TWI437034B - Hard coat film for molding - Google Patents

Description

Hard coating for molding

The present invention relates to a hard coating film for forming. In particular, it is related to a hard coating film for molding which is excellent in surface hardness and scratch resistance and excellent in moldability and solvent resistance at low temperature and low pressure. Further, it is also related to a hard coating film for light-resistant molding which is suitable for use in outdoor applications.

The sheet for molding has been conventionally represented by a polyvinyl chloride resin film, and is preferably used from the viewpoint of workability and the like. On the other hand, when the film is burned by a fire or the like, there is a problem of occurrence of a toxic gas and a problem of bleed out of the plasticizer. Since the environmental resistance is required in recent years, a new raw material having a small environmental burden is required.

In order to satisfy the above requirements, an unstretched sheet composed of a polyester, a polycarbonate, and an acrylic resin of a non-chlorine-based raw material is used in a wide range of fields. In particular, an unstretched sheet composed of a polyester resin is attracting attention because of its excellent mechanical properties and transparency, and excellent economic efficiency. For example, in the prior art documents 1 to 5, a substantially amorphous polyester resin in which about 30 mol% of an ethylene glycol component in polyethylene terephthalate is substituted with 1,4-cyclohexane dimethanol is used. Unstretched polyester-based sheet of the component (see Patent Documents 1 to 5).

The unstretched polyester-based sheet satisfies the market demand in terms of moldability or build-up suitability, but since it is an unstretched sheet, heat resistance and solvent resistance are insufficient, and the market demand is not satisfied. .

In order to solve the above problems, a method of biaxially stretching a polyethylene terephthalate film has been proposed (see, for example, Patent Documents 6 to 9).

However, the above method can improve the heat resistance and the solvent resistance, but the moldability is insufficient, and the market demand cannot be satisfied from the viewpoint of the balance of the total quality. Further, in use for outdoor use, the printed layer or the resin is easily denatured and deteriorated by sunlight, and the problem of being inferior to long-term use arises.

On the other hand, when the film for molding is attached to the external contact position, in order to prevent the injury, a hardened layer is provided on the surface for the purpose of reinforcing the surface hardness of the film for molding and improving the scratch resistance.

The method of providing a hardened layer in the film for molding is generally carried out by a pneumatic molding method or a vacuum molding method, and then the hardened layer is laminated by a post-processing method such as a dipping method or a spray method. However, in this method, the hard layer is laminated by a cluster type processing, so that the stability of the quality is also problematic in addition to the limited production speed. Therefore, it is now required to form a hardened layer on a film before molding by a roll to roll type process and then molding it to obtain a molded body.

In the manner of laminating the hardened layer before molding, the properties sought by the hardened layer are required to have the same degree of surface hardness and scratch resistance as the method of setting the hardened layer after the forming process, and also need to be accompanied by molding. Formability can be traced when deformation occurs. However, in general, the hardened layer resin has a problem that the hardened layer is too hard and has no moldability in order to satisfy the surface hardness, so that the hardened layer is cracked (the crack of the hardened layer) due to deformation during molding.

Therefore, there has been a prior art which proposes a hard coating film which laminates a resin having a certain degree of surface hardness after hardening but which is still soft, or which improves the moldability, or a layer having flexibility and a layer having a strong surface hardness on the substrate. A plurality of layers are laminated to obtain a hard coating film having strong surface hardness and flexibility (see Patent Documents 10 to 13).

(Patent Document 1) Japanese Patent Publication No. 9-156267

(Patent Document 2) JP-A-2001-71669

(Patent Document 3) JP-A-2001-80251

(Patent Document 4) JP-A-2001-129951

(Patent Document 5) JP-A-2002-249652

(Patent Document 6) Japanese Patent Publication No. 9-187903

(Patent Document 7) Japanese Patent Publication No. Hei 10-296937

(Patent Document 8) Japanese Patent Publication No. 11-10816

(Patent Document 9) Japanese Patent Publication No. 11-268215

(Patent Document 10) JP-A-2005-305383

(Patent Document 11) JP-A-2007-284626

(Patent Document 12) JP-A-2007-313728

(Patent Document 13) International Publication No. 2008/029666

However, the hard coating film proposed in Patent Documents 10 and 11 has a suitable surface hardness, but has only a bending property and a limited processing property for punching, and the hardening property proposed in Patent Document 12 is hard. Although the coating film has stretchability, the surface hardness cannot be satisfied. Further, although the hard coating film proposed in Patent Document 13 attempts to coexist with surface hardness and moldability, in the field where higher moldability or higher surface hardness is required, sufficient performance may not be exhibited. In other words, the above-mentioned patent document cannot provide a hard coating film for molding which satisfies both the characteristics of high surface hardness and high moldability without impairing the properties of the polyester film for molding having excellent properties of moldability and solvent resistance.

An object of the present invention is to solve the above problems, that is, a film for molding which is excellent in moldability and solvent resistance at a low temperature and a low pressure, and a hardened layer is processed and laminated on a film for forming before the molding. A hard coating film for molding that contributes to improving productivity and quality stability, and has both surface hardness, scratch resistance, and follow-up moldability when deformation occurs during molding.

The polyester film for molding of the present invention which can solve the above problems is composed of the following items.

According to a first aspect of the invention, there is provided a hard coating film for forming a base film comprising a biaxially oriented polyester film comprising a copolymerized polyester and a hardened layer obtained by curing a coating liquid, wherein the coating liquid is at least The free radiation curable compound having three or more functional groups and the free radiation curable compound having 1 and/or 2 functional groups, and the free radical curable compound contained in the coating liquid is free of 1 and/or 2 functional groups The content of the radiation-curable compound is 5% by mass or more and 95% by mass or less, and the base film satisfies the following requirements (1) to (3): (1) Stress at 100% elongation in the longitudinal direction and the width direction of the film Both are 40 to 300 MPa at 25 ° C and 1 to 100 MPa at 100 ° C; (2) the melting point is 200 to 245 ° C; (3) the plane orientation is 0.01 or more and 0.095 or less.

According to a second aspect of the invention, at least one of the free-radiation-curable compounds contained in the coating liquid is the above-mentioned hard coating film for forming an amine-containing free radiation-curable compound.

In the third aspect of the invention, the hardened layer contains the particles having an average particle diameter of 10 nm or more and 300 nm or less, and the content of the particles in the cured layer is 5% by mass or more and 70% by mass or less.

According to a fourth aspect of the invention, the copolyester is (a) a copolyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a diol component containing a branched aliphatic diol or an alicyclic diol. Or (b) the above-mentioned hard coating film for molding comprising a copolymerized polyester comprising an aromatic dicarboxylic acid component of citric acid and isononic acid and a glycol component containing ethylene glycol.

According to a fifth aspect of the invention, in the polyester constituting the biaxially oriented polyester film, the diol component contains the hard coating film for molding of 1,3-propanediol unit or 1,4-butanediol unit.

According to a sixth aspect of the invention, the biaxially oriented polyester film contains an ultraviolet absorber having a light transmittance of 50% or less at a wavelength of 370 nm.

The seventh invention is a molded body obtained by applying any of the above-described hard coating film for molding by vacuum molding, air pressure molding, and mold molding.

The hard coating film for molding of the present invention has excellent moldability at the time of heat molding at a low temperature and a low pressure, and has good solvent resistance. Further, the hard coating film for molding of the present invention has both surface hardness and scratch resistance and followability moldability which can follow the deformation at the time of molding. Since the hard coating film for molding of the present invention has high surface hardness and excellent stretchability, the embodiment can be suitably used for parts such as nameplates or building materials. Further, in the case of using the radical-curable resin and/or particles having an amine group in the embodiment of the present invention, it is possible to coexist both the surface hardness and the moldability, and it is suitable for use in parts such as a case. . Further, the present invention does not require the hard coating film processing after molding, and contributes to productivity and quality stability in molding processing.

Further, in a preferred embodiment of the present invention, the film contains an ultraviolet absorber to reduce the transmittance in the ultraviolet range, and it is possible to impart light resistance, and is particularly suitable as a molding material for use in outdoor applications.

Regarding the mode of carrying out the invention, the technical significance of the physical properties of the substrate film of the present invention will first be described. Next, a method of producing the substrate film of the present invention will be described. The hardened layer of the present invention will be further described.

(substrate film)

In the present invention, the stress (F100) at 100% stretching is a measure relating to the moldability of the film. The reason why F100 is closely related to the moldability of the film is that, for example, when the biaxially oriented polyester film is molded by a vacuum molding method, the film may be locally stretched by 100% or more in the vicinity of the corner of the mold. In the case of a film having a high F100, it is considered that a part of the extremely high stress is generated in such a localized stretching portion, and the concentration of the stress causes the film to be broken to cause a decrease in moldability. On the other hand, in the film in which F100 is too small, it is considered that the moldability is good, but only a very weak tension is generated at a portion which is uniformly stretched at the plane of the mold, and as a result, the film does not seem to be uniformly stretched at the portion.

In the present invention, the physical property relating to moldability in accordance with the temperature at the time of molding is a stress (F100 ₁₀₀ ) when 100% is stretched at 100 °C. Further, when molding is carried out using a mold having irregularities or depressions, the film before molding and the mold are gently formed in advance, and the physical properties relating to moldability are measured by using a tensile strength of 100% at 25 ° C ( F100 ₂₅ ).

The film of the present invention has a stress (F100 ₂₅ ) at 100% stretching at 25 ° C regardless of the length direction and the width direction of the film of 40 to 300 MPa.

When the F100 ₂₅ in the longitudinal direction and the width direction of the film is 40 to 300 MPa, the lower limit is preferably 50 MPa, more preferably 60 MPa, and more preferably 70 MPa. The upper limit is preferably 250 MPa, and more preferably 200 MPa and more preferably 180 MPa. If the F100 _{25 is} less than 40 MPa, when the roll-shaped film is pulled and unwound (unrolled), the workability is poor due to elongation or breakage of the film. On the other hand, if F100 ₂₅ exceeds 300 MPa, moldability is deteriorated. In particular, when molding is performed using a mold having irregularities or depressions, the film before molding may be formed in advance with such a mold. At this time, the film is less likely to adhere to the mold, and the design of the finished product is poor.

Further, in the film of the present invention, the stress (F100 ₁₀₀ ) at 100% stretching at 100 ° C is important in the longitudinal direction and the width direction of the film of 1 to 100 MPa.

The upper limit of the longitudinal direction and the width direction F100 ₁₀₀ of the film is preferably 90 MPa from the viewpoint of moldability, more preferably 80 MPa, and particularly preferably 70 MPa. On the other hand, the lower limit of F100 ₁₀₀ is preferably 5 MPa, more preferably 10 MPa, more preferably 20 MPa, and more preferably more than 35 MPa from the viewpoint of elasticity and form stability when a molded article is used.

The film of the present invention preferably has a heat shrinkage ratio of from 0.01 to 5.0% in the longitudinal direction and the width direction at 150 °C. The lower limit of the heat shrinkage at 150 ° C is preferably 0.1%, and preferably 0.5%. On the other hand, the upper limit of the heat shrinkage ratio at 150 ° C is preferably 4.5%, more preferably 4.1%, more preferably 3.2%. Even if the biaxially stretched polyester film for molding which has a heat shrinkage ratio of less than 0.01% in the longitudinal direction and the width direction of 150 ° C is produced, there is no significant difference in practical effect, and since the productivity is extremely lowered, There is no necessity to make the heat shrinkage rate at 150 ° C less than 0.01%. On the other hand, when the heat shrinkage rate of the film in the longitudinal direction and the width direction of 150 ° C exceeds 5.0%, the heat treatment such as vapor deposition, sputtering, or printing may cause the film to be deformed after the heat treatment, and may be post-processed. The film has poor appearance or design.

Further, the thickness unevenness of the base film of the present invention is preferably 5% or less. When the thickness unevenness exceeds 5%, the planarity of the surface of the molded body is deteriorated, and the strength of the molded body may be lowered. The thickness unevenness of the base film is preferably small, but from the viewpoint of productivity, it is preferably 0.5% or more.

Further, in the present invention, the haze of the film is preferably from 0.1 to 3.0%. The lower limit of haze is preferably 0.3% or more preferably 0.5%. On the other hand, the upper limit of the haze is preferably 2.5% or more and 2.0%. Films having a haze of less than 0.1% are difficult to produce on a general production scale due to poor slidability. On the other hand, when the haze of the film exceeds 3.0%, when the vapor deposition or the sputtering surface or the printing surface of the metal or the like is observed from the back surface of the film, the metal or the printed surface does not appear to be clear, and the design property is inferior.

In the present invention, the degree of planar orientation (ΔP) of the film is also related to the formability, and the degree of planar orientation is more oriented toward the plane in the direction of the polymer chain, so that the moldability is lowered. In the present invention, the film has a plane orientation of less than 0.11. The upper limit of the plane orientation is preferably 0.095 or less, more preferably 0.090. Further, the smaller the plane orientation degree, the better the moldability, but the strength of the film and the chemical resistance are easily reduced. Therefore, the lower limit of the plane orientation degree is 0.01 or more, and is preferably 0.02, more preferably 0.03, and particularly preferably 0.04.

