equivalent (referred to as Aeq.) Of the acrylic copolymer (A) and crosslinking with these functional groups The functional group equivalent (it is set as Beq.) In an agent (B) is a Beq. / Aeq. When it is blended so as to be = 0.01 to 3, the durability and the moldability of the hard coat layer are easily compatible. Beq. / Aeq. = 0.05 to 2 is more preferable, and further, Beq. / Aeq. It is more preferable that it is = 0.05-1.5.

  In order to improve moldability, compounds having a hydroxyl group or a carboxyl group other than the acrylic copolymer (A) can also be added. In that case, the hydroxyl and carboxyl group equivalents thereof are also said Aeq. It is preferable to determine the amount of the curing agent (B) to be added.

<Cellulose Nanofiber (C)>
The cellulose nanofiber (C) in the present specification refers to a cellulose fiber having a width of 3 to 100 nm and a length of 100 nm to several μm, and the high aspect ratio enables enhancement of the toughness of the decorative film and crack resistance Improve.
Usually, a crack of a resin sheet such as a decoration film is a crack in a film due to the resin chain being loosened or broken by an external stress, which is a starting point and occurs. By including cellulose nanofibers having a chain length longer than that of the resin chain, the occurrence of membrane cracking can be delayed. Since the cellulose nanofibers exist independently of the resin, they do not affect the inherent elastic modulus of the sheet, and the elongation of the film is improved by the suppression of the film cracks, which leads to the improvement of the toughness of the resin sheet.
Usually, it is possible to improve toughness by adding glass fiber, inorganic filler, etc., but since the size of a general filler is large, it is difficult to achieve compatibility with transparency. On the other hand, as described above, cellulose nanofibers do not have an optical influence with a fiber diameter of 100 nm or less, and since their refractive index is close to that of general-purpose resins, they maintain transparency in combination with resins. You can do it.

  The cellulose nanofiber (C) which can be used in the present invention is not particularly limited, but the fiber diameter of the cellulose nanofiber is preferably 3 to 100 nm, more preferably 3 to 50 nm, in order to maintain the transparency of the film in the combined system with the resin. Is preferable, and 3 to 20 nm is more preferable.

By the way, the hard coat layer may contain a component having 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, one having an alkylene oxide chain (hereinafter, also referred to as “an acrylic copolymer incorporating an alkylene oxide chain”) is used as the acrylic copolymer (A) Or a component having an alkylene oxide chain other than the acrylic copolymer (A) (hereinafter, also referred to as "component having an alkylene oxide chain") can be used. When the acrylic copolymer (A) has an alkylene oxide chain, a component having an alkylene oxide chain can be further used.

  As a method of incorporating an alkylene oxide chain into the acrylic copolymer (A), a monomer having an alkylene oxide chain may be copolymerized when obtaining the above-mentioned acrylic copolymer (A).

Examples of the monomer having an alkylene oxide chain include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polytetraethylene (meth) acrylate, alkoxypolyethylene glycol (meth) acrylate, alkoxypolypropylene glycol (meth) acrylate, and alkoxy Polytetraethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, phenoxy polytetraethylene glycol (meth) acrylate, or multimers thereof, and the like.
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, PDT-650, PDBE-200A, PDBE-250, PDBE-450A, PDBE-1300, ADE-200, ADE-300, ADE-400A, ADP-400, ADT-250),
Osaka Organic Chemical Industry Co., Ltd. biscoat # 192, bis coat # 192, bis coat # 190, bis coat # MTG, 2-MTA, MPE 400 A, MPE 550 A, bis coat # 310 HP, bis coat # 335 HP, bis coat # 700 HV, bis coat #, bis coat # 190 D , Viscote # 230 D,
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-4, A-BPEF, A-BPP-3, APG-100, APG-200, APG- 400, APG-700, A-PTMG-65, 2G, 3G, 4G, 9G, 14G, 23G, BPE-80N, BPE-100, BPE-200, BPE-500, BPE-900, BPE- 1300N, 1206PE, Although 9PG etc. are mentioned, this invention is not limited only to this illustration. The monomers having these alkylene oxide chains may be used alone or in combination.

