JP6430368B2 - Hard coat film for molding - Google Patents

Description

  The present invention relates to a molding hard coat film used for the production of a resin molded product by in-mold molding, insert molding, or vacuum molding.

  Resin molded products are often used for mobile information terminal devices such as mobile phones, smartphones, notebook computers, home appliances, automobile interior and exterior parts, and the like. As products become more commoditized, the need for differentiation in these products is increasing. Conventionally, as a method for decorating a resin molded product, a colored paint is applied to the surface of a three-dimensional resin molded product by injection molding or the like, or screen printing is performed. Furthermore, a method of applying a clear hard coat by spraying or dipping has been performed for the purpose of protecting the surface of the product.

However, such conventional methods are difficult to decorate with high design, and there is a concern about the impact on the work environment by chemical substances such as volatile solvents contained in the paint used in spray coating etc. There is. Therefore, as an alternative method, a decorative film provided with a hard coat layer by printing or coating of a film has come to be used, and in-mold molding in which a highly designable decoration is provided on the surface of a resin molded product has become widespread.
The in-mold molding method is a technique in which a decorative film is adhered to the surface of a resin molding by simultaneously performing vacuum molding and injection in an injection mold. There is an advantage that a product can be obtained in one process, and the process can be shortened and painting can be omitted.

  Another method is a film insert molding method, in which the decorative film is heated (preliminary heating) to obtain a molded product of the decorative film with a mold and then preliminarily molded by injection molding as the next step. In this method, the molded product and the resin molded product are bonded and integrated. This method has the advantage that a general-purpose device can be used, but it needs to go through two steps.

  In addition to the in-mold molding method, there is a vacuum molding method as a molding method using a decorative film. In this vacuum molding method, the decorative film is heated (preliminary heating) and softened under vacuum, and then the vacuum is applied to the decorative film, and the decorative film is bonded to the surface of the resin molding while being stretched. Thereafter, the molded product is taken out by cooling and releasing the vacuum. In this vacuum forming method, only a weak air pressure works rather than a mechanical strong force sandwiched between molds such as in-mold molding. Therefore, to make the decorative film follow the surface shape of the molded product, from the softening temperature of the film It is necessary to perform preheating at a sufficiently high temperature. If the preheating temperature is too low, when the decorative film is bonded to a resin molded product having a deep-drawn three-dimensional shape, the film is not stretched sufficiently. In the bent part, even if a decorative film is pasted, it does not become a sharp bend but becomes a shallow rounded shape, which impairs the original shape of the resin molded product. In addition, it is necessary to select an appropriate preheating temperature depending on the resin composition type used for the base film of the decorative film. Further, as an advantage, large-scale molding is easy.

  Various configurations have been conventionally proposed as a decorative film used in the molding method using the decorative film as described above (see Patent Documents 1 to 3).

JP 2012-193265 A JP 2012-81628 A JP 2012-512247 A

  As hard coating films for molding are used in various fields, the surface hardness is sufficient in addition to sufficient extensibility to follow three-dimensional molding (the hard coat layer does not crack when stretched). (Pencil hardness, scratch resistance) is also required. However, the highly extensible resin used for the hard coat layer of the molding hard coat film is soft and does not express sufficient surface hardness, and the resin excellent in surface hardness is hard and does not express sufficient extensibility. The surface hardness and extensibility are in a trade-off relationship.

  Therefore, an object of the present invention is to provide a molding hard coat film having improved moldability (elongation rate), surface hardness, and scratch resistance characteristics.

In order to solve the above-described problems, the present invention provides an invention having the following configuration.
In the first invention, a coating composition containing a resin obtained by mixing an ionizing radiation curable resin (a) below and an ionizing radiation curable resin (b) is applied onto a base film and cured. A hard coat film for molding, which is provided with a hard coat layer.
(a) An ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more.
(b) An ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less.

A second invention is a hard coat film for molding according to the first invention, wherein the coating composition further contains an ionizing radiation curable resin (c) below.
(c) An ionizing radiation curable resin having a weight average molecular weight Mw of more than 10,000 and less than 150,000.

A third invention is a hard coat film for molding according to the first or second invention, wherein the ionizing radiation curable resin (a) satisfies the following conditions.
Conditions: A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm ² is formed on a polyethylene terephthalate film is prepared. Next, a test piece having a width of 15 mm and a length of 150 mm was produced from the produced film, and the test piece was pulled at a tensile speed of 50 mm / min in an environment of a temperature of 25 ° C. and a humidity of 50% RH. The elongation rate until the coating film cracks is 50% or more, and the pencil hardness specified in JIS K5600 is B to H.

A fourth invention is a hard coat film for molding according to any one of the first to third inventions, wherein the ionizing radiation curable resin (b) satisfies the following conditions.
Conditions: A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm ² is formed on a polyethylene terephthalate film is prepared. Next, a test piece having a width of 15 mm and a length of 150 mm was produced from the produced film, and the test piece was pulled at a tensile speed of 50 mm / min in an environment of a temperature of 25 ° C. and a humidity of 50% RH. The elongation rate until cracks occur in the coating film is 1% or more, and the pencil hardness specified in JIS K5600 is H to 4H.

A fifth invention is a hard coat film for molding according to any one of the second to fourth inventions, wherein the ionizing radiation curable resin of (c) satisfies the following conditions.
Conditions: A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm ² is formed on a polyethylene terephthalate film is prepared. Next, a test piece having a width of 15 mm and a length of 150 mm was produced from the produced film, and the test piece was pulled at a tensile speed of 50 mm / min in an environment of a temperature of 25 ° C. and a humidity of 50% RH. The elongation rate until cracks occur in the coating film is 20% or more, and the pencil hardness specified in JIS K5600 is HB to 2H.