(Method of Manufacturing Substrate Film)

The polyester film for molding of the present invention uses a copolymerized polyester as a raw material. The copolyester is (a) a copolymerized polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a diol component containing a branched aliphatic diol or an alicyclic diol; or (b) A copolymerized polyester comprising an aromatic dicarboxylic acid component of citric acid and isophthalic acid and a glycol component containing ethylene glycol is suitable. Further, the polyester constituting the biaxially oriented polyester film preferably contains 1,3-propanediol unit or 1,4-butanediol unit as a diol component, and is preferable from the viewpoint of further improving moldability.

In the present invention, any of the film raw materials may be a copolymerized polyester alone, a blend of one or more kinds of homopolyester or copolymerized polyester, or a combination of a homopolyester and a copolymerized polyester. Among them, the blending method is suitable from the viewpoint of suppressing the decrease in the melting point.

As the above copolymerized polyester, when a copolymerized polyester composed of an aromatic dicarboxylic acid component, ethylene glycol, and a diol component containing a branched aliphatic diol or an alicyclic diol is used, the aromatic diol is used. The carboxylic acid component is preferably p-citric acid, isophthalic acid, naphthalene dicarboxylic acid or an ester-forming derivative thereof, and is 70 mol relative to the amount of the citric acid and/or naphthalene dicarboxylic acid component of the dicarboxylic acid component. More than % is preferable, and it is preferably 85 mol% or more, 95 mol% or more, and 100 mol%.

Further, examples of the branched aliphatic diol include neopentyl glycol, 1,2-propylene glycol, 1,3-propanediol, and 1,4-butanediol. The aliphatic diol can be exemplified by, for example, 1,4-cyclohexanedimethanol, dimethylol tricyclodecane, or the like.

Among them, neopentyl glycol and 1,4-cyclohexanedimethanol are particularly suitable. Further, in the present invention, it is more suitable to use 1,3-propanediol and 1,4-butanediol as a copolymerization component in addition to the above diol component. When these diols are used as a copolymerization component, it is suitable for imparting the above-mentioned characteristics, and is excellent in transparency and heat resistance, and is also suitable from the viewpoint of improving the adhesion to the adhesion-modifying layer.

Further, when the copolymerized polyester is composed of a copolymerized polyester composed of an aromatic dicarboxylic acid component containing p-citric acid and isophthalic acid and a glycol component containing ethylene glycol, the amount of the total diol component is The ethylene glycol is preferably 70 mol% or more, more preferably 85 mol% or more, more preferably 95 mol% or more, and particularly preferably 100 mol%. The diol component other than ethylene glycol is preferably the above-mentioned branched aliphatic diol, alicyclic diol or diethylene glycol.

The copolyester has an intrinsic viscosity of 0.50 dl/g or more, more preferably 0.55 dl/g or more, and more preferably 0.60 dl/g or more from the viewpoints of moldability, adhesion, and film stability. . When the intrinsic viscosity is less than 0.50 dl/g, the moldability tends to decrease. Further, when a filter is provided on the melt line (or in the middle of melting) to remove foreign matter, the upper limit of the intrinsic viscosity is preferably set to 1.0 dl/g from the viewpoint of discharging stability when the molten resin is extruded.

In the present invention, by using one or more kinds of homopolyester or copolyester as a raw material of a film, and blending the same to produce a film, transparency can be achieved while maintaining the same flexibility as that of the copolymerized polyester alone. High melting point (heat resistance). Further, it is possible to achieve flexibility and practically unproblematic melting point (heat resistance) while maintaining high transparency while using only a high melting point homopolyester (for example, bismuth phthalate). Further, when the base film has a multilayer structure of two or more layers, the amount of the copolymerization component of each layer may be the same or different, but a polyester resin having a different amount of two or more kinds of copolymerization components is also a preferred embodiment of the present invention. .

Further, at least one or more kinds of homopolyesters other than the above-mentioned copolymerized polyester and polyethylene terephthalate (for example, poly(p-butylene terephthalate) and polybutylene terephthalate) When it is blended and used as a raw material of the polyester film for molding of the present invention, it is more preferable from the viewpoint of moldability.

The melting point of the polyester film is preferably from 200 to 245 ° C from the viewpoint of heat resistance and moldability. By controlling the type and composition of the polymer to be used, and controlling the film forming conditions within the above-mentioned melting point range, a balance between moldability and completion is obtained, and a high-grade molded article can be produced economically.

Here, the melting point refers to the endothermic peak temperature at the time of melting detected by the differential scanning calorimetry (DSC, Differential Scanning Calorimetry). This melting point was measured using a differential scanning calorimeter (manufactured by Max Science Co., Ltd., DSC 3100S) at a temperature increase rate of 20 ° C / min. The lower limit of the melting point is more preferably 210 ° C and particularly preferably 230 ° C. When the melting point is less than 200 ° C, the heat resistance tends to deteriorate. Therefore, problems may occur when molding or when using a molded article, such as exposure to high temperatures. Further, an amorphous polyester having no melting point may cause problems in terms of mechanical strength and chemical resistance.

Further, the light transmittance of the base film at a wavelength of 370 nm is preferably 50% or less, more preferably 40% or less, and most preferably 30% or less. The light transmittance of the molding polyester film at a wavelength of 370 nm is controlled to 50% or less, and the light resistance of the printing layer can be improved when the film is printed. This is a preferred embodiment of the present invention.

The above method of controlling the light transmittance at a wavelength of 370 nm to 50% or less is a method in which a UV absorber is used in any layer of the base film constituent layer. The ultraviolet absorber may be either inorganic or organic as long as it can impart the above characteristics. Organic ultraviolet absorbers such as benzotriazole, benzophenone, cyclic imine, and the like, and combinations thereof. From the viewpoint of heat resistance, a benzotriazole-based or cyclic imide ester is preferable. When two or more types of ultraviolet absorbers are used, the ultraviolet absorption effect can be further improved by simultaneously absorbing ultraviolet rays of different wavelengths.

Examples of the benzotriazole-based ultraviolet absorber include 2-[2'-hydroxy-5'-(methacryloxymethyl)phenyl]-2H-benzotriazole and 2-[2'-hydroxyl group. -5'-(methacrylomethoxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloxypropyl)phenyl]-2H- Benzotriazole, 2-[2'-hydroxy-5'-(methacrylofluorenyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-3'-tertiary butyl -5'-(methacrylomethoxyethyl)phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-tertiary butyl-3'-(methacrylofluorene Phenyl]-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacrylomethoxyethyl)phenyl]-5-chloro-2H-benzotriazole, 2- [2'-Hydroxy-5'-(methacrylomethoxyethyl)phenyl]-5-methoxy-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryl醯Oxyethyl)phenyl]-5-cyano-2H-benzotriazole, 2-[2'-hydroxy-5'-(methacryloxyethyl)phenyl]-5-tertiary -2H-benzotriazole, 2-[2'-hydroxy-5'-(methacrylomethoxyethyl)phenyl]-5-nitro-2H-benzotriazole, etc., but is not particularly limited This is the case.

The cyclic imidate-based ultraviolet absorber may, for example, be 2,2'-(1,4-phenylene)bis(4H-3,1-benzo) 4-keto), 2-methyl-3,1-benzo 4-ketone, 2-butyl-3,1-benzo 4-ketone, 2-phenyl-3,1-benzo 4-ketone, 2-(1 or 2-naphthyl)-3,1-benzo 4-ketone, 2-(4-biphenyl)-3,1-benzo 4-ketone, 2-p-nitrophenyl-3,1-benzo 4-ketone, 2-metanitrophenyl-3,1-benzo 4-ketone, 2-p-benzoquinone-3,1-benzo 4-ketone, 2-p-methoxyphenyl-3,1-benzo 4-ketone, 2-o-methoxyphenyl-3,1-benzo 4-ketone, 2-cyclohexyl-3,1-benzo 4-ketone, 2-pair (or meta) quinone imine phenyl-3,1-benzo 4-ketone, 2,2'-(1,4-phenylene) bis(4H-3,1-benzo) -4-keto) 2,2'-bis(3,1-benzo) -4-keto), 2,2'-extended ethyl bis(3,1-benzo) -4-keto), 2,2 tetramethylene (or butyl) bis (3,1-benzo) -4-keto), 2,2'-decamethylene bis(3,1-benzo) -4-keto), 2,2'-p-phenylene bis(3,1-benzo) -4-keto), 2,2'-meta-phenylene (3,1-benzo) -4-keto), 2,2'-(4,4'-diphenyl)bis(3,1-benzo) -4-keto), 2,2'-(2,6- or 1,5-naphthalene) bis(3,1-benzo) 4-keto), 2,2'-(2-methyl-p-phenylene) bis(3,1-benzo) -4-keto), 2,2'-(2-nitro-p-phenylene) bis(3,1-benzo) -4-keto), 2,2'-(2-chloro-p-phenylene) bis(3,1-benzo) -4-keto), 2,2'-(1,4-cyclohexene) bis(3,1-benzo) -4-keto) 1,3,5-tris (3,1-benzo) 4-keto-2-yl)benzene, 1,3,5-tris(3,1-benzo) 4-keto-2-yl)naphthalene and 2,4,6-tris(3,1-benzo) 4-keto-2-yl)naphthalene, 2,8-dimethyl-4H,6H-benzo(1,2-d;5,4-d')bis(1,3)- -4,6-dione, 2,7-dimethyl-4H,9H-benzo(1,2-d;5,4-d')bis(1,3)- -4,9-dione, 2,8-diphenyl-4H,8H-benzo(1,2-d;5,4-d')bis(1,3)- -4,6-dione, 2,7-diphenyl-4H,9H-benzo(1,2-d;5,4-d')bis(1,3)- -4,6-dione, 6,6'-bis(2-methyl-4H,3,1-benzo 4-keto), 6,6'-bis(2-ethyl-4H,3,1-benzo) -4-keto), 6,6'-bis(2-phenyl-4H,3,1-benzo 4-keto), 6,6'-methylenebis(2-methyl-4H,3,1-benzophenone 4-keto), 6,6'-methylenebis(2-phenyl-4H,3,1-benzo 4-keto), 6,6'-extended ethyl bis(2-methyl-4H,3,1-benzo -4-keto), 6,6'-extended ethyl bis(2-phenyl-4H,3,1-benzo 4-keto), 6,6'-butyl bis(2-methyl-4H,3,1-benzo) 4-keto), 6,6'-butyl bis(2-phenyl-4H,3,1-benzo 4-keto), 6,6'-oxybis(2-methyl-4H,3,1-benzo 4-keto), 6,6'-oxybis(2-phenyl-4H,3,1-benzo 4-keto), 6,6'-sulfonyl bis(2-methyl-4H,3,1-benzo 4-keto), 6,6'-sulfonyl bis(2-phenyl-4H,3,1-benzo -4-keto), 6,6'-carbon fluorenyl bis(2-methyl-4H,3,1-benzo 4-keto), 6,6'-carbonindolyl bis(2-phenyl-4H,3,1-benzo 4-keto), 7,7'-methylenebis(2-methyl-4H,3,1-benzo 4-keto), 7,7'-methylenebis(2-phenyl-4H,3,1-benzo -4-keto), 7,7'-bis(2-methyl-4H,3,1-benzo 4-keto), 7,7'-extended ethyl bis(2-methyl-4H,3,1-benzo 4-keto), 7,7'-oxybis(2-methyl-4H,3,1-benzo 4-keto), 7,7'-sulfonyl bis(2-methyl-4H,3,1-benzo -4-keto), 7,7'-carbon fluorenyl bis(2-methyl-4H,3,1-benzo -4-keto), 6,7'-bis(2-methyl-4H,3,1-benzo -4-keto), 6,7'-bis(2-phenyl-4H,3,1-benzo 4-keto), 6,7'-methylenebis(2-methyl-4H,3,1-benzo -4-keto), and 6,7'-methylenebis(2-phenyl-4H,3,1-benzo -4-ketone) and the like.

When the organic ultraviolet absorber is blended in the film, since it is exposed to a high temperature in the extrusion step, the ultraviolet absorber is used as a UV absorber having a decomposition start temperature of 290 ° C or higher, thereby reducing process contamination at the time of film formation. More suitable. When an ultraviolet absorber having a decomposition starting temperature of 290 ° C or lower is used, the decomposition product of the ultraviolet absorber adheres to a roll group of a manufacturing apparatus in the film formation, and further adheres to the film or the damaged film to cause optical defects of the film. Not suitable.

Examples of the inorganic ultraviolet absorber include ultrafine particles of metal oxides such as cerium oxide, zinc oxide, and titanium oxide.

Further, in order to improve handleability such as slidability and take-up property of the film, it is preferable to form irregularities on the surface of the film. A method of forming irregularities on the surface of a film generally uses a method of containing particles in the film. The particles are, for example, internal precipitated particles having an average particle diameter of 0.01 to 10 μm, and external particles such as inorganic particles and/or organic particles.

Further, the average particle diameter of the particles is obtained by photographing at least 200 or more particles by electron microscopy, and then the particle profile is traced on the OHP film, and the trace image is converted into a diameter equivalent to a circle by an image analysis device. Find out.