As components having an alkylene oxide chain, polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkylate, polyoxypropylene alkylate, polyethylene glycol dialkylate, polypropylene glycol dialkylate, polyethylene glycol, polypropylene glycol, poly Examples thereof include butylene glycol, polytetraethylene glycol, polyoxyethylene monoalkyl ether, polyoxyethylene dialkyl ether, polyoxypropylene monoalkyl ether, polyoxypropylene dialkyl ether and the like, and as a commercial product, for example, manufactured by NOF Corporation Nonionic series (K-204, K-220, K-230, K-2100 W, P-208, P-2 0, P-213, E-202, E-202S, 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-507, HT-510, HT-512, HT-515, HT-518, MN-811, L- 2, L-4, S-2, S-4, S-6, S-15, S-15 K, S-15.4, S-15.4 V, S-40, O-2, O-3, O-4, O-6, DS-60HN, DO-4, DO-6), Persoft series (NK-60, NK-90C, NK-100, NK-100C), Dispanol series (TOC, 16, 16A, LS-100), Pronon series (# 102, # 1 4, # 201, # 202B, # 204, # 208), UniLub series (70DP-600B, 70DP-950B, MS-70K, 50DB-22, 50MB-2), PEG series (# 200T, # 200, #) 300, # 400, # 600, # 1000, # 1500, # 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) and the like. The present invention is not limited only to those exemplified.

  The content of the alkylene oxide chain is 0.5 to 20% by mass in the total 100% by mass of the acrylic copolymer (A), the curing agent (B), the cellulose nanofiber (C) and the component having the alkylene oxide chain. Is preferred. When the content of the alkylene oxide chain is 0.5 to 20% by mass, chemical resistance can be improved without deteriorating the heat and humidity resistance.

  From the viewpoint of design, the hard coat layer preferably has a total light transmittance of 40% or more. Further, the diffuse transmittance is more preferably 70% or less. When providing a coloring layer mentioned later to a decoration film, the design nature given by a coloring layer becomes is hard to be damaged because the total light transmittance of a hard court layer is 40% or more. The total light transmittance and the diffuse transmittance can be measured with a haze meter NDH 2000 manufactured by Nippon Denshoku Kogyo Co., Ltd. If the curable composition for hard-coat layer formation which is excellent in coatability is used, the hard-coat layer which is excellent in transparency can be formed, without impairing the transparency of curable composition itself.

  The hard coat layer of the present invention preferably has an elongation of 100% or more at the time of molding, for example, at 160 ° C. when broken. When the elongation rate is 100% 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 100 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).

  The hard coat layer preferably has an extensibility (toughness) at 25 ° C. of 150% or more. When the elongation percentage is 100% or more, physical strength such as impact resistance and bending resistance at room temperature use can be improved, and breakage and cracking can be prevented. Although the upper limit of the elongation rate is not particularly limited, the elongation rate is preferably 100 to 300% from the viewpoint of achieving both HC properties 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, 100% indicates that it is not stretched at all, and 200% 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 the present invention, the curable 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.
The solvent plays a role in adjusting the viscosity and the flowability of the curable composition. The solvent at the time of polymerization of the acrylic copolymer (A) may be used as it is, or may be further added at the time of preparation of the curable composition.

  In the present invention, for the purpose of imparting weather resistance to the formed acrylic resin layer, the curable composition for forming a hard coat layer 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. A UV absorber or UV stabilizer may be added as an additive to the curable composition, or a UV absorber or UV stabilizer having a functional group may be used by reacting with an acrylic copolymer. Also, it may be used by reacting with other resins. The UV absorber and UV stabilizer are used in an amount of 0.1 to 25 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the solid content of the curable composition excluding the UV absorber and UV stabilizer. It is preferable to use a part.

  In the present invention, a slip agent can be added to the curable composition 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 curable composition.

  In the present invention, since the curable composition for hard coat layer formation may be applied as a relatively thick film, 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 curable composition.

  In the present invention, by containing organic or inorganic fine particles in the curable composition, the surface of the acrylic film is made uneven to impart an antiblocking effect, to give a matte feeling due to the surface unevenness, or to a film. The strength can be given to make it hard to be scratched. It is preferable to contain 0.01-20 mass parts of these microparticles | fine-particles with respect to 100 mass parts of acrylic resin (a), 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 acrylic film excellent in moldability and not inhibiting 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.