A sixth invention is a hard coat film for molding according to any one of the first to fifth inventions, wherein the hard coat layer contains inorganic oxide fine particles having an average particle diameter of 5 to 50 nm. .
A seventh invention is the molding hard coat film according to the sixth invention, wherein the inorganic oxide fine particles contain aluminum as a main component.

According to an eighth invention, in the sixth or seventh invention, the content of the inorganic oxide fine particles is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the solid content of the coating composition. This is a hard coating film for molding.
According to a ninth invention, in any one of the first to eighth inventions, a decoration layer is formed on the surface of the base film opposite to the surface on which the hard coat layer is provided via a primer layer. The primer layer is a hard coat film for molding characterized by containing a vinyl chloride-vinyl acetate copolymer resin and a polymethyl methacrylate resin.
A tenth invention is characterized in that, in the ninth invention, the blending ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin and the polymethyl methacrylate resin is in the range of 80/20 to 25/75. Hard coat film for molding.

  ADVANTAGE OF THE INVENTION According to this invention, the hard coat film for shaping | molding which improved the characteristics of moldability (elongation rate), surface hardness, and abrasion resistance can be provided.

Hereinafter, embodiments of the present invention will be described in detail.
The molding hard coat film of the present invention is applied on a base film with a coating composition containing a resin obtained by mixing the following ionizing radiation curable resin (a) and ionizing radiation curable resin (b): A hard coat layer formed by curing is provided.
(a) An ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more.
(b) An ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less.
The ionizing radiation curable resin (a) and the ionizing radiation curable resin (b) will be described in detail later.

[Base film]
First, the said base film is demonstrated.
Although it does not specifically limit as a base film which can be used for this invention, It is a material which can be thermoformed, Comprising: The stress at the time of an expansion | extension is low, and it is preferable that it is a material which can be extended with weak force. In the present invention, for example, an acrylic film such as a polyethylene terephthalate (PET) film or a polymethyl methacrylate (PMMA) film, a polycarbonate (PC) film, or the like can be preferably used. In the case of the PET film, a general-purpose biaxially stretched PET film may be used, but in order to obtain better moldability, it is particularly preferable to use a biaxially stretchable easily molded PET film. This biaxially stretchable and easy-to-mold PET film has a low heat softening temperature, can be stretched with a weak force, and is a relatively inexpensive material.

The acrylic film and the polycarbonate (PC) film are both unstretched films and can be suitably used for any molding method.
Although there is no restriction | limiting in particular also about the thickness of a base film, For example, the film of thickness about 25 micrometers-150 micrometers is used.

[Hard coat layer]
Next, the hard coat layer will be described.
In the present invention, the resin contained in the hard coat layer can be used without particular limitation as long as it is a resin that forms a film, but in particular, imparts hardness (pencil hardness, scratch resistance) to the hard coat layer surface. In addition, the degree of cross-linking can be adjusted by the exposure amount of ultraviolet rays and the like, and the ionizing radiation curable type can be adjusted in the stretchability and surface hardness (pencil hardness, scratch resistance) of the hard coat layer. It is preferable to use a resin.

  The ionizing radiation curable resin used in the present invention is a transparent resin that is cured by irradiation with ultraviolet rays (hereinafter abbreviated as “UV”) or electron beams (hereinafter abbreviated as “EB”). It is not specifically limited, For example, it can select suitably from urethane acrylate resin, polyester acrylate resin, etc., for example. Preferred examples of the ionizing radiation-type resin include those made of a polyfunctional acrylate curable with UV or EB having two or more (meth) acryloyl groups in the molecule. Specific examples of UV or EB curable polyfunctional acrylates having two or more (meth) acryloyl groups in the molecule include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, Polymethyl polyacrylate such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A Diglycidyl ether diacrylate, neopentyl glycol diglycidyl ether diacrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, etc. Polyester (meth) acrylate, polyhydric alcohol, polyhydric isocyanate, and hydroxyl group-containing compounds that can be obtained by esterifying xyl (meth) acrylate, polyhydric alcohol and polyhydric carboxylic acid and / or anhydride and acrylic acid The urethane (meth) acrylate obtained by making (meth) acrylate react, polysiloxane poly (meth) acrylate, etc. can be mentioned. In addition, you may mix and use 3 or more types of polyfunctional acrylate.

In the hard coat film of the present invention, as described above, the characteristic configuration is that, as described above, a resin obtained by mixing the ionizing radiation curable resin (a) and the ionizing radiation curable resin (b) on the base film. That is, a hard coat layer formed by coating and curing the coating composition contained is provided.
Here, the ionizing radiation curable resin (a) is an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more, and the ionizing radiation curable resin (b) is a weight average molecular weight Mw of 10,000 or less. Ionizing radiation curable resin.
In the present invention, the weight average molecular weight Mw of the ionizing radiation curable resin is a value measured by gel permeation chromatography (GPC) using polystyrene as a standard sample.

  Thus, as a resin component of the hard coat layer, a mixture of an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more and an ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less is used for molding. It is possible to improve all the characteristics of the hard coat film, such as moldability (elongation), surface hardness, and scratch resistance.

  In the present invention, as the resin component of the hard coat layer, in addition to an ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more and an ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less, (c) As the ionizing radiation curable resin, it is more preferable to use a mixture of ionizing radiation curable resins having a weight average molecular weight Mw of more than 10,000 and less than 150,000.