The above external particles may be used, for example, wet and dry vermiculite, colloidal vermiculite, aluminum niobate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolinite, clay, hydroxyapatite, etc. Inorganic particles and organic particles having a constituent component such as styrene, polyfluorene, or acrylic. Among them, dry and wet vermiculite, dry colloidal vermiculite, alumina and other inorganic particles, and organic particles such as styrene, polyoxymethylene, acrylic acid, methacrylic acid, polyester, divinylbenzene, etc. More suitable for use. These internal particles, inorganic particles, and/or organic particles may be used in combination of two or more kinds within the range not impairing the characteristics specified in the present invention.

Further, the content of the above particles in the film is preferably in the range of 0.001 to 10% by mass. When the amount of the film is less than 0.001% by mass, the slidability of the film is deteriorated or the winding is difficult, and the handleability is easily lowered. On the other hand, when it exceeds 10 mass%, it becomes easy to form a coarse protrusion, and film-forming property or transparency deteriorates.

However, since the particles contained in the film usually have a different precipitation rate than the polyester, they are the main reason for reducing the transparency of the film. In order to improve the design creativity of the molded article, the film is printed on the surface of the film before molding. Since such a printing layer is often applied to the back surface of the film for molding, it is desirable from the viewpoint of printing sharpness that the film has high transparency.

Therefore, in order to obtain high transparency in order to maintain the film, a base film having a laminated structure of two or more layers is formed by using a laminate structure in which a base film having a main layer contains substantially no particles and only a surface layer contains particles. The laminated film can be effectively achieved, which is a preferred embodiment of the present invention. The upper limit of the thickness of the surface layer may be appropriately selected depending on the thickness of the film, but is preferably 10 μm, more preferably 5 μm, more preferably 3 μm, and particularly preferably 1 μm. Further, the lower limit of the thickness of the surface layer is preferably 0.01 μm from the viewpoint of productivity. Particles as exemplified above can be used at this time.

Further, when high transparency is required, the substrate film of the present invention preferably has a haze of 0.1 to 3.0%. The method for obtaining a film having high transparency is that the substrate film is substantially free of particles, and a layered structure in which an intermediate layer is provided between the hardened layer and the base film and only the intermediate layer contains particles as described later is also the present invention. A preferred embodiment.

Further, the above-mentioned "substantially free of particles in the base film", for example, in the case of inorganic particles, means that the inorganic element is quantified by fluorescent X-ray analysis, and the content is below the detection limit. This is because even if the particles are not intentionally added to the substrate film, there is a possibility that contaminated components from foreign matter may be mixed. Further, in order to obtain a film having a low haze and high design creativity, it is preferable that the substrate film contains substantially no particles, but if it is 30 ppm or less, it is also possible to add particles to the base film.

In the base film of the present invention, in order to impart other functions, a laminate structure can be formed by a known method using different types of polyester. The form of the laminated film is not particularly limited, and is a two-layer structure of two types of A/B, two types of three-layer structure of B/A/B, and three types of three-layer structure of C/A/B. As described above, when the ultraviolet absorbing agent is contained in the base film, it is also a preferred embodiment of the present invention if it is contained only in the intermediate layer.

The base film of the present invention is mainly a biaxially stretched film. In the present invention, the molecular orientation of the biaxial stretching can improve the solvent resistance and dimensional stability of the unstretched sheet. That is, while maintaining the good moldability of the unstretched sheet, the shortcomings of the solvent-resistant and dimensional stability of the unstretched sheet are improved, and it is one of the characteristics of the base film of the present invention.

The method for producing the biaxially stretched polyester film is not particularly limited, and if the polyester resin is dried as needed, it is supplied to a conventional melt extruder, and is extruded in a sheet form by a slit (and a long strip). The unstretched sheet is attached to a casting drum by static electricity or the like, and then cooled and hardened to obtain an unstretched sheet (raw sheet), and then the unstretched sheet is subjected to biaxial stretching.

The biaxial stretching method is a method of stretching and heat-treating an unstretched sheet in the longitudinal direction (MD) and the width direction (TD) of the film to obtain a biaxially stretched film having a target plane orientation. In this method, from the viewpoint of film quality, the MD/TD method of stretching in the longitudinal direction and then stretching in the width direction, and the TD/MD method of stretching in the width direction and then stretching in the longitudinal direction are gradually performed. The biaxial stretching method or the simultaneous biaxial stretching method in which the stretching is performed at the same time in the longitudinal direction and the width direction is suitable. Further, when the synchronous biaxial stretching method is employed, a tenter driven by a linear control motor can also be used. Further, a multi-step stretching method in which the stretching in the same direction is performed in multiple stages can be used as needed.

The stretching ratio in the biaxial stretching is preferably 1.6 to 4.2 times in the longitudinal direction and the width direction, and particularly preferably 1.7 to 4.0 times. In this case, the stretching ratio in the longitudinal direction and the width direction may be either large or the same magnification. The stretching ratio in the longitudinal direction is preferably 2.8 to 4.0 times, and the stretching ratio in the width direction is preferably 3.0 to 4.5 times.

The stretching conditions in the production of the polyester film for molding of the present invention are preferably as follows.

In the longitudinal direction, it is preferable to set the stretching temperature to 50 to 110 ° C and the stretching ratio to 1.6 to 4.0 times in order to smoothly carry out the subsequent transverse stretching.

When the polyethylene terephthalate film is usually stretched, if the stretching temperature is lower than the appropriate condition, the yield stress at the initial stage of the transverse stretching is sharply increased, so that the stretching cannot be performed. Further, even if it is stretchable, the thickness or the stretching ratio is likely to be uneven, which is not preferable.

Further, if the stretching temperature is higher than the appropriate condition, the yield stress at the initial stage of the transverse stretching is low, but the stress does not increase even if the stretching ratio is increased. Therefore, the formed film has a small stress at 100% stretching at 25 °C. Accordingly, when the optimum stretching temperature is employed, a film having a high degree of orientation can be obtained while ensuring stretchability.

However, when the copolymerized polyester contains 1 to 50 mol% of a copolymerization component, the tensile stress is drastically reduced when the stretching temperature is gradually increased to eliminate the yield stress. In particular, the tensile stress does not increase in the latter half of the stretching, so the orientation is not improved, and the stress is also reduced when the tensile strength is 100% at 25 °C.

Such a phenomenon easily occurs when the film thickness is 60 to 500 μm, and particularly, the film having a thickness of 100 to 300 μm is particularly remarkable. Therefore, in the film using the copolymerized polyester of the present invention, the transverse stretching temperature is preferably set to the following conditions.

First, the preheat treatment of the mixture (original sheet) of the film material after extrusion by an extruder is carried out by DSC measurement at a preheating temperature in the range of glass fragile temperature + 10 ° C to + 50 ° C. Next, the stretching temperature in the first half of the transverse stretching is preferably set to be -20 ° C to + 15 ° C from the preheating temperature. In the latter half of the transverse stretching, the stretching temperature is preferably set to be 0 ° C to -30 ° C higher than the first half stretching temperature, and particularly preferably in the range of -10 ° C to -20 ° C in the first half stretching temperature. With such a condition, it is easy to stretch due to a small yield stress in the first half of the transverse stretching, and is easily oriented in the latter half. Further, the transverse stretching ratio is preferably set to 2.5 to 5.0 times. As a result, a film satisfying the F100 ₂₅ or F100 ₁₀₀ prescribed by the present invention can be obtained.

Further, the heat treatment (heat setting treatment) after the biaxial stretching is carried out under the following conditions, preferably a melting point of -10 ° C and an upper limit of a melting point of -30 ° C, preferably a heat setting temperature. In general, the method of reducing the degree of planar orientation is known to have a method of reducing the draw ratio and a method of increasing the blending amount of the copolymer component, but the former method deteriorates the thickness unevenness of the film, and the latter method reduces the melting point of the film to heat resistance. It is not appropriate for sexual deterioration. In the present invention, in order to reduce the plane orientation of the biaxially oriented polyester film and the heat shrinkage rate at 150 ° C, heat setting is performed at a temperature higher than usual.

(middle layer)

The hard coating film for molding of the present invention is formed by laminating a hard layer on one surface of a base film, but it is preferable to provide an intermediate layer for the purpose of improving the adhesion between the base film and the hardened layer.

The constituent resin of the intermediate layer may, for example, be a polyester resin, a polyurethane resin, a polyester urethane resin, an acrylic resin, a melamine resin or the like, or the like, but It is important to select the base film and the hardened layer to have good adhesion. For example, when the resin constituting the base film and the hardened layer is an acrylic resin, the acrylic, copolyester, or polyester urethane is used. It is preferable to select at least one of the lines and the like.

For the purpose of improving adhesion and water resistance, a crosslinking agent may be contained in the intermediate layer to form a crosslinked structure. The crosslinking agent is, for example, urea, epoxy, melamine or isocyanate. Further, a graft copolymer resin having self-crosslinking property may be used as the resin without using a crosslinking agent.

In the intermediate layer, irregularities are formed on the surface of the base film before the formation of the hardened layer to improve the slidability, and various particles may be contained. The particles contained in the intermediate layer, such as inorganic particles such as vermiculite, kaolinite, talc, calcium carbonate, zeolite, alumina, organic particles such as acrylic acid, PMMA, nylon, styrene, polyester, guanamine/formaldehyde condensate. Further, from the viewpoint of transparency, it is preferred to select particles which are close to the refractive index of the resin to be used.

The method of setting the intermediate layer is preferably a coating method. The coating method uses, for example, a gravure coating method, a kiss coating method, a dip coating method, a spray coating method, a curtain coating method, an air knife coating method, a knife coating method, and a reverse roller. A conventional coating method such as a coating method, and a tantalum (or in-line) coating method in which a coating layer is provided in a production process of a base film, or a coating layer is formed after a base film is produced. The off-line coating method can be used to set the intermediate layer. Among these methods, the twist coating method is not only advantageous in terms of cost, but also contains particles as an intermediate layer, and it is not necessary to contain particles in the base film, and it is preferable to highly improve transparency.

(hardened layer)

In the hard coating film for molding of the present invention, a hardened layer is laminated on at least one surface of the base film directly or through an intermediate layer. In the present invention, the term "hardened layer" refers to a film (or film) having a hardness higher than that of the substrate film in order to reinforce the surface hardness of the substrate composed of the substrate film and to improve the scratch resistance, and has a pair of molding films. The deformation can also follow the layer (film) which is excellent in moldability. More specifically, the hard coating film for molding of the present invention has a surface hardness of at least H and a pencil hardness, and has an elongation of at least 10% or more according to the evaluation method described later, and is therefore suitable for use as a nameplate for home appliances or Use for parts such as building materials.

The hardened layer used in the present invention must have a free radiation curable resin as a main component. In this case, it is not necessary to heat treatment when the thermosetting resin is cured, and it is possible to reduce heat shrinkage of the base film due to heat, which is suitable. In the present invention, the free-radiation-curable compound is a compound which causes polymerization and/or reaction by irradiation with any of electron beam, radiation, or ultraviolet light, and the compound causes a polymerization layer and/or a reaction to form a hardened layer. The free-radiation-curable compound used in the present invention is, for example, a melamine-based, acrylic-based or organic-based free-radiation-type compound, and an acrylate-based free-radiation-curable compound is preferable from the viewpoint of obtaining high surface hardness.

Further, in the present invention, the radical radiation-curable compound is not limited to a monomer or a precursor, and of course, an free radiation-curable resin which is polymerized and/or reacted. For example, the acrylate-based free-radiation-type compound may, for example, be a polyurethane acrylate, a polyester acrylate, an epoxy acrylate, or a polyol acrylate, and is not particularly limited, and any of them may be used. The acrylate-based free radiation-curable compound.

The hardened layer of the present invention is obtained by applying a coating liquid containing at least three or more functional groups of an exogenous radiation-curable compound and a one-and/or two-functional free-radiation-type compound to a base film, and then using an electron beam. Any of radiation, ultraviolet light, irradiation, polymerization, and/or reaction to harden it.

When the acrylate-based free-radiation-type compound is used as the free-radiation-curable compound of the present invention, the monofunctional (monofunctional) acrylate-based free-radiation-type compound of the present invention contains at least one molecule in the molecule. The compound of the (meth)acrylonitrile group is not particularly limited. For example, acrylamide, (meth) propylene morpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide , isobornyl oxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl diethylene glycol (meth) acrylate, three Octyl (meth) acrylate, diacetone (meth) acrylamide, dimethylamine ethyl (meth) acrylate, diethylamine ethyl (meth) acrylate, lauryl (methyl) Acrylate, dicyclopentadienyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N , N-dimethyl(meth)acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, tetrahydroindenyl (meth) acrylate, Tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate Ester, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (A) Acrylate, 2-hydroxypropyl (meth) acrylate, vinyl caprolactam, N-vinylpyrrolidone, N-vinylformamide, phenoxyethyl (meth) acrylate, butoxy b Base (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate Ester, borneol based (meth) acrylate, methyl triethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, decyl phenyl (meth) acrylate, and caprolactone Derivatives such as amine conversion products, acrylic acid, etc., and the like, and the like.

