JP6391963B2 - Hard coat film for molding and method for producing the same - Google Patents

Description

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

  Resin-molded products are often used for portable information terminal devices such as mobile phones, notebook computers, home appliances, and automobile interior and exterior parts. 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 or screen printed on the surface of a three-dimensional resin molded product by injection molding or the like. 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, an in-mold molding method, a film insert molding method, or a vacuum molding method using a decorative film with high design in which a hard coat layer is provided on a printed base film has been proposed.

  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. Moreover, the said film insert molding method heats a decoration film (preliminary heating), and after obtaining the molding of a decoration film with a metal mold | die, the decoration film molding and resin which were preformed by injection molding as a next process In this method, the molded product is bonded and integrated. The vacuum molding method is a method in which the decorative film is heated (preliminary heating) and softened under vacuum, and then the decorative film is evacuated and bonded to the surface of the resin molding while being stretched ( (See Patent Document 1, Patent Document 2, etc.).

JP 2009-274378 A JP 2012-81628 A

  When a decorative film is produced by printing directly on a base film, the adhesion between the decorative layer (printing layer) and the base film tends to be insufficient, causing a problem of dropping off the decorative layer. For this reason, providing the primer layer which has adhesiveness with both a base film and a decoration layer between a base film and a decoration layer is common as a structure of a decoration film. When this decorative film is used as a film for molding, the physical properties (elongation) of following the elongation of the base film during molding, in addition to the adhesion between the base film and the decorative layer as the properties of the primer layer. Needed.

  However, in the primer layer made of, for example, a two-component urethane resin that is generally used in conventional decorative films, the adhesion of the base film and the decorative layer is good, but the base film is not suitable for molding. Since the physical property (elongation) following the elongation is insufficient, there is a problem that the decorative layer is broken at the time of molding. On the other hand, when a primer layer made of, for example, a polyester resin having physical properties (elongation) that follows the elongation of the base film at the time of molding is provided, the adhesion to the base film or the decorative layer is reduced, and There was a problem that the primer layer was eroded by the solvent component contained in the printing ink for forming the decorative layer.

  Therefore, the present invention has a primer layer that is excellent in adhesion between both the base film and the decorative layer, and has a moldability (elongation), a hard property, and a winding hard coat film that is excellent in winding properties. And it aims at providing the manufacturing method. In addition, the molding hard coat film of the present invention does not contain a halide and is environmentally friendly.

As a result of intensive studies to solve the above problems, the present inventor has found that the above problems can be solved by an invention having the following configuration.
That is, the present invention is as follows.

  The first invention is a molding hard coat film in which a decorative layer is formed on one surface of a base film via a primer layer, and a hard coat layer is formed on the other surface. It contains a urethane-modified acrylic resin and a urethane-modified polyester resin, and the blending ratio (parts by weight) of the urethane-modified acrylic resin and the urethane-modified polyester resin is in the range of 98/2 to 80/20. It is a hard coat film for molding.

  A second invention is a hard coat film for molding according to the first invention, wherein the primer layer contains inorganic fine particles or organic fine particles.

  According to a third invention, in the first or second invention, the urethane-modified acrylic resin is a resin obtained by graft polymerization of an acrylic resin and a urethane resin, and the urethane resin is a polyester urethane resin or a polycarbonate urethane. A hard coat film for molding, which is a resin.

  A fourth invention is the hard coat film for molding according to any one of the first to third inventions, wherein the hard coat layer contains an ionizing radiation curable resin.

  A fifth invention is the molding hard coat film according to any one of the first to fourth inventions, wherein the base film is a polyethylene terephthalate film, a polycarbonate film, or a polymethyl methacrylate film. is there.

  In a sixth aspect of the present invention, there is provided a primer layer paint containing a urethane-modified acrylic resin and a urethane-modified polyester resin on one surface of a base film in a blending ratio (parts by weight) of 98/2 to 80/20. After coating and drying, the other surface is coated with a coating for a hard coat layer containing an ionizing radiation curable resin and dried, and then the ionizing radiation curable resin is cured with ionizing radiation. A method for producing a hard coat film for molding, wherein a decorative layer is formed on the primer layer.