Among the ionizing radiation curable resins having the weight average molecular weight Mw of (a) of 150,000 or more, an ionizing radiation curable resin satisfying the following conditions is preferable.
Conditions: A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm ² is formed on a polyethylene terephthalate film is prepared. Next, a test piece having a width of 15 mm and a length of 150 mm was produced from the produced film, and the test piece was pulled at a tensile speed of 50 mm / min in an environment of a temperature of 25 ° C. and a humidity of 50% RH. The elongation rate until the coating film cracks is 50% or more, and the pencil hardness specified in JIS K5600 is B to H.

Among the ionizing radiation curable resins having a weight average molecular weight Mw of 10,000 or less in (b), the elongation measured by the same test method as described above is 1% or more and the pencil hardness is H to 4H. An ionizing radiation curable resin is preferable.
Among the ionizing radiation curable resins having a weight average molecular weight Mw of (c) of more than 10,000 and less than 150,000, the elongation measured by the same test method as described above is 20% or more, and the pencil hardness is HB. An ionizing radiation curable resin having ~ 2H is preferred.

In the present invention, the mixing ratio of the ionizing radiation curable resin (a) and the ionizing radiation curable resin (b) is (a) :( b) = 80: 20 to 60:40 (parts by weight). It is preferable. When the mixing ratio is outside this range, it is difficult to obtain the effect of using the ionizing radiation curable resin (a) and the ionizing radiation curable resin (b) in combination, moldability (elongation rate) and surface hardness, It becomes difficult to improve any of the characteristics of scratch resistance.
In the present invention, in addition to the ionizing radiation curable resin (a) and the ionizing radiation curable resin (b), when the ionizing radiation curable resin (c) is used in combination, these resins are used. The mixing ratio is preferably (a) :( b) :( c) = 40-60 : 5-30 : 20-55 (parts by weight). When the mixing ratio is outside this range, the effect of using the ionizing radiation curable resin (c) in addition to the ionizing radiation curable resin (a) and the ionizing radiation curable resin (b) is obtained. It becomes difficult.

  In addition to the ionizing radiation curable resin described above, the resin contained in the hard coat layer includes thermoplastic resins such as polyethylene, polypropylene, polystyrene, polycarbonate, and polyester, phenol resins, urea resins, and unsaturated polyesters. Further, a thermosetting resin such as epoxy or silicon resin may be contained within a range that does not impair the effects of the present invention, that is, the extensibility, hardness, and scratch resistance of the hard coat layer.

As the photopolymerization initiator for the ionizing radiation curable resin contained in the hard coat layer, known ones such as acetophenones and benzophenones can be used.
In the present invention, the hard coat layer preferably contains inorganic oxide fine particles. In this case, the average particle diameter of the inorganic oxide fine particles is preferably 5 to 50 nm, and more preferably 10 to 20 nm. If the average particle diameter is less than 5 nm, it is difficult to obtain sufficient surface hardness. On the other hand, when the average particle diameter exceeds 50 nm, the gloss and transparency of the hard coat layer are lowered, and the flexibility is also lowered.

In the present invention, examples of the inorganic oxide fine particles include alumina and silica. Among these, alumina containing aluminum as a main component is particularly suitable because it has a high hardness and can obtain an effect with a smaller amount of addition than silica.
In this invention, it is preferable that content of inorganic oxide microparticles | fine-particles is 0.1-5.0 weight part with respect to 100 weight part of solid content of the coating composition for hard-coat layers. When the content is less than 0.1 parts by weight, it is difficult to obtain the effect of improving the scratch resistance. On the other hand, if the content exceeds 5.0 parts by weight, the haze increases, and the design of the molded body using the molding hard coat film may be impaired.

  Further, as other additives to be added to the hard coat layer, as long as the effect of the present invention is not impaired, an antifoaming agent, a leveling agent, a surface tension adjusting agent, an antifouling agent, an antioxidant, an antistatic agent, You may contain a ultraviolet absorber, a light stabilizer, etc. as needed.

  In the present invention, the thickness of the hard coat layer is not particularly limited, but is preferably in the range of, for example, about 1 to 10 μm. If the coating thickness is less than 1 μm, it will be difficult to obtain the required hardness. Moreover, when the coating film thickness is thicker than 10 μm, it becomes difficult to obtain good extensibility.

  The hard coat layer, in addition to the ionizing radiation type resin described above, is coated on the base film with a paint in which inorganic oxide fine particles, a polymerization initiator, other additives, etc. are dissolved and dispersed in an appropriate solvent. It is formed by drying. The solvent can be appropriately selected depending on the solubility of the resin contained therein, and may be any solvent that can uniformly dissolve or disperse at least a solid content (resin, polymerization initiator, other additives, etc.). Examples of such a solvent include ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), ethers (dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic hydrocarbons ( Cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (methanol, ethanol, isopropanol, Butanol, cyclohexanol, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides, amides and the like. Moreover, a solvent may be used individually or may be used in mixture of 2 or more types.

The coating method of the hard coat layer is not particularly limited, but it is usually easy to adjust the coating thickness, such as gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, etc. Coating is possible by the method. The film thickness of the coated hard coat layer can be measured, for example, by actually measuring with a micrometer.
In the molding hard coat film of the present invention, a decorative layer such as a printing layer, a coloring / adhesive film, or the like may be provided on the opposite side of the base film from the side on which the hard coat layer is provided. .