When the acrylate-based free radiation ray-curable compound is used as the radical radiation ray-curable compound, the bifunctional acrylate-based free radiation ray-curable compound of the present invention can have two or more alcoholic hydroxyl groups in one molecule. The compound in which the hydroxyl group forms two (meth) acrylate compounds in the polyvalent alcohol. Specific examples thereof include (a) (meth)acrylic acid diesters of alkylene glycol having 2 to 12 carbon atoms: ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and 1 , 4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc.; (b) polyoxyalkylene (meth)acrylic acid diesters of diol: diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate , diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, etc.; (c) methacrylic acid diester of polyvalent alcohol : neopentyl alcohol di (meth) acrylate, etc.; (d) bisphenol A or bisphenol A hydride ethylene oxide and propylene oxide adduct (meth) acrylate diester: 2, 2'-bis(4-propoxyethoxyphenyl)propane, 2,2'-bis(4-propenyloxypropoxyphenyl)propane, etc.; (e) polyvalent isocyanate compound and The terminal obtained by reacting two or more alcoholic hydroxyl groups in advance contains an isocyanate group-containing compound, a urethane (meth) acrylate having two (meth) acryloyloxy groups in a molecule obtained by reacting an alcoholic hydroxyl group-containing (meth) acrylate; (f) acrylic acid Or an epoxy group (meth) acrylate having two (meth) propylene fluorenyl groups in the molecule obtained by reacting methacrylic acid with a compound having two or more epoxy groups in the molecule.

When the acrylate-based free radiation-curable compound is used as the free-radiation-curable compound, the acrylate-based free-radiation-curable compound having a trifunctional or higher functional group of the present invention can be specifically used (a) pentaerythritol III (A) Acrylate, neopentyl alcohol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol five ( (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, etc.; (b) polyvalent isocyanate compound and two or more alcoholic hydroxyl groups The compound obtained by reacting the compound in advance with an isocyanate group-containing compound, and reacting with an alcoholic hydroxyl group-containing (meth) acrylate to obtain a urethane having 3 or more (meth) propylene fluorenyl groups in the molecule (methyl group) An acrylate (m) an epoxy group having three or more (meth) propylene fluorenyl groups in a molecule obtained by reacting acrylic acid or methacrylic acid with a compound having three or more epoxy groups in a molecule. ) acrylates and the like.

In the present invention, it is important that the free radiation curable compound contained in the coating liquid contains one or more kinds of free radiation curable compounds having three or more functional groups in addition to the free radiation curable compound having one or two functional groups. . Thus, in the hardened layer after hardening, the free radiation curable compound component having a higher crosslinking density and having a trifunctional or higher functional group exists as a hard segment, and the free radiation hardening compound having 1 and/or 2 functional groups is The hard segment is combined in such a manner that the free radiation curable compound component of the 1 and/or 2 functional groups exists as a soft segment. As a result of adjusting the free radiation curable compound of two or more different functional groups to a specific concentration range, a hetero crosslinked structure can be introduced into the hardened layer to impart surface hardness and scratch resistance to the hard segment, and a soft segment is used. The stretchability imparts formability, and it is a remarkable effect of obtaining contradictory characteristics.

In the present invention, in order to coexist with high surface hardness and excellent moldability, that is, specifically, a pencil hardness of H or more and an elongation of 10% or more, one of the free radiation curable compounds contained in the coating liquid and The content of the free radiation curable compound of the bifunctional group is preferably 5% by mass or more and 95% by mass or less. When the content is less than 5% by mass, the flexibility of the film (or the film) is reduced, and it is not preferable to cause cracking in the hardened layer during molding. Moreover, when the content is more than 95% by mass, it is difficult to obtain a cured film having sufficient surface hardness and scratch resistance. The lower limit of the above content is preferably 10% by mass or more, more preferably 20% by mass or more. Further, the upper limit of the above content is preferably 90% by mass or less, more preferably 80% by mass or less, and most preferably 70% by mass or less. When the content of the free radiation curable compound of the 1 and/or 2 functional groups in the free radiation curable compound is 20% by mass or more and 80% by mass or less, it is possible to achieve a higher degree of surface hardness and moldability, specifically It is possible to coexist with a pencil hardness of 2H or more and an elongation of 20% or more, and is suitable for a hard coating film for molding which requires high hardness and high workability, such as a nameplate for an automobile or a case for a portable device.

In addition to the above-described embodiment, the inventors of the present invention have found that the free radiation curable compound having an amine group can be used as a free radiation curable compound, and it has been found that surface hardness and moldability can be made more high. In other words, it is preferred that at least one of the free radiation curable compounds contained in the coating liquid has an amine group. The above effects caused by using a compound having an amine group as a free radiation hardening type compound are as follows. If the hardness distribution of the hardened layer is locally different, local cracking (grain cracking) is likely to occur when the hardened layer is stretched. The reason for the difference in the local hardness distribution is the polymerization inhibition effect (oxidation inhibition) of the free radiation hardening resin by oxygen. Here, when a compound having an amine group is used as the radical radiation-curable compound, the amine group can capture radical oxygen, and the oxidation inhibition which affects the surface layer hardening reaction of the hardened layer is reduced, so that uniform hardening can be performed in the entire hardened layer. reaction. According to this, the stress applied to the hardened layer at the time of molding is dispersed to the entire hardened layer, so that cracking during molding is also suppressed. Therefore, it is possible to coexist with higher surface hardness and moldability. Further, in addition to the above effects, the radical-curable resin having an amine group has an effect of being quick-hardening of the coating film. Therefore, when compared with the case where no amine group is contained, the hardening of the surface of the hardened layer is further promoted, and the surface hardness can be improved.

The content of the radical radiation-curable compound having an amine group in the radical radiation-curable compound contained in the coating liquid is preferably 2.5% by mass or more and 95% by mass or less. The lower limit of the content of the radical radiation-curable compound having an amine group in the free radiation curable compound contained in the coating liquid is preferably 5% by mass or more, more preferably 10% by mass or more. Further, the upper limit of the above content is preferably 92.5% by mass or less, more preferably 90% by mass or less, and most preferably 50% by mass or less. When the content of the radical-hardening type compound having an amine group in the free radiation-curable compound contained in the coating liquid is less than 2.5% by mass, the entire hardened layer is hardly uniformly hardened, so that it is difficult to obtain resistance against cracking during molding. Sex. In addition, when the radical radiation-curable compound having an amine group has a high concentration, the hardening layer yellowing due to the amine group is strong, and when the content is more than 95% by mass, the high transparency may be impaired. For example, when the printing process is performed on the uncovered layer of the hardened layer, the color tone b of the film is preferably 2 or less. In this case, the content of the free radiation curable compound having an amine group is preferably 9.5% by mass or less.

In the coating liquid of the present invention, the free radiation curable compound having 1 and/or 2 functional groups and the free radiation curable compound having 3 or more functional groups are used, but in the above embodiment, as long as a part of them is free The radiation hardening type compound may have an amine group. Further, any of the monofunctional radical radiation-curable compound, the bifunctional radical radiation-curable compound, or the free radiation-curable compound having three or more functional groups is an free-radiation-curable compound having an amine group. Good implementation.

When an acrylate-based free radiation-curable compound is used as an exoradiation-curable compound having an amine group, an acrylate-based free radiation-curable compound having an amine group such as acrylamide, 7-amino-3,7-di Methyl octyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, tertiary octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylamine ethyl (Meth) acrylate, diethylamine ethyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, N-ethylene methamine Wait.

Moreover, in addition to the above-described embodiment, the inventors of the present invention have found that when the hardened layer contains particles, the moldability can be further improved, and the surface hardness and the moldability can be made higher. As a result of the fact that the hardened layer contains particles, the effect of further improving moldability can be as follows. When the hardness of the hardened layer is increased, a strong stress temporarily occurs in the hardened layer having a high hardness during molding, resulting in cracking (grain cracking) of the hardened layer at once. Here, as a result of the particles contained in the hardened layer, the internal stress applied to the hardened layer during molding is moderated at the interface between the radical radiation-curable compound and the particles, and the occurrence of cracking in the hardened layer does not impair the appearance of the appearance. It is impossible to visually confirm the effect of the micro-cracking, and the delayed hardening layer is fatally cracked, and the effect of improving the moldability is exhibited.

As for the particles contained in the hardened layer, such as amorphous vermiculite, crystalline vermiculite, vermiculite-alumina composite oxide, kaolinite, talc, calcium carbonate (calcite type, vaterite type), zeolite, alumina, hydrogen and oxygen Inorganic particles such as apatite, crosslinked acrylate particles, crosslinked PMMA particles, crosslinked polystyrene particles, nylon particles, polyester particles, guanamine/formaldehyde condensate particles, guanamine/melamine/formaldehyde condensate particles The heat-resistant polymer particles such as melamine/formaldehyde condensate particles and the organic/inorganic mixed particles such as a vermiculite/acrylic composite compound are not particularly limited in the present invention.

The shape of the particles is, for example, a spherical shape, a block shape, a plate shape, a fiber shape, a flake shape, or the like, but is not particularly limited, and is preferably spherical in view of dispersibility and particle detachment when it comes into contact with other parts.

In the present invention, the average particle diameter of the particles is preferably 10 nm or more and 300 nm or less, and the lower limit is 40 nm or more, and the upper limit is 200 nm or less. More preferably, the lower limit is 50 nm or more, and the upper limit is 100 nm or less. When the average particle diameter of the particles is less than 10 nm, the average particle diameter is too small, and the effect of improving the surface hardness, the scratch resistance, and the moldability of the added particles may be reduced to all or a part. Further, when it exceeds 30 nm, the hardened layer may become weak and the moldability may be lowered. In addition, the average particle diameter is obtained by dispersing particles in a solvent which does not swell the particles using a Coilter counter (manufactured by Beckman Coulter, Inc., MULTISIZER-II type).

In the present invention, the content of the particles contained in the hardened layer is preferably 5% by mass or more and 70% by mass or less based on the solid content in the hardened layer. In particular, the lower limit of the content is 15% by mass or more, and the upper limit is 50% by mass or less. good. When the particle content is less than 5% by mass, the effect of improving the surface hardness, scratch resistance, and moldability of the added particles may be reduced to all or a part. On the other hand, when the content of the particles exceeds 70% by mass, a large amount of the aforementioned minute crack occurs during molding, and the haze is increased (whitening) to impair the transparency of the molded body.

In the present invention, in order to use the hard coating film for molding as described above, it is preferred to use a compound having an amine group and an additive particle in a hardened layer or the like in an appropriate selection or combination of the above-mentioned free radiation ray-curable compound. A particularly suitable method for this combination. According to this, the surface hardness and the moldability of the hardened layer can be extremely high. Specifically, a molding having a surface hardness of 2H or more and an elongation of 20% or more, or even a surface hardness of 2H or more and an elongation of 30% or more can be obtained. The hard coating film is suitable for use in a cover part of an automobile or the like, a case, a container, or the like in a deep bottom.

In the present invention, the method of polymerizing and/or reacting the coating liquid is a method of irradiating electron beams, radiation, or ultraviolet rays. However, it is preferred to add a photopolymerization initiator to the coating liquid when irradiated with ultraviolet rays.

Specific examples of the photopolymerization initiator, such as acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorodi Benzophenone, 4,4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoic acid methyl ester, p-isopropyl-α-hydroxy phenyl isobutyl ketone, α-hydroxy phenyl isobutyl ketone, 2, 2-dimethoxy a carbonyl compound such as benzyl-2-phenylacetophenone or 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, tetramethylammonium thioformate, sulfur (thioxanthene), 2-chlorosulfur 2-methylsulfide A sulfur compound such as a sulfur compound, a benzoyl peroxide or a bis(tributyl) peroxide. Examples of such a photopolymerization initiator include peroxide compounds such as a tertiary butyl peroxide. These photopolymerization initiators may be used singly or in combination of two or more kinds. The amount of the photopolymerization initiator to be added is preferably 0.01 parts by mass or more and 15 parts by mass or less per 100 parts by mass of the free radiation curable compound contained in the coating liquid. When the amount used is small, not only the reaction is slow, but also the productivity is poor. Unreacted materials remain and sufficient surface hardness and scratch resistance cannot be obtained. On the other hand, if the amount of addition is too large, there is a problem that the hardened layer is yellowed by the polymerization initiator.

In the present invention, in order to prevent thermal reaction during production or dark reaction during storage, a conventional thermal polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether or 2,5-tributylhydroquinone is added to the above coating liquid. It is appropriate. The amount of the thermal polymerization inhibitor to be added is preferably 0.005 parts by mass or more and 0.05 parts by mass or less per 100 parts by mass of the free radiation ray-curable compound contained in the coating liquid.

In the above-mentioned coating liquid, in order to improve the workability at the time of coating and to control the thickness of the coating film at the time of coating, an organic solvent can be blended in the range which does not impair the object of the present invention.

The organic solvent preferably has a boiling point of 50 ° C or more and 150 ° C or less. Specific examples include alcohol solvents such as methanol, ethanol, and isopropyl alcohol; acetate solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; and aromatic solvents such as toluene. ,two A cyclic ether solvent such as an alkane. These solvents may be used alone or in combination of two or more.

In the above coating liquid, in order to reduce the surface tension of the coating liquid and to improve the coating appearance of the hardened layer (especially due to the loss caused by the micro foam, the depression caused by the adhesion of the foreign matter, and the rejection during the drying step), Contains a surfactant.

Surfactant can be appropriately used the conventional cationic, ^anionic, nonionic, but the coating solution by the deterioration of adhesion or cured layer of the base film of adverse problems such as not having a nonionic polar group of preferred Further, an organic fluorene-based surfactant or a fluorine-based surfactant which is excellent in interfacial activity is more preferable.