Further, if necessary, a curing accelerator may be added to the curable composition as long as the effects of the present invention are not impaired.
Examples of the curing accelerator include tin compounds, metal salts and bases, and specific examples include tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, tin chloride, iron octylate, cobalt octylate, naphthenate Acid zinc, triethylamine, triethylenediamine and the like. These can be used alone or in combination.

  In the curable composition, if necessary, a filler, a thixotropy imparting agent, an antiaging agent, an antioxidant, an antistatic agent, a flame retardant, a thermal conductivity improving agent, to the extent that the effects of the present invention are not impaired. Add various additives such as plasticizer, anti-sagging agent, antifouling agent, antiseptic, disinfectant, antifoaming agent, antifoaming agent, leveling agent, curing agent, thickener, pigment dispersant, silane coupling agent etc. It is also good.

<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 curable 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 thermally cured product obtained by thermally curing a curable composition for forming a hard coat layer comprising the above-mentioned acrylic copolymer (A) and a curing agent (B).

  The method of providing a hard-coat layer on a base material layer is demonstrated. The heart coat layer can be provided for coating and curing the above-mentioned curable composition on one side of the substrate layer. Specifically, the above-mentioned curable composition is applied to the base material layer, and immediately put into a drying oven to evaporate the solvent. After the solvent has volatilized, aging is carried out if necessary, and the hydroxyl group / carboxyl group in the acrylic copolymer (A) and the functional group in the curing agent (B) are reacted and cured to obtain a hard coat layer Can.

Alternatively, the hard coat layer can be provided on the base layer using an adhesive.
Specifically, a curable composition for forming a hard coat layer is coated on a peelable sheet, and put into a drying oven to evaporate the solvent. After the solvent is volatilized, aging is carried out if necessary, and the hydroxyl group / carboxyl group in the acrylic copolymer (A) and the functional group in the curing agent (B) are reacted to form a cured coating (cast film) obtain. 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 layer The decorative film which has and a base material layer can be obtained. The peelable sheet is properly peeled before and after lamination.

  As the method of applying the curable composition, 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 curable composition is preferably dried at 50 to 200 ° C, more preferably 70 to 120 ° 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 hydroxyl group / carboxyl group of the acrylic copolymer (A) and the functional group of the curing agent (B) normally proceeds in an environment of about room temperature to about 200 ° C. for about 10 minutes to 10 days (aging ). Further, it is also possible to select a method in which the temperature of the oven is raised to about 100 to 200 ° C. in the aforementioned drying step, and the reaction is terminated while passing through the oven.

  The solvent may be dried in an oven, and the removed laminate may be aged in a single sheet, or may be wound in a roll and aged. In any case, tackiness may remain in the coating before aging, and blocking may occur if 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 curable composition for forming a hard coat layer is preferably defoamed before being applied to the substrate layer or the peelable sheet. When bubbles are contained in the curable composition, the bubbles are mixed into the coating film being formed when the composition is applied to the base material layer or the releasable sheet, and the bubbles are formed on the surface of the coating film after drying or curing. There may be a cracked crack. 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 adhesive strength and 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 curable composition to a substrate layer and drying it, applying it to a substrate layer, drying, aging, or applying it to a substrate layer and irradiating it with light A method of printing and drying the substrate layer, a method of printing on the substrate layer and light irradiation, a method of vapor-depositing a metal on the substrate layer, and the like can 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.
Antiblocking of decorative film during production, prevention scratched, preventing scratched during molding, the mold mark prevention, in terms of preventing contamination until after molding decorative molded article Ru is put into use, on the acrylic film 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 applied on a film, dried, and if necessary, aged to form a hard coat layer or an adhesive layer, a method of bonding to a substrate layer or a decorative film may, for example, be 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.
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 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").