  According to the present invention, the urethane-modified acrylic resin and the urethane-modified polyester resin are contained in a blending ratio (parts by weight) of the urethane-modified acrylic resin and the urethane-modified polyester resin in the range of 98/2 to 80/20, Hard coat for molding that has a primer layer that has excellent adhesion between the base film and the decorative layer, and that does not contain halides that are also excellent in moldability (elongation), hard properties, and winding properties. A film can be provided.

It is sectional drawing which shows the layer structure of the hard-coat film for shaping | molding concerning this invention.

Hereinafter, although the form for implementing this invention is demonstrated in detail, this invention is not necessarily limited to the following embodiment.
As shown in FIG. 1, a molding hard coat film 5 according to an embodiment of the present invention has a decorative layer 3 formed on one surface of a base film 1 with a primer layer 2 interposed therebetween. A hard coat layer 4 is formed on the other surface.
As will be described below, the base film, primer layer, and hard coat layer constituting the hard coat film for molding of the present invention contain no halide.

[Base film]
First, the base film 1 will be described.
In the present invention, the base film 1 of the molding hard coat film 5 is preferably a film that can be thermoformed and has a low elongation stress and can be stretched with a weak force. Specifically as a base film 1, a polyethylene terephthalate film, a polymethylmethacrylate film, and a polycarbonate film can be illustrated preferably.

In the case of the polyethylene terephthalate film, a general-purpose biaxially stretched polyethylene terephthalate film may be used, but in order to obtain better moldability, it is particularly preferable to use a biaxially stretchable polyethylene terephthalate film. This biaxially stretchable polyethylene terephthalate film has a low heat softening temperature, can be stretched with a weak force, and is a relatively inexpensive material.
Moreover, both the said polycarbonate film and the said polymethylmethacrylate film are unstretched films, and can be utilized suitably for any shaping | molding method.

  In the present invention, the thickness of the base film 1 is not particularly limited, but the primer layer, the decorative layer, the processing conditions of the hard coat layer, and the economics, mechanical strength, handling properties, etc. of the base film. Therefore, it is preferably in the range of 25 μm to 250 μm, more preferably in the range of 50 μm to 125 μm.

  When the surface of the base film 1 is subjected to surface treatment such as corona treatment or low-temperature plasma treatment, or when the base film 1 is formed, a benzotriazole type or benzophenone type for the purpose of imparting light resistance to the resin material Addition of ultraviolet absorbers, addition of lubricants for the purpose of improving film runnability, and easy adhesion treatment using a thermoplastic resin or a thermosetting resin during or after the formation of the base film 1 You can also. In addition, for the purpose of imparting antistatic properties, antistatic treatment and the like can also be performed.

[Primer layer]
Next, the primer layer 2 will be described.
In the present invention, the primer layer 2 contains a urethane-modified acrylic resin and a urethane-modified polyester resin as main components, and the blending ratio (parts by weight) is urethane-modified acrylic resin / urethane-modified polyester resin = 98 / 2-80. It is important to be in the range of / 20. More preferably, it is the range of 97 / 3-85 / 15, More preferably, it is the range of 95 / 5-90 / 10.
By adjusting the blending ratio of the urethane-modified acrylic resin and the urethane-modified polyester resin within the above range, excellent adhesion between the primer layer, the base film, and the decorative layer and good winding-up property are exhibited. In addition, by adjusting the blending ratio to the above range, the compatibility between the urethane-modified acrylic resin and the urethane-modified polyester resin is good, and the transparency of the molding hard coat film is not lowered, so that a high decorative property is expressed. To do.

  If the blending ratio of the urethane-modified acrylic resin to the urethane-modified polyester resin exceeds 98 parts by weight, for example, the adhesion between the decorating layer 3 using the polyester resin as a binder and the primer layer 2 tends to decrease, such being undesirable. In addition, when the blending ratio of the urethane-modified acrylic resin is less than 80 parts by weight, the decorative layer 3 having a binder with an acrylic resin, a urethane resin, or a UV resin, for example, a decrease in compatibility between the urethane-modified polyester resin and the urethane-modified acrylic resin. And the adhesion between the primer layer 2 and the primer layer 2 are liable to be lowered.