Examples of the organic lanthanoid surfactant include dimethyl hydrazine, amino decane, propenyl decane, vinylbenzylsilane, vinylbenzylaminosilane, glycidylsilane, and sulfhydryl. Decane, dimethyl decane, polydimethyl siloxane, polyalkoxy siloxane, hydrodiene modified siloxane, vinyl modified siloxane, hydroxy modified siloxane, Amine modified siloxane, carboxyl modified siloxane, halogenated modified siloxane, epoxy modified siloxane, methacryloxy modified siloxane, thiol modified oxane, A fluorine-modified siloxane, an alkyl-modified siloxane, a phenyl-modified siloxane, an alkylene oxide-modified siloxane or the like.

Examples of the fluorine-based surfactant include tetrafluoroethylene, perfluoroalkylammonium salt, perfluoroalkyl alkanesulfonamide, sodium perfluoroalkylsulfonate, perfluoroalkyl potassium salt, and perfluoroalkane. Base carbonate, perfluoroalkyl sulfonate, perfluoroalkyl ethylene oxide adduct, perfluoroalkyl trimethyl ammonium salt, perfluoroalkyl amine sulfonate, perfluoroalkyl phosphate, Perfluoroalkylalkyl compounds, perfluoroalkylalkylbetaines, perfluoroalkyl halides, and the like.

From the viewpoint of improving the coating appearance and slidability, the coating liquid constituting the hardened layer preferably has a surfactant content of 0.01% by mass or more. On the other hand, since the surfactant bleeds out of the surface of the hardened layer to contaminate the contact hardened layer, the surfactant content is preferably 2.00% by mass or less.

Further, the surfactant to be used preferably has an HLB of 2 or more and 12 or less. When a surfactant having an HLB of 2 or more is used, the leveling property can be improved by the interfacial activity. The HLB of the surfactant is preferably 3 or more, more preferably 4 or more. On the other hand, when a surfactant having an HLB of 12 or less is used, deterioration of slidability can be suppressed.

Further, the HLB is an abbreviation of Hydrophil Lyophil Balance, which is named by W.C. Griffin of Atlas Powder, Inc., and is a value obtained by characterizing the balance between a hydrophilic group and a lipophilic group contained in a surfactant molecule as a characteristic value. It means that the lower the HLB value, the higher the lipophilicity, and the higher the HLB value, the higher the hydrophilicity.

The hardened layer of the present invention can be formulated to match various additives. In the case of a fluorine-based or organic anthraquinone-based compound which imparts water repellency, an antifoaming agent for improving coatability and appearance, an antistatic agent, a dye for coloring, a pigment, and the like.

In the present invention, the hardened layer is preferably applied to a base film by applying a coating liquid containing an exothermic radiation-curable compound, particles, a photopolymerization initiator, and a surfactant in an organic solvent, followed by drying.

A method of laminating the hardened layer may be a conventional method, but a method of applying the above coating liquid to a substrate film after drying and hardening is suitable. Examples of the coating method include gravure coating, kiss coating, dip coating, spray coating, curtain coating, air knife coating, blade coating, reverse roll coating, bar coating, and lip. A conventional coating method such as Lip coating. Among them, a gravure coating method capable of uniformly coating a roll-to-roll method, in particular, a reverse gravure coating method is preferred.

The method of dissolving or dispersing the free radiation curable compound, the particles, the photopolymerization initiator, and the like contained in the coating liquid in an organic solvent is preferably a method of stirring and dispersing the mixture under heating. When the coating liquid is heated, the solubility of the radical radiation-curable compound, the particles, and the photopolymerization initiator can be improved. Therefore, deterioration of the coating appearance due to undissolved matter can be suppressed.

A conventional machine can be used for the disperser. Specifically, for example, ball mill, sand mill, Attritor, roller mill, mixer, colloid mill, ultrasonic homogenizer, emulsifier, bead mill, wet jet honing machine, paint shaker, butterfly Mixer, planetary mixer, Hanschel mixer, etc.

The solid content concentration of the radiation-hardening type compound, the particles, and the photopolymerization initiator contained in the coating liquid is preferably 5% by mass or more and 70% by mass. When the solid content concentration of the coating liquid is adjusted to 5% by mass or more, it is possible to suppress the decrease in productivity due to the elongation of the drying time after coating. On the other hand, when the solid content concentration of the coating liquid is adjusted to 70% by mass or less, it is possible to prevent deterioration of the coating property due to an increase in the viscosity of the coating liquid and to deteriorate the coating appearance due to the coating. In addition, from the viewpoint of the coating appearance, the solid content of the coating liquid, the type of the organic solvent, and the type of the surfactant are adjusted so that the viscosity of the coating liquid is preferably 0.5 cps or less and 300 cps or less.

The thickness of the hardened layer after application and hardening depends on the degree of elongation at the time of molding, but the thickness of the hardened layer after molding is preferably 0.5 μm or more and 50 μm or less. Specifically, the lower limit of the thickness of the hardened layer before molding is preferably 0.6 μm or more, more preferably 1.0 μm or more. Further, the upper limit of the thickness of the hardened layer before molding is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, and most preferably 20 μm or less. When the thickness of the hardened layer is thinner than 0.6 μm, it is difficult to obtain hardenability, and when it exceeds 100 μm, it tends to cause hardening of the hardened layer or poor curling due to hardening shrinkage.

When the coating liquid is pre-dried in combination with an organic solvent or the like, it is applied to a substrate film and dried, such as a conventional hot air drying, an infrared heater, etc., but it is preferably dried by hot air at a fast drying speed.

The drying after application is preferably carried out at a temperature of from 40 ° C to 120 ° C, more preferably from 45 ° C to more than 80 ° C. When it is less than 40 ° C, problems such as whitening may occur in addition to the fact that the organic solvent contained in the coating liquid cannot be sufficiently removed. On the other hand, when the temperature exceeds 120 ° C, slight defects such as minute coating loss, minute repulsion, and cracking of the foam are likely to occur, and the appearance may be poor. Further, since the base film is strongly shrunk by heat, the heat ridges deteriorate the planarity of the base film, so that uniform elongation cannot be obtained at the time of molding, or local elongation occurs, and the base film is broken or the like, resulting in poor moldability.

The tension applied to the base film during drying is preferably 50 N/m or more and 300 N/m or less, and particularly preferably a lower limit of 100 N/m or more and an upper limit of 250 N/m or less. When the substrate film tension is less than 50 N/m, the substrate film which is traveling is snaking, so that the coating liquid cannot be applied. On the other hand, when it exceeds 300 N/m, the base film is creped, and the flatness is deteriorated or the appearance of the wound base film is poor. Further, when the low-temperature moldability of the base film is good, the base film during drying is stretched in the advancing direction, but shrinks in the width direction, and in the worst case, breakage occurs, which causes problems in productivity.

In the present invention, the hardened layer, the antistatic layer, the easy-adhesion layer, the adhesive layer, the easy-slip layer, the electromagnetic wave absorbing layer, the dye-containing or pigment can be imparted to the surface of the hardened layer without hindering the effects of the present invention. Other functions such as the resin layer of the pigment.

In the present invention, ultraviolet rays are irradiated onto the coating liquid to form a hardened layer. The cumulative amount of light to be irradiated is preferably 50 mJ/cm ² or more and 1000 mJ/cm ² or less, and particularly preferably a lower limit of 300 mJ/cm ² or more and an upper limit of 700 mJ/cm ² or less. Moreover, when irradiated in a nitrogen atmosphere, it is preferable to reduce oxidation suppression and to improve scratch resistance. When the cumulative amount of light is less than 50 mJ/cm ² , the polymerization reaction of the free reflection-curable compound cannot be promoted, and the surface hardness of the hardened layer is remarkably reduced. When the cumulative amount of light exceeds 1000 mJ/cm ² , the base film may be deformed by the influence of heat. Further, the integrated light amount of the present invention can be measured by "UVR-T35" manufactured by TOPCON.

Further, when the coating liquid is hardened by electron beam, the irradiation amount is preferably 5 kGy or more and 100 kGy or less, and particularly preferably 30 kGy or more, and the lower limit is 70 kGy or less. When it is less than 5 kGy, the polymerization reaction of the free reflection line hardening type compound cannot be promoted, and the surface hardness of the hardened layer is remarkably reduced. When the temperature exceeds 100 kGy, the life of the electron beam irradiation tube is remarkably reduced, which is disadvantageous in terms of production cost.

(hard coating for molding)

The hard coating film for molding of the present invention is a film excellent in surface hardness. In the hard coating film for molding of the present invention, in addition to exhibiting good moldability, a base film having specific properties having good mechanical properties can be used, and a more excellent surface hardness can be exhibited. This is because the strength (hardness) of the substrate film contributes to the surface hardness of the hardened layer. Specifically, in the hard coating film for molding of the present invention, the pencil hardness measurement value is preferably H or more, and more preferably 2H or more. Here, the evaluation of the pencil hardness was performed on the basis of JIS-K5600.

The method of adjusting the surface hardness may be a content of a 1 or 2 functionalized radical radiation-hardening compound or a content of a free-reflective-hardening type compound having an amine group in a free reflection-line-hardening compound contained in a coating liquid for forming a hardened layer, and hardening The amount of particles present in the layer, the thickness of the hardened layer, and the like are changed.

The hard coating film for molding of the present invention is a film excellent in scratch resistance. Specifically, according to JIS-K5600, the steel wire of #0000 is loaded on the surface 20 times with a load of 500gf to visually observe the occurrence of scratches and the degree of scratching. It is preferable to deeply scratch a small amount of scratches of 10 or less, and to completely No deep scratches are particularly good.

The method of adjusting the scratch resistance by using the content of the 1 or 2 functional group of the free reflection line hardening type compound in the coating liquid for forming the hardened layer or the content of the free reflection line hardening type compound having an amine group, The amount of particles present in the hardened layer is changed.

The hard coating film for molding of the present invention is a film excellent in moldability. Specifically, the elongation at room temperature and the actual film temperature of 160 ° C is preferably 10% or more, more preferably 20% or more, and particularly preferably 30% or more. Here, the elongation is a thin rectangular shape having a length of 10 mm and a width of 150 mm, which is formed by a hard coating film for forming, and the elongation ratio of the hardened layer when the film is stretched or whitened at the actual film temperature of 160 ° C is taken as Elongation(%).

The method of adjusting the moldability (elongation) may be a content of a 1 or 2 functional group free reflection line hardening type compound or a free reflection line hardening type having an amine group in a free reflection line hardening type compound contained in a coating liquid for forming a hardened layer. The content of the compound, the amount of particles present in the hardened layer, and the like are changed.

When the hard coating film for molding of the present invention is subjected to printing processing on one side of the layer hardened layer, it is preferred that coloring is not performed. Specifically, the value of the hue b* is preferably 2.0 or less. The method of adjusting the color tone b* can be changed by using the content of the radical reflection-hardening type compound having an amine group or the amount of the photopolymerization initiator added to the free reflection line-hardening type compound contained in the coating liquid for forming the hardened layer. Here, the hue b* is a value obtained by measuring the hue b by a C light source and a viewing angle of 2 degrees using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., ZE-2000), and averaging the measured values five times.

(hard coating roller for molding)

The hard coating film roll for molding of the present invention is obtained by continuously winding a long hard coating film for molding into a cylindrical core roll in a roll form. When a hard coating roll for molding is used, the productivity at the time of processing can be improved, and the stability of the molded body quality can be improved. The length of the hard coating film for forming the hard coating film in which the hard coating film is continuously wound into a cylindrical core is not particularly limited depending on the application, but is preferably 50 m or more and 5000 m or less, and more preferably 100 m or more. More preferably below 3000m. When the winding length is short, the workability is deteriorated because the frequency of replacement of the hard coating roller for molding is high when the printing layer is processed in the post-process. On the other hand, when the winding length is long, the hard coating film for molding expands and contracts due to the external environmental temperature, and the winding is caused to cause a defect in the appearance of the core portion.

The width of the hard coating roll for molding is not particularly limited, and is preferably 100 mm or more and 2000 mm or less, and more preferably 500 mm or more and 1500 mm or less from the viewpoint of workability.

The cylindrical core of the hard coating film for coil forming is preferably made of a plastic core. When a paper core used in general is used, paper powder or the like adheres to the hardened layer and is liable to be a defective product. The plastic core is suitable for use by a conventional one, but it is preferably made of a polypropylene core or an FRP core from the viewpoint of strength. The cylindrical core has a size of preferably 3 inches or more and 6 inches or less in diameter. When a cylindrical core having a small diameter is used, winding of the core portion is entangled, resulting in poor workability in the post-process. On the other hand, when the diameter is large, the diameter of the roller is also large, and the handleability is poor.

When the hard coating film for molding is wound around a cylindrical core, it is preferable to fix the hard coating film for molding to the core after double-sided tape. When the double-sided tape is not used, the film roll is likely to occur during winding or handling. The double-sided tape can be used by a conventional one, but it is preferable that the adhesive film is provided on both sides of the plastic film from the viewpoint of occurrence of paper powder or strength. The thickness of the double-sided tape is preferably 5 μm or more and 50 μm or less. When the thickness is thinner, the workability is poor, and the fixing force of the film is also reduced. On the other hand, when the thickness is thick, the flatness of the hard coating film for forming the core portion is poor due to the difference in height of the tape.