  The said decoration layer is comprised by the pattern layer and / or a concealment layer, a metal vapor deposition layer, etc., for example. Here, the pattern layer is a layer provided to express a pattern such as a pattern or characters, and the concealing layer is a solid layer, and is a layer provided to conceal the coloring of the resin or the like. . Moreover, a metal vapor deposition layer is the layer which vapor-deposited one part or the whole surface, and is provided for the purpose of expressing the layer provided for concealing coloring etc. of resin etc., or a resin layer in a metal tone. Is a layer.

  The decorative layer (for example, the pattern layer and / or the concealment layer) can be formed by a known printing method such as gravure printing, offset printing, or screen printing. Although there is no restriction | limiting in particular in the formation thickness of a decoration layer, 3-50 micrometers is preferable from a viewpoint of design property, More preferably, it is 10-30 micrometers. Moreover, the said metal vapor deposition layer can be formed into a film by methods, such as sputtering.

  Examples of printing ink binders used to form the decorative layer include polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyurethane resins, acrylic two-component curable resins, cellulose resins, and acrylic resins. it can. The printing ink is usually provided in a form dissolved or dispersed in a solvent. Solvents include aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, ester solvents such as ethyl acetate and butyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone and anone. A ketone solvent, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, butanol, or a mixture of the above solvents can be used. Usually, a general-purpose solvent used for adjusting the solvent-based paint can be used.

  In addition, when the said decoration layer is formed by printing directly on a base film, the adhesion of a decoration layer (printing layer) and a base film becomes inadequate, and the problem of dropping off of a decoration layer generate | occur | produces. There is a fear. For this reason, it is preferable to provide the primer layer which has adhesiveness with both a base film and a decoration layer between a base film and a decoration layer. In addition, when the decorative film provided with this primer layer is used as a film for molding, in addition to the adhesion between the base film and the decorative layer as a characteristic of the primer layer, the elongation of the base film at the time of molding It is also necessary that the following physical properties (elongation) are good.

  In the present invention, the primer layer preferably includes a vinyl chloride-vinyl acetate copolymer resin and a polymethyl methacrylate resin as main components. In this case, the blending ratio (parts by weight) is preferably in the range of vinyl chloride-vinyl acetate copolymer resin / polymethyl methacrylate resin = 80/20 to 25/75.

  If the blending ratio of the vinyl chloride-vinyl acetate copolymer resin to the polymethyl methacrylate resin is more than 80 parts by weight, the solvent resistance of the dried coating film of the primer layer 2 decreases, so that the paint (ink Etc.) primer layer (for example, typical composition of ink solvent: NPR (n-propyl alcohol) / toluene / ethyl acetate / MEK (methyl ethyl ketone) = 30/30/20/20 (parts by weight)) Since the coating film is eroded and the decorativeness and adhesion are likely to be lowered, and the heat resistance is lowered, operational problems may occur. Furthermore, problems such as crimping or blocking occur when the molding film is wound up. On the other hand, when the blending ratio of the vinyl chloride-vinyl acetate copolymer resin to the polymethyl methacrylate resin is less than 25 parts by weight, the adhesion with the base film or the decorative layer is lowered.

  The ratio of vinyl chloride and vinyl acetate in the vinyl chloride-vinyl acetate copolymer resin is not particularly limited, but is preferably vinyl chloride / vinyl acetate = 65/35 to 90/10 (parts by weight). More preferably, it is 70/30 to 90/10 (parts by weight). When the ratio of vinyl chloride is low, there are concerns that operational problems due to a decrease in heat resistance, problems such as crimping and blocking during winding, and the like may occur. For example, when the ratio of vinyl chloride is less than 65 parts by weight, there is a problem that the hardness and solvent resistance of the coating film are likely to be lowered. On the other hand, if the ratio is more than 90 parts by weight, the solubility in a solvent is lowered with a decrease in flexibility and an improvement in solvent resistance, which is not preferable.

The ratio between vinyl chloride and vinyl acetate can be calculated from the following formula I.
[Formula I]
Glass transition temperature of vinyl chloride-vinyl acetate copolymer resin (Tg) = glass transition temperature of polyvinyl chloride (87 ° C.) × ratio of vinyl chloride (a) + glass transition temperature of polyvinyl acetate (29 ° C.) × vinyl acetate Ratio (b = 1-a)

  In the present invention, the glass transition temperature (Tg) of the vinyl chloride-vinyl acetate copolymer resin is preferably 65 ° C. or higher. When the glass transition temperature is less than 65 ° C., there are concerns that operational problems due to a decrease in heat resistance, and problems such as pressure bonding and blocking when the film is wound up may occur. The polymethyl methacrylate resin is a homopolymer and usually has a glass transition temperature of 105 ° C.

  The primer layer has a UV absorber such as benzotriazole or benzophenone for the purpose of imparting light resistance, various leveling agents (fluorine, siloxane, acrylic, etc.) for the purpose of improving coating properties, light It is also possible to blend stabilizers, antistatic treatment agents, antifoaming agents, antistatic agents, flame retardants, and the like. In addition, when used as a solvent for primer layer paints, aromatic solvents such as toluene and xylene, aliphatic solvents such as cyclohexane, methylcyclohexane and ethylcyclohexane, ester solvents such as ethyl acetate and butyl acetate, A ketone solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and anone, an alcohol solvent such as methanol, ethanol, isopropyl alcohol, n-propyl alcohol, and butanol, or a mixture of the above solvents can be used. Usually, a general-purpose solvent used for adjusting the solvent-based paint can be used.