  In general, an acrylic resin and a polyester resin have no affinity. Therefore, when these resins are mixed, there is a compatibility problem such as separation or cloudiness, so that they are rarely used in combination. On the other hand, the present invention is that the acrylic resin and the polyester resin are modified with urethane so that the compatibility between the two becomes good in a specific blending ratio range, and the above-described adhesion and winding properties are excellent. It is a headline.

The urethane-modified acrylic resin is obtained by graft-polymerizing a urethane resin to the main chain of the acrylic resin, and the graft amount of the urethane resin with respect to the acrylic resin is about 90/10 to 40/60. In this case, the urethane resin is preferably a polyester urethane resin or a polycarbonate urethane resin.
On the other hand, the urethane-modified polyester resin is obtained by modifying a polyester resin with a urethane resin. The modification amount of the urethane resin with respect to the polyester resin is about 90/10 to 70/30.

In addition, the primer layer 2 is required to have operational problems (for example, running properties, rolls taken) when producing a hard coat film for molding, pressure bonding when blocking, blocking, etc. It is desirable to have the above heat resistance, and it is desirable to have some flexibility from the viewpoint of moldability. For this reason, it is preferable to adjust so that the load average of the glass transition temperature (Tg) of the urethane modified acrylic resin and urethane modified polyester resin used for a primer layer may be in the range of 50 to 80 degreeC.
The urethane-modified acrylic resin constituting the primer layer 2 is preferably a resin having a glass transition temperature of 55 ° C. or higher, and the polyester-modified urethane resin is preferably a resin having a glass transition temperature of 50 ° C. or lower. In consideration of this point, it is preferable to adjust so that the load average of the glass transition temperature (Tg) is in the range of 50 ° C to 80 ° C.

  The primer layer 2 has an ultraviolet 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 stabilizers, antistatic treatment agents, antifoaming agents, antistatic agents, flame retardants and the like can also be blended. Further, when the primer layer 2 is eroded by the internally added solvent of the decorative ink to cause poor adhesion, it is possible to add a necessary number of polymethyl methacrylate resins having excellent solvent resistance. Furthermore, when used as a solvent for the primer layer paint, 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 2 is formed by a known coating method such as gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, screen printing method, or the like. After installation, it is usually dried at a temperature of about 50 to 100 ° C.

  The coating thickness of the primer layer 2 after drying is not particularly limited, but it is usually preferably in the range of 0.1 μm to 7.0 μm, more preferably in the range of 0.5 μm to 5.0 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 7.0 μm, the cost is increased, and whitening tends to occur when the molding film is stretched.

  It is preferable to add inorganic or organic fine particles to the primer layer 2 from the viewpoint of preventing pressure bonding and blocking when the molding film is wound. In this case, the blending amount (part by weight) is the thermoplastic resin forming the primer layer 2 (including the resin when the resin of the present invention is included) / inorganic or organic fine particles = 99.8 / 0.2 to 90 It is preferably 0.0 / 10.0. If the blended amount of the fine particles exceeds 10.0 parts by weight, it is not preferable because the transparency is lowered and whitening is likely to occur during stretching of the molding hard coat film. On the other hand, there exists a possibility that the said effect may not fully be expressed as the compounding quantity of the said fine particle is less than 0.2 weight part.

  Examples of inorganic fine particles include fine particles such as alumina, zinc oxide, silica, titanium oxide, and cerium oxide. Examples of organic fine particles include fine particles such as acrylic, melamine / formaldehyde condensate, polyethylene, styrene acrylic, and polyester. It can be illustrated. As the particle size, for example, it is preferable to use fine particles of 0.05 μm to 0.50 μm. When the particle diameter is less than 0.05 μm, blocking does not occur when the primer layer surface and the hard coat layer surface are rolled up, but it 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.