Synthesis Example A-1 "Acryl-based copolymer 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, 82 parts of methyl methacrylate, 4 parts of 2-hydroxyethyl acrylate, 9 parts of methacrylate, 5 parts of ethoxyethoxyethyl acrylate, azobis A monomer solution in which 0.1 part of isobutyro nitrile was 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. The reaction was terminated by cooling when the amount of unreacted monomer was 1% or less, and an acrylic copolymer A-1 solution with a solid content of about 40% was obtained.
The acrylic copolymer A-1 had a glass transition temperature of 90 ° C., a hydroxyl value of 19 mg KOH / g, an acid value of 59 mg KOH / g, and a weight average molecular weight of 55,000.
The solid content, the glass transition temperature (Tg), the acid value, the hydroxyl value and the mass average molecular weight (Mw) were measured by the methods 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 150 ° C. oven for 10 minutes to dry. 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

<< Measurement of glass transition temperature (Tg) >>
An aluminum pan containing a sample of about 10 mg of resin dried to a solid content of 100% and an aluminum pan containing no sample are set in a differential scanning calorimetry (DSC) apparatus, and this is set in a nitrogen stream. Using liquid nitrogen, perform cooling processing to the predicted glass transition temperature minus 50 ° C, and then heat it up to the predicted glass transition temperature plus 50 ° C at a heating rate of 10 ° C / min and plot the DSC curve . A straight line extending the baseline on the low temperature side of this DSC curve (the DSC curve portion in the temperature range where no transition and reaction occur in the specimen) to the high temperature side, and the slope of the curve of the step change portion of the glass transition is maximized The extrapolated glass transition start temperature (Tig) was determined from the point of intersection with the tangent drawn at such a point, and this was taken as the glass transition temperature.

<< 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)

<< Measurement of mass average molecular weight (Mw) >>
It measured using Showa Denko Shodex GPC-104 / 101 system.
Column Shodex KF-805L + KF-803L + KF-802
Detector Differential Refractometer (RI)
Column temperature 40 ° C
Eluent tetrahydrofuran (THF)
Flow rate 1.0 ml / min
Sample concentration 0.02%
Standard sample for calibration curve TSK standard polystyrene

Synthesis Example A-2 to A-27 "acrylic copolymer A-2 to A-27 solution",
Comparative Synthesis Example A-101 to A-106 "Acryl-based copolymer A-101 to A-106 solution"
The reaction was carried out according to the composition of Table 1 to obtain acrylic copolymer A-2 to A-27 solution and A-101 to A-106 solution. The glass transition temperature, acid value, hydroxyl value and mass average molecular weight are shown in Table 1. The solid content was all adjusted to be 40%.

Example 1
Preparation of Hard coat curable composition “HC-1”
In the acrylic copolymer (A-1) solution obtained in Synthesis Example A-1 containing 100 parts by mass of the acrylic copolymer (A-1), a nurate of hexamethylene diisocyanate as a curing agent of the isocyanate compound type Add 31 parts by mass (solid mass) of Duranate “MHG-80B” manufactured by Asahi Kasei Co., Ltd. and 13 parts by mass of cellulose nanofiber “N-03” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. so that the solid content is 20%. To the mixture was added methyl ethyl ketone (MEK) and the mixture was stirred to obtain a hard coat curable composition (HC-1).

<Preparation of a cured coating film>
Using a doctor blade, the hard coat curable composition (HC-1) is applied to a 100 μm thick poly (methyl methacrylate) (PMMA) film and dried in an oven at 100 ° C. for 1 minute to volatilize solvents I did. The doctor blade was selected so that the film thickness after drying was 20 μm. Next, it is left in a temperature-controlled room at 50 ° C. for 4 days to allow the reaction between the acrylic copolymer and the curing agent to proceed (age) to form a cured coating film (hard coating layer) on the PMMA film, and a decorative film I got
About the obtained decorative film, according to the method mentioned later, productivity, extensibility, chemical resistance, and abrasion resistance were evaluated. The results are shown in Table 5.

«Evaluation of productivity»
The resulting curable composition is left to stand at 25 ° C., and the time taken for the viscosity of the curable composition to thicken up to 10000 mPa · s at which it becomes difficult to apply is measured, and from that time as a decorative film The productivity of was evaluated based on the following criteria.
4: 10 hours or more. Excellent productivity.
3: 6 hours or more, less than 10 hours. Good productivity.
2: 3 hours or more, less than 6 hours. Productivity is acceptable.
1: less than 3 hours. Not productive.
The viscosity was measured using a B-type viscometer (rotational speed 60 rpm) and was measured at 25 ° C. environment.