  The primer layer can be formed by a known coating method such as gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, or screen printing method. After that, it is usually dried at a temperature of about 50 to 100 ° C.

  The coating thickness of the primer layer after drying is not particularly limited, but it is usually preferably in the range of 0.1 μm to 1.0 μm, more preferably in the range of 0.2 μm to 0.5 μm. When the coating thickness is less than 0.1 μm, when the decoration layer is formed on the primer layer, the adhesion layer is eroded by the solvent in the decoration layer paint and the adhesion layer is eroded. There is a problem that it tends to cause a decrease. On the other hand, if the coating thickness exceeds 1.0 μm, the effect of improving the adhesion with the base film and the decorative layer cannot be obtained, and on the contrary, the cost becomes high, and when the film for molding is stretched, Whitening tends to occur, which is not preferable.

  It is preferable to add inorganic or organic fine particles to the primer layer from the viewpoint of preventing pressure bonding and blocking when the molding film is wound. In this case, the blending amount (parts by weight) is preferably thermoplastic resin / inorganic or organic fine particles forming the primer layer = 99.8 / 0.2 to 95.0 / 5.0. When the blending amount of the fine particles exceeds 5.0 parts by weight, it is not preferable because the transparency is lowered and whitening is likely to occur when the molding hard coat film is stretched. On the other hand, there is a concern that a sufficient effect is not exhibited when the amount of the fine particles is less than 0.2 parts by weight.

  Examples of the inorganic fine particles include fine particles such as alumina, zinc oxide, and silica, and examples of the organic fine particles include fine particles such as polymethyl methacrylate and melamine / formaldehyde condensate. As the particle size, for example, it is preferable to use fine particles of 0.085 μm to 0.50 μm. When the particle diameter is less than 0.085 μm, blocking does not occur when the primer layer surface and the hard coat layer surface are rolled up, but this is not preferable because it is easy to press-bond. On the other hand, if the particle diameter is more than 0.50 μm, it is not preferable because the effect of preventing further pressure bonding or blocking cannot be obtained, and on the contrary, the cost is increased and the external haze is increased and the transparency is easily lowered.

  As described above, it is preferable that the vinyl chloride-vinyl acetate copolymer resin and the polymethyl methacrylate resin have a blending ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin and the polymethyl methacrylate resin of 80/20. By providing a primer layer contained in a range of ˜25 / 75, the primer layer is excellent in adhesion between both the base film and the decorative layer, and the base film and the decorative layer through the primer layer Adhesiveness can be improved. Moreover, the primer layer by the said structure has the favorable physical property (elongation) which follows the elongation of the base film at the time of shaping | molding.

The following examples illustrate the invention, but are not intended to limit the invention.
Unless otherwise specified, “parts” and “%” described below represent “parts by weight” and “% by weight”, respectively.
The urethane acrylate UV curable resin “8BR-500 (trade name)” used below has a weight average molecular weight of Mw 180,000, and the elongation is not cracked until the base substrate PET breaks, and the pencil hardness is HB. Yes, it corresponds to the ionizing radiation curable resin (a). The urethane acrylate UV curable resin “UN904 (trade name)” has a weight average molecular weight Mw of 4,100, an elongation of 4.0% and a pencil hardness of 2H, and corresponds to the ionizing radiation curable resin (b) described above. The acrylic polymer UV curable resin “8KX-012C (trade name)” has a weight average molecular weight Mw of 29,000, an elongation of 40%, and a pencil hardness of H, which is equivalent to the ionizing radiation curable resin (c) described above. To do.
In addition, said weight average molecular weight Mw was measured by the gel permeation chromatography (GPC). Polystyrene was used as a standard sample for GPC measurement.

[Example 1]
<Preparation of paint>
Urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37%, Taisei Fine Chemical) 80 parts and urethane acrylate UV curable resin “UN904 (trade name)” (solid content 100%, Negami 20 parts by industry), 5 parts by Irgacure 184 (photopolymerization initiator, manufactured by BASF), 0.5 parts by hindered amine compound “TINUVIN770DF (trade name)” (manufactured by BASF), and hydroxyphenyltriazine compound “ TINUVIN 479 (trade name) (manufactured by BASF), leveling agent RS75 (fluorine-based leveling agent, manufactured by DIC Corporation) 0.3 part and aluminum fine particles "ALMIBKH06 (trade name) ) ”(Average particle size 13 nm, made by CIK Nanotech) 3% solid content in butyl acetate / n-propyl alcohol = 50/50 (wt%) in UV curable resin paint Solid content concentration was prepared hard coat layer coating was sufficiently stirred and diluted to 20%.

<Hard coat film production>
For the elongation test, the paint was applied to one side of a 125 μm thick biaxially stretchable PET film “Lumirror U463 (trade name)” (manufactured by Toray) with a bar coater and dried with hot air at 80 ° C. for 1 minute. Then, it was hardened with an ultraviolet light quantity of 450 mJ / m ² . The thickness of the obtained coating film was 5 μm. Next, the paint was applied to one side of a 75 μm thick PMMA film (manufactured by Sumitomo) for pencil hardness and scratch resistance tests, dried with hot air at 80 ° C. for 1 minute, and then irradiated with ultraviolet light of 450 mJ / Cured at m ² . The thickness of the obtained coating film was 1.5 μm.