[Decorative layer]
Next, the decoration layer 3 will be described.
The decorative layer 3 formed on the primer layer is composed of, for example, a picture layer and / or a concealing layer, a metal vapor deposition layer, and the like. 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 3 (for example, a pattern layer and / or a concealing layer) can be formed on the primer layer 2 by a known printing method such as gravure printing, offset printing, or screen printing with a printing ink. Although there is no restriction | limiting in particular in the formation thickness of the decoration layer 3, For example, 3-50 micrometers is preferable from a design viewpoint, 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 3 include polyester resins, vinyl chloride-vinyl acetate copolymer resins, polyurethane resins, acrylic two-component curable resins, cellulose resins, and acrylic resins. It can be illustrated. 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.

[Hard coat layer]
Next, the hard coat layer 4 will be described.
In the present invention, the resin contained in the hard coat layer 4 can be used without any particular limitation as long as it is a resin that forms a film. In particular, the surface of the hard coat layer is imparted with hardness (pencil hardness, scratch resistance). In addition, it is possible to adjust the degree of cross-linking by the amount of UV light exposure, and it is possible to adjust the hard coat layer extensibility and surface hardness (pencil hardness, scratch resistance). 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”). For example, it is not specifically limited, For example, it can select suitably from urethane acrylate-type resin, polyester acrylate-type resin, etc. Preferred examples of the ionizing radiation curable resin include those composed 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 present invention, a coating containing one or a mixture of the above ionizing radiation curable resins is applied to a base film (for example, polyethylene terephthalate film) with a dry coating thickness of 3 μm, and then cured by UV or EB irradiation. When a test piece having a width of 15 mm and a length of 150 mm was prepared 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, a crack occurred in the hard coat layer. The hard coat layer (ionizing radiation curable resin) having an elongation rate of 1 to 150% (based on the test method specified in JIS K5600-5-4) and a pencil hardness specified in JIS K5600 of B to 2H ) Is preferable.

  Moreover, as resin contained in the said hard-coat layer 4, other than the above-mentioned ionizing radiation curable resin, thermoplastic resins, such as polyethylene, a polypropylene, a polystyrene, a polycarbonate, polyester, an acryl, styrene-acryl, a fiber, Thermosetting resins such as phenolic resins, urea resins, unsaturated polyesters, epoxies, and silicon resins may be included within the range that does not impair the effects of the present invention, that is, the extensibility and hardness of the hard coat layer, and scratch resistance. .

  As the photopolymerization initiator for the ionizing radiation curable resin contained in the hard coat layer 4, known ones such as acetophenones and benzophenones can be used.

  In the present invention, it is preferable that the hard coat layer 4 contains inorganic oxide fine particles from the viewpoint of improving the surface hardness (scratch resistance). In this case, the average particle diameter of the inorganic oxide fine particles is preferably in the range of 5 to 50 nm, more preferably in the range of 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 the present invention, the content of the inorganic oxide fine particles is preferably 0.1 to 10.0 parts by weight with respect to 100 parts by weight of the solid content of the hard coat layer coating composition. When the content of the inorganic oxide fine particles is less than 0.1 parts by weight, it is difficult to obtain an effect of improving the surface hardness (abrasion resistance). On the other hand, if the content exceeds 10.0 parts by weight, the haze increases, and the design properties of the resin molded body using the molding hard coat film may be impaired.

Further, as other additives to be added to the hard coat layer 4, as long as the effects of the present invention are 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 addition to the ionizing radiation curable resin described above, the hard coat layer 4 is formed on the base film 1 with a paint in which inorganic oxide fine particles, a polymerization initiator, other additives and the like are dissolved and dispersed in an appropriate solvent. It is formed by coating and 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 solids (resin, polymerization initiator, and other additives). Examples of such 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 and methyl isobutyl. A ketone solvent such as ketone, an alcohol solvent, or a mixture of the above solvents can be used.

The coating thickness of the hard coat layer 4 is not particularly limited, but is preferably in the range of 1 to 10 μm, for example. 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 coating method of the hard coat layer 4 is not particularly limited, but the coating thickness can be adjusted such as gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, etc. Coating is possible with an easy method. In addition, the coating-film thickness of the hard-coat layer 4 can be measured by actually measuring with a micrometer.