In the present invention, it is preferable to provide irregularities (embossing) at both ends in the width direction of the hard coating film for molding. When the unevenness is applied, the mark caused by the double-sided tape is less likely to adhere to the core portion, and the hardened layer is brought into contact with the surface of the base film opposite to the surface of the substrate, or the contact with the functional layer film as described above is laminated on the base film. Partially reduced, the roll shape is well preserved. The lower limit of the height of the concavities and convexities is preferably 10 μm or more preferably 15 μm. On the other hand, the upper limit of the uneven height is preferably 40 μm or more preferably 35 μm. When the unevenness height is too low, the effect of improving the storage stability of the roll shape by the unevenness is small. On the other hand, when the unevenness height is too high, the film roll is likely to occur during transportation. A conventional method can be used for the method of imparting irregularities. Specifically, it is a method in which a metal roll having a protrusion on the surface is pressed to provide unevenness. Further, in the uneven processing, it is preferable to perform the uneven processing on the base film before forming the hardened layer on the base film.

(molded body)

The hard coating film for molding of the present invention is suitable for use as vacuum molding, air pressure molding, mold molding, press molding, laminate molding, in-mold molding, extrusion molding, bending molding, stretch molding, and the like. A molding material formed by a molding method. When the hard coating film for molding of the present invention is used for molding, the hardened layer is not cracked by deformation at the time of molding, and surface hardness and scratch resistance can be maintained.

The thickness of the cured layer of the molded article formed by the hard coating film for molding is preferably 5 μm or more and 50 μm or less, and more preferably 0.5 μm or more and 10 μm or less. When the thickness of the hardened layer of the molded body is thinner than 0.5 μm, the hardenability cannot be obtained, and from the viewpoint of heat resistance, such as when it is heated to the molded body, the shrinkage of the base film cannot be followed, and the surface of the hardened layer is caused to cause waves to impair the appearance. On the other hand, when it exceeds 50 μm, it is not superior to the surface hardness of the 50 μm thick hardened layer, and the quality is less advantageous.

Since the molded body thus formed has a hardened layer to reinforce the surface hardness, it can be suitably used as a nameplate for home appliances, an automobile nameplate, an empty can, a building material, a cosmetic board, a cosmetic steel plate, and the like which are required to be attached to an external contact position and required to have scratch resistance. Use for molded parts such as transfer sheets.

Example

The invention is illustrated in detail by the following examples. Further, the properties of the films obtained in the respective examples were measured and evaluated by the following methods.

(1) Intrinsic viscosity of resin

0.1 g of a resin sheet sample was accurately weighed, dissolved in a mixed solvent of 25 ml of phenol/tetrachloroethane = 60/40 (mass ratio), and measured at 30 ° C using an Oswald viscometer (Ostwald's viscometer). Further, the measurement was carried out three times, and the average value was obtained.

(2) Melting point (Tm) of raw material (object)

Using a differential scanning calorimeter (Differential Scanning Calorimeter, manufactured by Max Science Co., Ltd., DSC3100S), about 7 mg of the raw material extruded under the conditions of each example was placed in a sample tray and capped, from room temperature to 300 under a nitrogen atmosphere. The temperature was raised and measured at a temperature increase rate of 20 ° C /min. The melting point is determined by the melting peak temperature (Tpm) as defined in item 9.81.

The melting point of the base film was also measured in the same manner, and the melting peak temperature (Tpm) was determined.

(3) Uneven thickness of the substrate film

A film having a length of 3 m in the transverse direction and a width of 5 cm in the direction of the longitudinal direction was taken from the obtained base film, and wound into a continuous strip sample, and a film thickness continuous measuring machine (manufactured by ANRITSU Co., Ltd.) was used. The film thickness was measured and recorded on a recorder. The maximum value (Tmax), the minimum value (Tmin), and the average value (Tav) of the thickness were obtained from the recording chart, and the thickness unevenness (%) was calculated by the following formula. Further, the measurement was carried out three times, and the average value was obtained. Further, when the length in the transverse stretching direction is less than 3 m, it is carried out after the connection. The measured value of the connected part is deleted.

Uneven thickness (%) = [(Tmax - Tmin) / Tav] × 100

(4) Thickness of the substrate film

The obtained base film was measured using a millitron, and each of 5 pieces was made up of 5 pieces of 15 points, and the average value was obtained.

(5) Stress and elongation at break of 100% elongation of the base film

A rectangular square shape sample having a length of 180 mm in the longitudinal direction and a width of 10 mm in the width direction was cut out from the obtained base film by a single-sided blade. Next, the above-mentioned elongated square-shaped sample was stretched using a tensile tester (manufactured by Toyo Seiki Co., Ltd.), and the stress (MPa) and elongation at break (%) at 100% elongation in each direction were obtained from the obtained load-deformation curve.

Further, the temperature was measured at a temperature of 25 ° C, with an initial length of 40 mm (ie, the distance between the punctuation points of the tensile test), a distance between the chucks of 100 mm, a crosshead speed of 100 mm/min, a recording speed of the recorder of 200 mm/min, and a force measuring device. The measurement was carried out under the conditions of 25 kgf. Further, the measurement was carried out 10 times, and the average value was obtained.

Further, the tensile measurement was carried out under the same conditions as above at a temperature of 100 °C. At this time, the sample was measured at a temperature of 100 ° C for 30 seconds. Further, the measurement was carried out 10 times, and the average value was obtained.

(6) Thermal shrinkage rate of the substrate film at 150 ° C

An elongated square-shaped sample having a length of 150 mm in the longitudinal direction and a width of 20 mm in the width direction was cut out from the obtained base film. Two marks were placed at intervals of 100 mm in the longitudinal direction of each sample, and the interval A between the two marks was first measured under no load. Next, under no load, one side of each of the elongated square-shaped samples was hung in a basket with a clip, placed in a geer oven at 150 ° C and started to be timed. After 30 minutes, the basket was taken out of the aged oven and left at room temperature for 30 minutes. Next, the interval B between the two marks is measured under no load. The heat shrinkage ratio at 150 ° C was calculated from the following equation by measuring the interval A and the interval B.

Heat shrinkage rate (%) = [(A-B) / A] × 100

(7) Solvent resistance of the substrate film

The sample was immersed in toluene adjusted to a temperature of 25 ° C for 30 minutes, and the appearance change before and after the immersion was judged by the following criteria, and passed ○. Further, the haze value was measured by the following method (see item 9).

○: There is no change in appearance, and the change in haze value is less than 1%.

X: identifiable appearance change, or haze value change of 1% or more

(8) Plane orientation (Δ P)

The obtained hard coating film for molding was observed from the opposite side of the hardened layer using a sodium D line (wavelength: 589 nm) as a light source, and the refractive index (Nx) and width in the longitudinal direction of the film were measured using an Abbe refractometer. The refractive index of the direction (Ny) and the refractive index of the thickness direction (Nz) are calculated by the following equation (ΔP).

Δ P=[(Nx+Ny)/2]-Nz

(9) Haze of hard coating for molding

The haze of the film was measured by using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., 300A) in accordance with JIS-K7136-2000. Further, the measurement was carried out twice, and the average value was obtained.

(10) Light transmittance of a hard coating film for molding at a wavelength of 370 nm

The light transmittance of the film was measured using a spectrophotometer (manufactured by Shimadzu Corporation, UV-1200) to measure the light transmittance of the film at a wavelength of 370 nm.

(11) Light resistance of hard coating film for molding

The printed sample of the offset printing was placed on the printing side as the back side, and placed in a 3 cm position straight down in a black box (a U-shaped fluorescent lamp FUL9EX manufactured by Matsushita Electric Co., Ltd.). Subsequently, the fluorescent lamp was irradiated for 2,000 hours, and the color (a*, b*, L*) on the printing surface side before and after the light irradiation was measured, and the color difference (ΔE value) was measured in accordance with JIS-Z-8730. The smaller the color difference (ΔE value), the smaller the color change before and after the light irradiation, that is, the light resistance is excellent. The pass standard for light fastness is a color difference (ΔE value) of 0.5 or less. Further, the chromatic aberration (ΔE value) is obtained by the following formula.

ΔE=√(Δa ² +Δb ² +L ² Δ)

(12) Formability of hard coating film for molding

The film was subjected to grid printing of 5 mm square, and the film was heated by an infrared heater heated at 500 ° C for 10 to 15 seconds, and then vacuum molded at a mold temperature of 30 to 100 ° C. Further, the heating conditions of the respective films are selected from the above ranges to select the most suitable conditions. The shape of the mold used was a cup shape, the opening diameter was 50 mm, the bottom diameter was 45 mm, and the depth was 5 mm, and all the corners were made to have a curvature of 0.5 mm in diameter.

Five molded articles were obtained by vacuum molding under the most suitable conditions, and the moldability and completeness were evaluated, and the order was ranked by the following criteria. Also, ◎ and ○ are passing, and X is failing.

◎: (i) the molded product is not broken,

(ii) the radius of curvature of the corner of the molded article is 1 mm or less, and the printing deviation is 0.1 mm or less.

(iii) there is no apparent appearance of X;

○: (i) the molded product is not broken,

(ii) the radius of curvature of the corner of the molded article exceeds 1 mm but is 1.5 mm or less, or the printing deviation exceeds 0.1 mm but is 0.2 mm or less.

(iii) there is no molded article equivalent to the appearance of X, which is practically problem-free;

X: (i) The molded article is cracked or not broken but is equivalent to any of the following items (i) to (iv):

(i) the radius of curvature of the corner of the molded article exceeds 1.5 mm,

(ii) large wrinkles and poor appearance,

(iii) the film is whitened and the transparency is reduced,

(iv) Printing deviation exceeds 0.2 mm.

(13) Printing grade of hard coating for molding

The hard coating film before printing was heat-treated at 90 ° C for 30 minutes, and then 4-color screen printing was performed on the reverse side of the hardened layer.

This hard coating of the printed layer was dried at 80 ° C for 30 minutes. The printing grade was evaluated by the following printing appearance such as transparency, printing suitability, and printing deviation, and was visually judged by the hard coating film on the reverse side of the printing surface, not by the printing surface. The judgment criterion is ○: all items have no problem, △: at least one item has a problem, and X: two or more items have a problem.

a. Transparency: The printed pattern is not obscured by the substrate film or the coating layer.

b. Printing suitability: no color unevenness or loss due to poor transfer of printing ink occurs.

c. Printing deviation: The printing deviation cannot be determined visually.

(14) Elongation of hardened layer

In order to determine the elongation of the hardened layer, it was evaluated by the aforementioned method. Here, the elongation is 10% or more, and it is judged that the moldability is excellent, and the elongation is 30% or more, and it is judged that the moldability is excellent.

(15) pencil hardness of hardened layer

In order to judge the surface hardness of the hardened layer, it was evaluated by the aforementioned method. Here, the pencil hardness was judged to have an excellent surface hardness of H or more, and it was judged to have a superior surface hardness of 2H or more.

(16) Scratch resistance of hardened layer

In order to determine the scratch resistance of the hardened layer, the evaluation was carried out by the above method, and the level was determined according to the following criteria. When the scratch resistance level is C or more, scratch resistance is determined, and when the grade is B or more, it is judged that the scratch resistance is good.

A: no scratches occurred, or a small amount of shallow scratches were observed;

B: shallow scratches were observed, but no deep scars were observed;

C: shallow scratches were observed and a small amount of deep scars were observed;

D: A lot of deep scars were observed.

(17) The hue of the hard coating film for molding b*

In order to evaluate the degree of coloring (yellowing) of the hardened layer, it was evaluated by the aforementioned method. When the b* value is 2.0 or less, the judgment is good, and when it exceeds 2.0, the yellow of the hardened layer becomes large and it is judged to be defective.

(18) Pencil hardness and hardened layer thickness after molding

In the evaluation of the elongation described above, the stretching was stopped immediately before the occurrence of the cleavage, and the pencil hardness at this time was evaluated in the same manner as the above evaluation method. In addition, the thickness of the hardened layer at this time was measured by a spectrophotometer (manufactured by Shimadzu Corporation, UV-3150 type) to obtain a fractional light reflectance, and the waveform of a wavelength of 400 nm or more and 600 nm or less was used to calculate the thickness of the hardened layer by a peak valley method. . The refractive index required at this time was a single layer film of a hardened layer, and the refractive index was measured by an Abbe refractometer (manufactured by ATAGO Co., Ltd., NAR-1T SOLID).

(19) Whether or not crepe occurs when the coating liquid for coating a hardened layer is applied

In order to determine whether the drying temperature and the film tension at the time of drying after application of the coating liquid for a hardened layer were appropriate, it was evaluated whether or not crepe was generated. When the base film having a width of 700 mm was applied for 100 m, it was judged to be good (○) if no crepe was generated, and was determined to be defective (X) when crepe was generated.

(20) Coating appearance of the hardened layer

The coating appearance was evaluated in order to determine whether or not the drying temperature at the time of drying after application of the coating liquid for a hardened layer was appropriate. When the base film having a width of 1060 mm was applied for 100 m, the hardened layer after hardening was judged to be good (○) if it was completely free from whitening, coating loss, or rejection, and was judged to be defective (X) if it was defective.