[Example 2]
<Preparation of paint>
Urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37%, Taisei Fine Chemical) 70 parts and urethane acrylate UV curable resin “UN904 (trade name)” (solid content 100%, Negami 30 parts by weight (manufactured by Kogyo Co., Ltd.) was used as the main agent, and the other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 3]
<Preparation of paint>
Urethane acrylate UV curable resin "8BR-500 (trade name)" (solid content 37%, Taisei Fine Chemical) 65 parts and urethane acrylate UV curable resin "UN904 (trade name)" (solid content 100%, Negami (Manufactured) 35 parts as a main ingredient, other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 4]
<Preparation of paint>
Urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical) 60 parts and urethane acrylate UV curable resin “UN904 (trade name)” (solid content 100%, Negami 40 parts by weight) (manufactured by Kogyo Co., Ltd.) were used as the main ingredients, and other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 5]
<Preparation of paint>
Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 45 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 5 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). Other additives were prepared according to Example 1. did.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 6]
<Preparation of paint>
Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). Other additives were prepared according to Example 1. did.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 7]
<Preparation of paint>
Acrylic polymer UV curable resin "8KX-012C (trade name)" (solid content 39%, manufactured by Taisei Fine Chemical) 35 parts and urethane acrylate UV curable resin "8BR-500 (trade name)" (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 15 parts of urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). Other additives were prepared according to Example 1. did.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 8]
<Preparation of paint>
30 parts of acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 20 parts of urethane acrylate UV curable resin “UN904 (trade name)” (solid content: 100%, manufactured by Negami Kogyo Co., Ltd.). Other additives were prepared according to Example 1. did.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 9]
<Preparation of paint>
Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical Co., Ltd.) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.) (Trade name) ”(average particle size 40 nm, manufactured by Big Chemie) was added to 3% solids. Other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 10]
<Preparation of paint>
Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotec) was added to 0.05% solids. Other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 11]
<Preparation of paint>
Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotech) was added to 1.0% solids. Other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 12]
<Preparation of paint>
Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) "(Average particle size 13 nm, manufactured by CIK Nanotech) was added to 2.0% solids. Other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 13]
<Preparation of paint>
Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotech) was added to 5.0% solids. Other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 14]
<Preparation of paint>
Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotech) was added to 10% solids. Other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 15]
<Preparation of paint>
Acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical) 40 parts and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content 37% , Manufactured by Taisei Fine Chemical) and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.). ) ”(Average particle size 13 nm, manufactured by CIK Nanotech) was added at 15% of solids. Other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test, pencil hardness, and scratch resistance was prepared in the same manner as in Example 1.

[Example 16]
<Preparation of paint>
It was prepared by excluding fine particles mainly composed of aluminum from the coating material of Example 6.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test and scratch resistance was produced in the same manner as in Example 1.

[Comparative Example 1]
<Preparation of paint>
100 parts of an acrylic polymer ultraviolet curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical Co., Ltd.) was used as a main agent, and other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test and scratch resistance was produced in the same manner as in Example 1.

[Comparative Example 2]
<Preparation of paint>
100 parts of urethane acrylate-based ultraviolet curable resin “8BR-500 (trade name)” (solid content 37%, manufactured by Taisei Fine Chemical Co., Ltd.) was used as a main agent, and other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test and scratch resistance was produced in the same manner as in Example 1.

[Comparative Example 3]
<Preparation of paint>
100 parts of urethane acrylate ultraviolet curable resin “UN904 (trade name)” (100% solids, manufactured by Negami Kogyo Co., Ltd.) was used as a main agent, and other additives were prepared according to Example 1.
<Hard coat film production>
Using the coating material, a hard coat film for elongation test and scratch resistance was produced in the same manner as in Example 1.

The hard coat films of Examples and Comparative Examples produced as described above were evaluated for the following items, and the results are summarized in Table 1.
(1) Pencil hardness Pencil hardness was measured by the test method shown in JIS K5600.
(2) Formability (elongation rate)
A test piece having a sample size width of 15 mm and a length of 150 mm is prepared using the above-described hard coat film for elongation test. The sample was pulled at a pulling rate of 50 mm / min and a distance between chucks of 100 mm, and the tensile elongation until cracking occurred in the hard coat layer on the surface was measured.
(3) Scratch resistance A fastness test against abrasion and friction of the hard coat layer was performed by a fastness tester (manufactured by Tester Sangyo). The hard coat layer coated on the PMMA film and steel wool # 0000 were rubbed against each other with a load of 102 g / cm ² × 10, and the difference between the haze values before and after the test was measured (hereinafter abbreviated as “ΔHaze”). To do.) The haze value was measured using a haze meter “HM150” manufactured by Murakami Color Research Laboratory.
ΔHaze = (Haze value after scratch resistance test) − (Haze value before scratch resistance test)
A lower ΔHaze indicates less scratches on the hard coat surface.

As is apparent from the results in Table 1 above, according to the examples of the present invention, a molding hard coat film having good moldability (elongation rate), surface hardness, and scratch resistance is obtained. Furthermore, when Example 2 and Example 6, Example 4 and Example 7 are compared, the resin 2 component (Examples 2 and 4) and the resin 3 component (Examples 6 and 7) have the same haze value. However, the resin 3 component shows higher elongation. Therefore, the resin 3 component is superior to the resin 2 component.
On the other hand, in Comparative Examples 1 to 3 in which any one of the ionizing radiation curable resins (a), (b), and (c) is used alone as a resin component of the hard coat layer, moldability (elongation rate) and At least one of the surface hardness and the scratch resistance is poor, and it is difficult to improve all of these properties.