«Evaluation of extensibility at 160 ° C»
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: 160 ° C
Tension speed: 1 mm / min
Chuck distance: 10 mm
The surface of the hard coat layer after 200% elongation was observed and evaluated according to the following criteria.
4: No cracks were observed 3: No cracks were found in 1 to 5 places 2: No cracks were found in 6 or more places 1: Hard coat layer was 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.
4: No appearance defects such as generation of wrinkles or discoloration were observed in both the hard coat layer and the base material layer.
3: A part of the hard coat layer floats from the substrate layer.
2: Discoloration of the substrate layer is observed in part.
1: Discoloration of the substrate layer is generally observed.

«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: 4 or less wounds 3: 5 to 19 wounds 2: 20 to 49 wounds 1: 50 or more wounds

«Evaluation of elongation at 25 ° C (toughness)»
The obtained decorative film was stretched under the following conditions, and the elongation at break was measured.
Tensile tester: "Small desktop tester EZ-SX 500N" (made by Shimadzu Corporation)
Sample width: 5 mm
Temperature: 25 ° C
Tension speed: 10 mm / min
Chuck distance: 2.4 mm
Elongation rate: ((Elongation at break + distance between chucks) / (distance between chucks)) × 100%

«Evaluation of permeability»
Conduct measurement of total transmittance and haze under the following conditions for the obtained decorative film.
Turbidimeter: "HAZE Meter NDH 2000" (manufactured by Nippon Denshoku Kogyo Co., Ltd.)
Number of measurements: 3 times (adopt average)
[Total transmittance]
3: 90% or more 2: 85% or more and less than 90% 1: 85% or less [Haze]
3: 1% or less 2: 1% or more 2% or less 1: 2% or more

[Examples 2 to 56]
After obtaining curable compositions HC-1 to 56 for hard coating according to the compositions of Tables 2 and 3 in the same manner as Example 1, the resulting curable composition is coated on a PMMA film to obtain a decorative film. The
The evaluation was performed in the same manner as in Example 1. The results are shown in Table 5.

Comparative Example 1
<Preparation of a curable composition “HC-B1” for a hard coat for comparison>
In the acrylic copolymer (A-101) solution obtained in Comparative Synthesis Example A-101 containing 100 parts by mass of an acrylic copolymer (A-101), as a curing agent for an isocyanate compound, manufactured by Asahi Kasei Corporation, 31 parts by mass (solid mass) of "Duranate MHG-80B" was added, and methyl ethyl ketone (MEK) was further added to a solid content of 30%, followed by stirring to obtain a curable composition (HC-101) for hard coating .
The resulting curable composition was used to obtain a decorative film in the same manner as in Example 1. The productivity, extensibility, chemical resistance, and abrasion resistance were evaluated in the same manner. The results are shown in Table 6.

[Comparative examples 2 to 11]
After the curable composition for hard coat HC-102 to 111 was obtained according to the composition of Table 4 in the same manner as Comparative Example 1, the obtained curable composition was coated on a PMMA film to obtain a decorative film.
The evaluation was performed in the same manner as in Example 1. The results are shown in Table 6.

  As shown in Table 5, in Examples 1 to 56, a decorative film having a hard coat layer which is a cured product of a suitable acrylic copolymer and a curing agent contained in cellulose nanofibers is extensible at 160 ° C. Excellent chemical resistance, abrasion resistance, and elongation at 25 ° C.

  On the other hand, as shown in Table 6, in Comparative Examples 1 to 11, since the cellulose nanofibers are not contained, the extensibility at 25 ° C. is insufficient.

  In addition, as shown in Table 5, in Examples 1 to 56, a decorative film having a hard coat layer which is a cured product of a suitable acrylic copolymer and a curing agent contained in cellulose nanofibers contains a filler. In spite of the above, it has high total transmittance and low haze, and has the same transparency as Comparative Examples 1 to 9 in which no filler is added.