(21) Wide shrinkage rate when applying a hardened layer

In order to determine whether the drying temperature and the film tension at the time of drying after application of the coating liquid for a hardened layer were appropriate, the width shrinkage ratio was evaluated. When the base film having a width of 700 mm was applied for 100 m, the width shrinkage ratio of the base film before and after coating was measured. When the shrinkage ratio was 1.5% or less, it was judged to be good, and when it exceeded 1.5%, it was judged to be bad.

(Example 1) (Preparation of coating liquid)

The transesterification reaction and the polycondensation reaction are carried out according to the usual method to prepare a water-dispersible copolymerized polyester resin containing a sulfonic acid metal salt group; the composition thereof is 46% by mole of p-citric acid (relative to the total dicarboxylic acid component, the same below) , isoammonic acid 46 mol%, and 5 sulfonate sodium citrate 8 mol% as a dicarboxylic acid component, ethylene glycol 50 mol% (relative to the total diol component, the same below), And neopentyl glycol 50 mol% as a diol component. Next, 51.4 parts by weight of water, 38 parts by weight of isopropyl alcohol, 5 parts by weight of n-butyl sialoside, and 0.06 parts by weight of a nonionic surfactant were mixed and heated and stirred, and when the temperature reached 77 ° C, the water dispersion was added thereto. 5 parts by weight of a copolymerized polyester resin containing a sulfonic acid metal salt group, and stirring was continued until the resin-free block was present, and the aqueous resin dispersion was cooled to room temperature to obtain a uniform water-dispersible copolyester having a solid content concentration of 5.0% by weight. Resin solution. Further, 3 parts by weight of the aggregated vermiculite particles (manufactured by FUJI-SILYSIA Co., Ltd., SYLYSIA 310) was dispersed in 50 parts by weight of water, and then 0.54 parts by weight of the aqueous dispersion of SYLYSIA 310 was added to the above-mentioned dispersible copolymerized polyester resin liquid 99.46. In the parts by weight, 20 parts by weight of water was added while stirring, to obtain a coating liquid.

(modulating the substrate film)

The copolyester (constituting component is 100% by mole of citric acid unit as an aromatic dicarboxylic acid component, ethylene glycol unit 40 mol%, and neopentyl glycol unit 60 mol% as a diol component, and the intrinsic viscosity is Resin sheet (A) of 0.69 dl/g and polyethylene terephthalate (intrinsic viscosity: 0.69 dl/g, 0.04% by mass of amorphous vermiculite having an average particle diameter (SEM method) of 1.5 μm and benzotriene After the resin sheet (B) of the azole-based ultraviolet absorber (N) (manufactured by CIBA SPECIALITY CHEMICALS CO., LTD., TINUVIN 326) was dried, the resin sheet (A) and the resin sheet (B) were mass ratio of 25:75. mixing. Next, the resin sheet mixture was melt-extruded at 270 ° C from the T-die slit of the extruder, and rapidly solidified on a cooling roll having a surface temperature of 40 ° C, while being electrostatically applied to make the amorphous film adhered to the cooling roll. Stretch the sheet.

The unstretched sheet was stretched 3.3 times in the longitudinal direction at 90 ° C between the heating roll and the cooling roll.

Then, the coating liquid was applied to both sides of the uniaxially stretched film, and dried at 120 ° C to provide an intermediate layer (containing 0.003 mass% of vermiculite having an average particle diameter of 0.2 μm) having a solid concentration of 0.08 g/m ² .

Next, the uniaxially stretched film was introduced into a tenter, and after preheating at 120 ° C for 10 seconds, the first half was stretched 3.9 times in the transverse direction at 110 ° C and the second half at 100 ° C. Further, heat treatment was carried out at 235 ° C under a relaxation treatment of 7% in the transverse direction by heat treatment to obtain a substrate film having a thickness of 100 μm.

(making a hard coating)

The following coating liquid A was applied to the obtained substrate film using a wiper so that the film thickness after drying was 2 μm, dried by hot air at a temperature of 80 ° C for 60 seconds, and at a position of 20 cm under a high pressure mercury lamp having an output of 120 W/cm. The hard coating film for molding was obtained by passing at a speed of 10 m/min.

(hard coating liquid A)

The following materials were mixed in the following mass ratio and stirred for 30 minutes or more to dissolve. Next, the undissolved matter was filtered off using a filter having a nominal filtration precision of 1 μm to prepare a coating liquid A.

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 11.45% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.73% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 5.72% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 2)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid B described below, a hard coating film for molding was obtained.

(coating liquid B)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 17.18% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 2.86% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 2.86% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 3)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid C described below, a hard coating film for molding was obtained.

(coating liquid C)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 8.02% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 7.44% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 7.44% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 4)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid D described below, a hard coating film for molding was obtained.

(coating liquid D)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 21.75% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 0.58 mass%

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 0.57 mass%

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 5)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid E described below, a hard coating film for molding was obtained.

(coating solution E)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 1.15% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 0.58 mass%

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 21.17% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 6)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid F described below, a hard coating film for molding was obtained.

(coating liquid F)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 21.75% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 1.15% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 7)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid G described below, a hard coating film for molding was obtained.

(coating solution G)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 1.15% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 21.75% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 8)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid H described below, a hard coating film for molding was obtained.

(coating liquid H)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 1.15% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Dimethylamine ethyl methacrylate 21.75% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 9)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid I described below, a hard coating film for molding was obtained.

(coating solution I)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 11.45% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.73% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● diethylamine ethyl methacrylate 5.72% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DE, functional base 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.04% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Embodiment 10)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid J described below, a hard coating film for molding was obtained.

(coating solution J)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 11.45% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.73% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● N-vinylformamide 5.72% by mass

(Arakawa Chemical Industry Co., Ltd., BEAMSET 770, functional group number 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 11)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid K described below, a hard coating film for molding was obtained.

(hard coating liquid K)

● methyl ethyl ketone 67.93 mass%

● Neopentyl alcohol triacrylate 11.58% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.79% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 5.79% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 7.72% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.16% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Embodiment 12)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid L described below, a hard coating film for molding was obtained.

(coating liquid L)

● methyl ethyl ketone 4.24% by mass

● Neopentyl alcohol triacrylate 6.22% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 3.12% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 3.12% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 82.73% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 0.55 mass%

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.02% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 13)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid M described below, a hard coating film for molding was obtained. (coating liquid M)

● methyl ethyl ketone 71.46% by mass

● Neopentyl alcohol triacrylate 11.72% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.86% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 5.86% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 3.90% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.17% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 14)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid N described below, a hard coating film for molding was obtained.

(coating liquid N)

● Neopentyl alcohol triacrylate 5.28% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 2.64% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 2.64% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 88.88% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 0.55 mass%

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.02% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 15)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid O described below, a hard coating film for molding was obtained.

(coating liquid O)

● methyl ethyl ketone 58.76% by mass

● Neopentyl alcohol triacrylate 11.45% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.73% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 5.72% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 17.17% by mass

(made by Fuso Chemical Industry Co., Ltd., PL2L-MEK, solid content rate: 20%, average particle size: 20 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Embodiment 16)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid P described below, a hard coating film for molding was obtained.

(coating liquid P)

● methyl ethyl ketone 58.76% by mass

● Neopentyl alcohol triacrylate 11.45% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.73% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 5.72% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 17.17% by mass

(made by Fuso Chemical Industry Co., Ltd., PL30L-MEK, solid content rate: 20%, average particle size: 297 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 17)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid Q described below, a hard coating film for molding was obtained.

(coating solution Q)

● methyl ethyl ketone 58.76% by mass

● Neopentyl alcohol triacrylate 11.45% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.73% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 5.72% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 17.17% by mass

(made by Nippon Shokubai Co., Ltd., SEAHOSTAR KE-E50, solid content rate: 20%, average particle size: 511 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Embodiment 18)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid R described below, a hard coating film for molding was obtained.

(coating liquid R)

● methyl ethyl ketone 72.50% by mass

● Neopentyl alcohol triacrylate 11.45% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.73% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 5.72% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Melamine/formaldehyde condensate particles 3.43% by mass

(made by Nippon Shokubai Co., Ltd., EPOSTAR S, average particle size: 196 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Embodiment 19)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid S described below, a hard coating film for molding was obtained.

(coating liquid S)

● methyl ethyl ketone 75.08% by mass

● Neopentyl alcohol triacrylate 11.85% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.93% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 5.92% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Photopolymerization initiator 1.19% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Embodiment 20)

In the first embodiment, a hard coating film for molding was obtained in the same manner as in Example 1 except that the thickness of the hardened layer formed by the coating liquid was 1.11 μm.

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 21)

In Example 1, a hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid was applied so that the thickness of the hardened layer formed after curing was 50 μm.

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Example 22)

In Example 1, a hard coating film for molding was obtained in the same manner as in Example 1 except that the coating liquid was applied to have a thickness of the cured layer formed by hardening of 0.5 μm.

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has many defects in surface hardness. This is the reason why the surface hardness of the hard coating layer can be maintained to be thinned out of the range. The results obtained are shown in Table 1.

(Example 23)

In the first embodiment, a hard coating film for molding was obtained in the same manner as in Example 1 except that the thickness of the hardened layer formed by the coating liquid was 60 μm.

The hard coating film for molding obtained was excellent in moldability, surface hardness, scratch resistance, and coloration degree, and was excellent as a hard coating film for molding. Further, the molded body formed by using the obtained hard coating film for molding has a good surface hardness. The results obtained are shown in Table 1.

(Comparative Example 1)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid T described below, a hard coating film for molding was obtained.

(coating liquid T)

● methyl ethyl ketone 64.48% by mass

● Neopentyl alcohol triacrylate 22.90% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained was excellent in surface hardness, scratch resistance, and coloration, but was inferior in moldability, and was also inferior as a hard coating film for molding. The results obtained are shown in Table 1.

(Comparative Example 2)

In the same manner as in Example 1, except that the coating liquid for forming the hardened layer was changed to the coating liquid U described below, a hard coating film for molding was obtained.

(coating liquid U)

● methyl ethyl ketone 64.48% by mass

●Tri-propylene glycol diacrylate 11.45% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 11.45% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

The hard coating film for molding obtained is excellent in moldability and coloration, but has poor surface hardness and scratch resistance, and is also inferior as a hard coating film for molding. The results obtained are shown in Table 1.

(Example 24)

A film roll having a width of 1000 mm and a length of 200 m was applied by a micro-gravure method and a coating liquid V described below in a roll-to-roll manner, and the thickness of the hardened layer after coating hardening was 2 μm, and then the film tension was 180 N/m. The film was dried by hot air at a temperature of 80 ° C for 60 seconds, and was hardened at a speed of 10 m/min at a position of 20 cm (accumulated light amount of 300 mJ/cm ² ) under a high-pressure mercury lamp having an output of 160 W/cm, and then the hard coating film for molding was wound up. A cylindrical core made of polypropylene having a diameter of 6 inches was formed into a hard coated roll for molding having a width of 1000 mm and a length of 200 m.

(coating liquid V)

The following materials were mixed in the following mass ratio, and stirred for 30 minutes or more to dissolve. Next, the undissolved matter was filtered off using a filter having a nominal filtration precision of 1 μm to prepare a coating liquid V.

● methyl ethyl ketone 28.24% by mass

● Toluene 36.24% by mass

● Neopentyl alcohol triacrylate 11.45% by mass

(Manufactured by Shin-Nakamura Chemical Co., Ltd., NK ESTER A-TMM-3LM-N, functional group number 3)

● Tri-propylene glycol diacrylate 5.73% by mass

(New Nakamura Chemical Co., Ltd., NK ESTER APG-200, functional base 2)

● Dimethylamine ethyl methacrylate 5.72% by mass

(produced by Kyoeisha Chemical Co., Ltd., LIGHT ESTER DM, functional group number 1)

● Vermiculite particles 11.45% by mass

(made by Nissan Chemical Industry Co., Ltd., MEK-ST-L, solid content rate: 30%, average particle diameter: 50 nm)

● Photopolymerization initiator 1.14% by mass

(manufactured by CIBA SPECIALITY CHEMICALS, IRGACURE 184)

● Organic lanthanide surfactant 0.03% by mass

(DOW CORNING TORAY company, DC57)

When the base film is coated and hardened to form a hardened layer, the traveling film does not undergo meandering or crepe, so that the productivity can be made into a hard coating without any problem. The obtained hard coating film for molding has a good coating appearance and a good shrinkage ratio in the width direction. Further, the obtained hard coating film for molding had the same moldability, surface hardness, and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The results obtained are shown in Table 2.

(Embodiment 25)

In the same manner as in Example 24 except that the drying temperature was changed to 40 ° C in Example 24, a hard coating roll for molding was obtained.

When the base film is coated and hardened to form a hardened layer, the traveling film does not undergo meandering or crepe, so that the productivity can be made into a hard coating without any problem. The obtained hard coating film for molding has a good coating appearance and a good shrinkage ratio in the width direction. Further, the obtained hard coating film for molding had the same moldability, surface hardness, and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The results obtained are shown in Table 2.

(Example 26)

In the same manner as in Example 24 except that the drying temperature was changed to 120 ° C in Example 24, a hard coating roll for molding was obtained.