[Example A]
On the surface opposite to the surface provided with the hard coat layer of the molding hard coat film (base film is the PMMA film) prepared in Example 1, the following primer layer paint was applied with a bar coater at 90 ° C. Drying with hot air for 1 minute formed a primer layer having a coating thickness of 0.3 μm (Evaluation Sample 1). Next, a 200 μm screen mesh was used on the primer layer of the evaluation sample 1, and a decorative layer coating (two-component reaction curable screen ink “SS16-000 (trade name)” (urethane-based, manufactured by Toyo Ink Manufacturing Co., Ltd.) ) Was solid-printed and dried with hot air at 60 ° C. for 30 minutes to form a decorative layer (solid print layer) having a coating thickness of 20 μm (Evaluation Sample 2).
Further, for the elongation test described later, on the surface opposite to the surface provided with the hard coat layer of the hard coat film for molding using the biaxially stretchable easily-formed PET film prepared in Example 1 as a base film, In the same manner, a primer layer was formed (Evaluation Sample 3).

<Preparation of primer layer paint>
Vinyl chloride-vinyl acetate copolymer resin “Solvine C (trade name)” (glass transition point 70 ° C., manufactured by Nissin Chemical Industry Co., Ltd.) with a mixed solvent consisting of ethyl acetate / methyl isobutyl ketone = 40/60 (parts by weight) Dissolved to prepare a solution having a solid content of 15%. Next, 50 parts of dissolved vinyl chloride-vinyl acetate copolymer resin “Solvine C” and polymethyl methacrylate resin “Acryt 0404EA-P (trade name)” (solid content 40%, glass transition point 105 ° C., Taisei Fine Chemical Co., Ltd.) 50 parts main product, leveling agent “BYK-354 (trade name)” (acrylic leveling agent, manufactured by Big Chemie Japan) 0.2 part, UV absorber “TINUVIN 928 (trade name)” (benzotriazole type) A primer layer coating material was prepared by adjusting 1.0 part of a UV absorber (manufactured by BASF) with toluene / methyl isobutyl ketone = 30/70 (wt%) so that the solid content in the coating material would be 5%.
In Example A, the compounding ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin “Solvine C” used for the primer layer coating material and the polymethyl methacrylate resin is 50/50.

[Example B]
For molding in the same manner as in Example A, except that the blending ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin “Solvine C” and the polymethyl methacrylate resin used for the primer layer coating was changed to 80/20. A hard coat film was produced.

[Example C]
For molding in the same manner as in Example A, except that the blending ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin “Solvine C” and the polymethyl methacrylate resin used for the primer layer coating was changed to 25/75. A hard coat film was produced.

[Example D]
To the primer layer coating, spherical silica “MEK-ST-ZL (trade name)” fine particle dispersion (solid content 30%, particle size 0.085 μm, manufactured by Nissan Chemical Industries, Toluene / ethyl acetate = 50 / A hard coat film for molding was prepared in the same manner as in Example A except that 2 parts of glass beads were added to 50 mixed solvents and beads dispersed).

[Example E]
A molding hard coat film was produced in the same manner as in Example A except that the primer layer was not provided (that is, a decorative layer was formed directly on the surface of the base film).

  The following items were evaluated for the molding hard coat films of Examples A to E produced as described above, and the results are summarized in Table 2 below.

(1) Solvent resistance A 3 cm square absorbent cotton is placed on the primer layer coating film, and a mixed solvent “NPR / toluene / ethyl acetate / MEK = 30/30/20/20 (parts by weight)” is dropped on the absorbent cotton. Then, after the solvent test for 3 minutes, the absorbent cotton was removed, the surface state of the primer layer was visually observed, and the surface state of each sample was evaluated in three stages. The evaluation criteria are as follows. In addition, (circle) and (circle) evaluation product determined that solvent resistance was a pass.
Evaluation criteria ◎: No change ○: Slightly whitened △: Fully whitened ×: Dissolved (2) Heat resistance Using a film on which a primer layer is formed, folded so that the primer layers face each other, thermal gradient tester HG-100 -2 "Toyo Seiki Co., Ltd.", pressure was applied at 3 kg / cm ² , time 10 seconds, the pressure-bonding surface was peeled off, and the temperature without surface roughness was defined as the heat resistant temperature. In addition, the heat-resistant temperature of 70 degreeC or more was determined to be acceptable.

(3) Adhesiveness Evaluation sample 1 for the base film and primer layer and adhesiveness in the hard coat film for molding obtained in each of the above examples, and evaluation sample 2 for adhesiveness between the primer layer and the decorative layer Evaluation was made by the following method.
For evaluation samples 1 and 2, 100 cross-cuts of 1 mm ² were prepared under constant temperature and humidity conditions (23 ° C., 53% RH) using a cross-cut peel test jig, and Sekisui Chemical Co., Ltd. adhesive tape No. 252 was affixed on it, pressed uniformly with a spatula, peeled in the direction of 90 degrees, and the remaining number of each layer was evaluated in four stages. The evaluation criteria are as follows, and ◎ and ○ evaluation products were judged to have passed. In addition, the item “PR layer” in Table 2 is an evaluation result of adhesion between the primer layer and the base film, and “decoration layer” is an evaluation result of adhesion between the primer layer and the decoration layer.
Evaluation criteria ◎: 100 pieces ○: 99 to 95 pieces Δ: 94 to 50 pieces ×: 49 to 0 pieces In addition, the adhesion between the hard coat layer and the base film (the item “HC layer” in Table 2) is also included. When evaluated by the same method, it passed in any of the examples.