On the other hand, as shown in Table 6, in Comparative Examples 10 to 11, the transparency is impaired by adding the filler.

[Example 57]
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 7.

[Examples 58 to 61]
A decorative film was obtained using the base material (each thickness 100 μm) shown in Table 7 instead of the polycarbonate base material used in Example 57, and the same evaluation as in Example 57 was performed. The results are shown in Table 7.
In Example 58, a hard coat layer was formed on the polymethacrylic side of the two-layered film of polymethacrylic and polycarbonate.

[Example 62]
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 an acrylic copolymer (A-1), 60 parts by mass (solid mass) of P301-75E (polyisocyanate compound manufactured by Asahi Kasei Chemicals) as a polyisocyanate compound, MA100 (Mitsubishi Chemical Corporation) Carbon black) 5 parts by mass (solid mass), BYK- 9076 (BYK company dispersant) 0.5 parts by mass (solid mass), and methyl ethyl ketone (MEK) to a solid content of 30% The mixture was stirred to obtain a colored curable resin composition.

The colored curable resin composition is applied to the polycarbonate film side of the member 1 using a bar coater and dried in an oven at 100 ° C. for 1 minute to volatilize the solvent to provide a colored layer having a thickness of 5 μm. The
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, the decorative film is vacuum formed on the surface of the steel member with a vacuum suction force of about 1.5 atmosphere while heating to about 160 ° C. 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 63 to 83]
A decorative film with an adhesive layer and a colored layer was obtained in the same manner as in Example 62 except that the adhesive shown in Table 8 was used instead of the adhesive used in Example 62.

Then, molding and adhesion were evaluated on the objects to be decorated described in Table 8 in the same manner as in Example 62.
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 62.

[Example 84]
A decorative film having a colored layer was obtained in the same manner as in Example 62 except that the adhesive layer was not provided.
The obtained decorative film is inserted into the cavity of an injection molding die, vacuum suction is performed under the condition of about 1.5 atmospheric pressure while heating to about 160 ° 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 62 for the obtained decorative molded body.

[Example 85]
A decorated molded body was produced in the same manner as in Example 84 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 (109) : Decorative film

Claims (8)

A decorative film comprising a laminate including a hard coat layer and a substrate layer, wherein the hard coat layer comprises an acrylic copolymer (A), a curing agent (B) and a cellulose nanofiber (C). A decorative film comprising a thermosetting product of a curable composition and satisfying the following conditions (1) to (5).
(1) The glass transition temperature of the said acryl-type copolymer (A) is 30-150 degreeC.
(2) The acrylic copolymer (A) has at least one of a hydroxyl group and a carboxyl group.
(3) The sum of the hydroxyl value and the acid value of the acrylic copolymer (A) is 1 mg KOH / g or more and 300 mg KOH / g or less.
(4) The mass average molecular weight of the acrylic copolymer (A) is 55,000 to 1,000,000.
(5) The curing agent (B) comprises a compound having an isocyanate group or a precursor thereof, a compound having an aziridinyl group, a compound having a carbodiimide group, a metal chelate compound, a metal alcoholate compound and a compound system having an epoxy group It is chosen from the group.   The content ratio of cellulose nanofibers (C) contained in the total 100 mass% of the acrylic copolymer (A), the curing agent (B) and the cellulose nanofibers (C) is 0.5 to 20 mass% The decorative film according to claim 1.   The decorative film according to claim 1 or 2, wherein the base material layer comprises a single layer or a multiple layer selected from the group consisting of polyester, polycarbonate, polymethyl methacrylate, polyethylene and polypropylene.   The decorative film according to any one of claims 1 to 3, 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 4, further comprising at least one of an adhesive layer and a colored layer.   The decorative film according to claim 5, wherein the adhesive layer is laminated between the base layer and the hard coat layer.   The decorative film according to claim 5, wherein the adhesive layer is laminated on the non-facing surface side of the hard coat layer of the base material layer. A to-be-decorated body is provided, and a decorative film which covers at least a part of the to-be-decided body, the decorative film is the decorative film according to any one of claims 1 to 7; Decorative molded body.