When the base film is coated and hardened to form a hardened layer, the traveling film does not undergo meandering or crepe, so that the productivity can be made into a hard coating without any problem. The obtained hard coating film for molding has a good coating appearance and a good shrinkage ratio in the width direction. Further, the obtained hard coating film for molding had the same moldability, surface hardness, and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The results obtained are shown in Table 2.

(Example 27)

In the same manner as in Example 24 except that the film tension was changed to 50 N/m, the hard coating roll for molding was obtained in Example 24.

When the base film is coated and hardened to form a hardened layer, the traveling film does not undergo meandering or crepe, so that the productivity can be made into a hard coating without any problem. The obtained hard coating film for molding has a good coating appearance and a good shrinkage ratio in the width direction. Further, the obtained hard coating film for molding had the same moldability, surface hardness, and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The results obtained are shown in Table 2.

(Embodiment 28)

In the same manner as in Example 24 except that the film tension was changed to 300 N/m, the hard coating roll for molding was obtained in Example 24.

When the base film is coated and hardened to form a hardened layer, the traveling film does not undergo meandering or crepe, so that the productivity can be made into a hard coating without any problem. The obtained hard coating film for molding has a good coating appearance and a good shrinkage ratio in the width direction. Further, the obtained hard coating film for molding had the same moldability, surface hardness, and scratch resistance as those of Example 1, and the surface hardness of the molded body was also good. The results obtained are shown in Table 2.

(Comparative Example 3)

In the same manner as in Example 24 except that the drying temperature was changed to 30 ° C in Example 24, a hard coating roll for molding was obtained.

When the base film is coated and hardened to form a hardened layer, the traveling film does not undergo meandering or crepe, so that the productivity can be made into a hard coating without any problem. The obtained hard coating film for molding has a good shrinkage ratio in the width direction, but the coating appearance is whitened and poor. The results obtained are shown in Table 2.

(Comparative Example 4)

In the same manner as in Example 24 except that the drying temperature was changed to 140 ° C in Example 24, a hard coating roll for molding was obtained.

When the base film is coated and hardened to form a hardened layer, the traveling film does not wrap and is creped, so that productivity is not suitable. The hard coating film for molding obtained has a coating appearance which is poor in micro coating loss or repulsion, and is also inferior in shrinkage in the width direction. The results obtained are shown in Table 2.

(Comparative Example 5)

In the same manner as in Example 24 except that the film tension was changed to 40 N/m, the hard coating roll for molding was obtained in Example 24.

When the base film is coated and hardened to form a hardened layer, no wrinkles occur, but the traveling film is meandering, so that productivity is not suitable. Since the traveling film is meandered, a hard coating film for molding cannot be obtained.

(Comparative Example 6)

In the same manner as in Example 24 except that the film tension was changed to 320 N/m, the hard coating roll for molding was obtained in Example 24.

When the base film is coated and hardened to form a hardened layer, the traveling film does not wander, but crepe is generated, so that productivity is not suitable. The hard coating film for molding obtained was excellent in coating appearance, but was inferior in shrinkage in the width direction. The results obtained are shown in Table 2.

(Comparative Example 7)

In the first embodiment, a base film was produced in the same manner as in Example 1 except that the heat setting temperature was changed to 205 ° C to obtain a hard coating film for molding.

(Example 29)

In the same manner as in Example 1, except that the resin sheet (B) was changed to a resin sheet (C) of polyethylene terephthalate containing no ultraviolet absorber, a hard coating film for molding was obtained.

(Embodiment 30)

The following resin sheets (D), (E), and (F) were prepared as the film raw material of Example 30.

The constituent component of the resin sheet (D) is an aromatic dicarboxylic acid component, an ethylene glycol unit of 70 mol%, and a neopentyl glycol unit of 30 mol% as a diol component, and contains benzene. A resin sheet of a copolyester having a triazole-based ultraviolet absorber (N) (manufactured by CIBA SPECIALITY CHEMICALS CO., LTD., TINUVIN 326) of 0.5% by mass and having an intrinsic viscosity of 0.77 dl/g.

Resin sheet (F) is a resin containing polyethylene terephthalate containing benzotriazole-based ultraviolet absorber (N) (manufactured by CIBA SPECIALITY CHEMICALS CO., LTD., TINUVIN 326) at 0.67 mass% and having an intrinsic viscosity of 0.77 dl/g. sheet.

The resin sheet (E) is a propylene terephthalate (PPT) containing a benzotriazole-based ultraviolet absorber (N) (manufactured by CIBA SPECIALITY CHEMICALS CO., LTD., TINUVIN 326) of 0.67 mass% and an intrinsic viscosity of 0.75 dl/g. ) Resin sheet.

After the respective resin sheets were dried, the resin sheet (D), the resin sheet (F) and the resin sheet (E) were mixed at a mass ratio of 50:10:40. Next, the resin sheet mixture was melt-extruded at 270 ° C from the T-die slit of the extruder, and rapidly solidified on a cooling roll having a surface temperature of 40 ° C, while being electrostatically applied to make the amorphous film adhered to the cooling roll. Stretch the sheet.

The unstretched sheet was stretched 3.5 times in the longitudinal direction at 83 ° C between the heating roll and the cooling roll.

Next, the coating liquid of Example 1 was applied and dried on the single side of the uniaxially stretched film in the same manner as in Example 1, and an intermediate layer was provided. Next, the uniaxially stretched film provided with the coating layer was introduced into a tenter, and after preheating at 95 ° C for 10 seconds, the first half was stretched 3.9 times at 80 ° C and the second half at 75 ° C in the transverse direction. Further, heat treatment was carried out at 205 ° C under a 7% relaxation treatment in the transverse direction to obtain a base film having a thickness of 50 μm. Using the obtained base film, a hard coating film for molding was obtained in the same manner as in Example 1.

(Example 31)

The resin sheet (D) and the resin sheet (F) were mixed as a core material at a mass ratio of 50:50 as a raw material of the core layer, and the mixed resin sheet was put into another extrusion. After melting at 280 ° C, the core material was joined with a feedblock to make the surface layer/core layer/surface layer = 10/80/10, and then extruded from the T die at 270 ° C, and the transverse stretching and heat setting were performed. The base film was produced in the same manner as in Example 30 except that the treatment was changed to the same as in Table 6, and a hard coating film for molding was obtained.

(Example 32)

In addition to the above resin sheet (F), the following resin sheet (H) and resin sheet (I) were prepared as the film raw material of Example 32.

The constituent component of the resin sheet (H) is 60 mol% of citric acid unit and 40 mol% of isononanoic acid as an aromatic dicarboxylic acid component, and ethylene glycol unit 100 mol% as a diol component, and has an intrinsic viscosity. A resin sheet of a copolyester of 0.71 dl/g.

The constituent component of the resin sheet (I) is 60 mol% of a decanoic acid unit and 40 mol% of a naphthalenedicarboxylic acid unit as an aromatic dicarboxylic acid component, and an ethylene glycol unit of 100 mol% as a diol component, and has an intrinsic viscosity. A resin sheet of a copolyester of 0.71 dl/g.

The resin sheet (F) and the resin sheet (H) of the above copolymerized polyester and the resin sheet (I) of polyethylene terephthalate were mixed at a mass ratio of 50:25:25 and dried. Next, the resin sheet mixture was melt-extruded at 270 ° C from the T-die slit of the extruder, and rapidly solidified on a cooling roll having a surface temperature of 40 ° C, while being electrostatically applied to make the amorphous film adhered to the cooling roll. Stretch the sheet.

The unstretched sheet was stretched 3.5 times in the longitudinal direction at 90 ° C between the heating roll and the cooling roll. Next, the uniaxially stretched film was introduced into a tenter, and after preheating at 120 ° C for 10 seconds, the first half was stretched 3.9 times in the transverse direction at 110 ° C and the second half at 100 ° C. Further, heat treatment was carried out at 238 ° C under a 7% relaxation treatment to obtain a substrate film having a thickness of 100 μm. Using the obtained base film, a hard coating film for molding was obtained in the same manner as in Example 1.

(Comparative Example 8)

The resin sheet (G) was prepared as the film material of Comparative Example 8. The resin sheet (G) is a resin sheet (G) having an intrinsic viscosity of 0.64 dl/g and a polyethylene terephthalate having an average particle diameter (SEM method) of 1.5 μm and an amorphous vermiculite of 0.08% by mass.

The PET resin sheet (G) was vacuum dried at 180 ° C for 4 hours, and then supplied to a melt extruder, and extruded into a sheet shape by a slit-like die to obtain an unstretched sheet. This unstretched sheet was first stretched 3.0 times in the longitudinal direction by a calender roll heated to a temperature of 105 ° C, and then stretched 3.2 times in the width direction at a stretching temperature of 125 ° C, and then subjected to a relaxation treatment of 6% under 195. The film was heat-fixed at ° C to obtain a substrate film having a thickness of 100 μm and a plane orientation of 0.138. Using the obtained base film, a hard coating film for molding was obtained in the same manner as in Example 1.

(Comparative Example 9)

In addition to the commercially available A-PET unstretched sheet (made by Toyobo Co., Ltd., PETMAX) A hard coat film for molding was obtained in the same manner as in Example 1 except that the base film was used as the base film.

(Comparative Example 10)

In addition to the commercially available polycarbonate unstretched sheet (manufactured by Teijin Chemical Co., Ltd., PANLITE A hard coating film for molding was obtained in the same manner as in Example 1 except that the base film was used as the base film.

(Comparative Example 11)

In addition to the commercially available acrylate unstretched sheet (made by Mitsubishi Chemical Corporation, ACRYPLEN) HBS006, thickness: 125 μm) A hard coating film for molding was obtained in the same manner as in Example 1 except that the base film was used.

The raw material composition and polymer properties of the polymer to be used are shown in Table 1, and the production conditions and characteristics of the film are shown in Tables 2 to 5. The properties of the hard coating film for molding are shown in Tables 6 and 8. The characteristics of the hard coating roll for molding are shown in Table 7.

[Industry use possibility]

Since the hard coating film for molding of the present invention is excellent in moldability when it is heated and molded at a low temperature and a low pressure, it is suitably used in a wide range of molding methods, and when the molded article is used in a normal temperature environment, elasticity and form stability ( It is excellent in heat shrinkage characteristics and thick spots, and is excellent in solvent resistance and heat resistance, and has an environmental burden. Further, since the hard coating film for molding of the present invention has a hardened layer to reinforce the surface hardness of the base film, the molded body formed by using the hard coating film for molding of the present invention is suitable for scratch resistance. Housings for home appliances, car nameplates or building materials, mobile phone handsets, stereos, portable recorders, IC recorders, car satellite navigators, PDA phones, and other portable devices such as laptops or notebook computers. In addition, in the molding process, the hardened layer is processed and laminated on the base film before molding, which contributes to improvement in productivity and quality stability, and contributes greatly to the industry.

In addition, the film contains an ultraviolet absorber to reduce the light transmittance under ultraviolet light, and it is possible to impart light resistance, and is particularly suitable for use as a molding material for outdoor use (automobile exterior or building materials).

Claims (7)

A hard coating film for molding, which comprises a base film formed of a biaxially oriented polyester film containing a copolymerized polyester and a hard coating film for forming a hardened layer obtained by curing a coating liquid, and the coating liquid An epitaxial radiation-curable compound having at least three functional groups and an exogenous radiation-curable compound having 1 and/or a bifunctional group, wherein the coating liquid contains a 1 and/or 2 functional group in the free radiation-curable compound The content of the free-radiation-type compound is 5% by mass or more and 95% by mass or less, and at least one of the free-radiation-curable compounds contained in the coating liquid is an free-radiation-curable compound having an amine group; the base film satisfies the following ( 1)~(3) Necessary conditions (1) The stress at 100% stretching in the longitudinal direction and the width direction of the film is 40 to 300 MPa at 25 °C and 1 to 100 MPa at 100 °C; (2) the melting point is 200~245°C; (3) The plane orientation degree is 0.01 or more and less than 0.11. The hard coating film for molding according to the first aspect of the invention, wherein the content of the radical-curable compound having an amine group in the free radiation curable compound contained in the coating liquid is 2.5% by mass or more and 95% by mass or less. . The hard coating film for molding according to the first aspect of the invention, wherein the hardened layer contains particles having an average particle diameter of 10 nm or more and 300 nm or less, and is hard. The content of the particles in the layer is 5% by mass or more and 70% by mass or less. The hard coating film for molding according to the first aspect of the invention, wherein the copolyester is (a) an aromatic dicarboxylic acid component, ethylene glycol, and a branched aliphatic diol or an alicyclic two a copolyester composed of an alcohol diol component; or (b) a copolymerized polyester composed of an aromatic dicarboxylic acid component containing p-citric acid and isophthalic acid and a glycol component containing ethylene glycol. The hard coating film for molding according to the fourth aspect of the invention, wherein the polyester constituting the biaxially oriented polyester film contains a 1,3-propanediol unit or a 1,4-butanediol unit. The hard coating film for molding according to the first aspect of the invention, wherein the biaxially oriented polyester film contains an ultraviolet absorber having a light transmittance of 50% or less at a wavelength of 370 nm. A molded body obtained by molding any of the hard coating films for molding according to any one of claims 1 to 6 by vacuum molding, pneumatic molding, and die molding.