(4) Transparency With respect to each molding hard coat film produced in each example, the total light transmittance was measured by the test method shown in JIS K7136. The evaluation criteria are as follows, and ◎ and ○ evaluation products were judged to have passed transparency.
Evaluation criteria ◎: 92% or more ○: 91% or more and less than 92% ×: Less than 91% (5) Elongation Using the above-described film for elongation test (evaluation sample 3), a test piece of size 15 mm × length 150 mm Make it. The sample was pulled at a pulling rate of 50 mm / min and a distance between chucks of 100 mm, and the tensile elongation until cracking occurred in the hard coat layer on the surface was measured.

(6) Pencil hardness About each molding hard coat film produced in each Example, pencil hardness was measured by the test method shown by JISK5600. Table 2 shows the hardness with no scratch on the surface. (7) Winding suitability For each molding hard coat film prepared in each example, each sample was cut into 10 cm squares, and two sets of samples each having a primer layer surface and a hard coat layer surface were overlaid, and the temperature was 40 ° C. After being stored for 48 hours in the above environment, the sample was taken out, and evaluated according to four levels according to the pressure state of the front and back surfaces and the surface state of each surface when the sample was peeled off. The evaluation criteria are as follows, and the applicability of winding up ◎ and ○ evaluation products was determined to be acceptable.
Evaluation criteria ◎: Crimping, no surface roughness ○: Crimping is somewhat, but there is no surface roughness △: Crimping is strong, no surface roughness ×: Crimping is strong, surface roughness is large

As is apparent from the results in Table 2 above, the primer layer is excellent in adhesion between the base film and the decorative layer, and in addition to moldability (elongation), hardware (pencil hardness), and winding ability. Further, a molding hard coat film excellent in solvent resistance, heat resistance and transparency can be obtained.
Moreover, in Example E which formed the decorating layer directly on the base film surface, without providing the said primer layer, solvent resistance and adhesiveness with a decorating layer fall significantly. Also, problems such as crimping or blocking are likely to occur when the molding film is wound up.

Claims (10)

On the base film, the following ionizing radiation curable resin (a) and ionizing radiation curable resin (b) are mixed in an ionizing radiation curable resin (a): (b) ionizing radiation curable resin. A molding hard coat film provided with a hard coat layer formed by applying and curing a coating composition containing a resin mixed in a resin = 80: 20 to 60:40 (parts by weight) .
(a) An ionizing radiation curable resin having a weight average molecular weight Mw of 150,000 or more.
(b) An ionizing radiation curable resin having a weight average molecular weight Mw of 10,000 or less. The hard coating film for molding according to claim 1, wherein the coating composition further contains an ionizing radiation curable resin (c) below.
(c) An ionizing radiation curable resin having a weight average molecular weight Mw of more than 10,000 and less than 150,000. The hard coat film for molding according to claim 1 or 2, wherein the ionizing radiation curable resin (a) satisfies the following conditions.
Conditions: A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm ² is formed on a polyethylene terephthalate film is prepared. Next, a test piece having a width of 15 mm and a length of 150 mm was produced from the produced film, and the test piece was pulled at a tensile speed of 50 mm / min in an environment of a temperature of 25 ° C. and a humidity of 50% RH. The elongation rate until the coating film cracks is 50% or more, and the pencil hardness specified in JIS K5600 is B to H. The hard coat film for molding according to any one of claims 1 to 3, wherein the ionizing radiation curable resin (b) satisfies the following conditions.
Conditions: A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm ² is formed on a polyethylene terephthalate film is prepared. Next, a test piece having a width of 15 mm and a length of 150 mm was produced from the produced film, and the test piece was pulled at a tensile speed of 50 mm / min in an environment of a temperature of 25 ° C. and a humidity of 50% RH. The elongation rate until cracks occur in the coating film is 1% or more, and the pencil hardness specified in JIS K5600 is H to 4H. The hard coat film for molding according to any one of claims 2 to 4, wherein the ionizing radiation curable resin (c) satisfies the following conditions.
Conditions: A film in which a 1.5 μm coating film of an ionizing radiation curable resin cured with an ultraviolet light quantity of 50 to 1000 mJ / cm ² is formed on a polyethylene terephthalate film is prepared. Next, a test piece having a width of 15 mm and a length of 150 mm was produced from the produced film, and the test piece was pulled at a tensile speed of 50 mm / min in an environment of a temperature of 25 ° C. and a humidity of 50% RH. The elongation rate until cracks occur in the coating film is 20% or more, and the pencil hardness specified in JIS K5600 is HB to 2H.   The hard coat film for molding according to any one of claims 1 to 5, wherein the hard coat layer contains inorganic oxide fine particles having an average particle diameter of 5 to 50 nm.   The hard coat film for molding according to claim 6, wherein the inorganic oxide fine particles are mainly composed of aluminum.   The hard coat for molding according to claim 6 or 7, wherein the content of the inorganic oxide fine particles is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the solid content of the coating composition. the film.   A decorative layer is formed on the surface of the base film opposite to the surface provided with the hard coat layer via a primer layer, and the primer layer comprises a vinyl chloride-vinyl acetate copolymer resin and polymethyl methacrylate. The hard coat film for molding according to any one of claims 1 to 8, comprising a resin. The hard coat film for molding according to claim 9, wherein a blending ratio (parts by weight) of the vinyl chloride-vinyl acetate copolymer resin and the polymethyl methacrylate resin is in a range of 80/20 to 25/75. .