  As described above, in the present invention, the urethane-modified acrylic resin and the urethane-modified polyester resin have a blending ratio (parts by weight) of the urethane-modified acrylic resin and the urethane-modified polyester resin of 98/2 to 80/20. By providing a primer layer contained in a range, the primer layer is excellent in adhesion between the base film and the decorative layer, and the adhesion between the base film and the decorative layer through the primer layer is improved. Can be improved. In addition, according to the present invention, a molding hard coat film excellent in moldability (elongation), hard property, and winding property can be obtained, and it is possible to cope with environmental aspects due to dehalogenated products.

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.

[Example 1]
<Preparation of hard coat layer paint>
40 parts of acrylic polymer UV curable resin “8KX-012C (trade name)” (solid content 39%, manufactured by Taisei Fine Chemical Co., Ltd.) and urethane acrylate UV curable resin “8BR-500 (trade name)” (solid content) 37 parts, 50% by Taisei Fine Chemical Co., Ltd., and 10 parts urethane acrylate UV curable resin “UN904 (trade name)” (100% solids, Negami Kogyo Co., Ltd.), Irgacure 184 (photopolymerization initiator) 5 parts, hindered amine compound “TINUVIN 770DF (trade name)” (BASF) 0.5 part, and hydroxyphenyltriazine compound “TINUVIN 479 (trade name)” (BASF) 0. 5 parts, leveling agent RS75 (fluorine leveling agent, manufactured by DIC) 0.3 part and aluminum 3 parts of a fine particle “ALMIBKH06 (trade name)” (average particle size 0.013 μm, manufactured by CIK Nanotech Co., Ltd.) with butyl acetate / n-propyl alcohol = 50/50 (parts by weight) The hard coating layer coating material was prepared by diluting until the solid content concentration in the coating material reached 20% and stirring sufficiently.
The acrylic polymer UV curable resin 8KX-012C has a weight average molecular weight Mw of 2,5000, an elongation of 40%, and a pencil hardness of H. The urethane acrylate ultraviolet curable resin 8BR-500 has a weight average molecular weight Mw of 180,000 and an elongation ratio of pencil hardness HB without cracking until the base substrate (polyethylene terephthalate film) is broken. The urethane acrylate ultraviolet curable resin UN904 has a weight average molecular weight Mw of 4,900, an elongation of 4.0%, and a pencil hardness of 2H.

<Preparation of primer layer paint>
Urethane-modified acrylic resin “Acryt 8UA-347A (trade name)” (grafted polymer of acrylic resin and polycarbonate-based urethane resin, manufactured by Taisei Fine Chemical, glass transition temperature 75 ° C.) 95 parts and urethane-modified polyester resin “Byron UR-3200” "Product name)" (manufactured by Toyobo, glass transition temperature -3 ° C) 5 parts, leveling agent "BYK-354 (trade name)" (acrylic leveling agent, manufactured by Big Chemie Japan) 0.2 parts, UV 1.0 part of an absorbent “TINUVIN 928 (trade name)” (benzotriazole ultraviolet absorber, manufactured by BASF) is toluene / methyl ethyl ketone = 50/50 (wt%) so that the solid content in the paint is 12%. The primer layer coating material was prepared.

<Decorative layer paint>
A two-component reaction curable screen ink “SS16-000 (trade name)” (urethane type, manufactured by Toyo Ink Manufacturing Co., Ltd.) was used.

<Production of hard coat film for molding>
1. For the heat resistance test and adhesion test, the primer layer paint is applied to one side of a 75 μm-thick polymethylmethacrylate film (manufactured by Sumitomo) with a bar coater, and dried with hot air at 90 ° C. for 1 minute. A primer layer having a film thickness of 0.3 μm was formed to prepare Sample No. 1 for the heat resistance test and the adhesion test between the primer layer and the substrate film. Furthermore, on the primer layer of sample No.1, using a 200 μm screen mesh, solid printing with the above decorative layer paint (screen printing ink), drying with hot air at 60 ° C. for 30 minutes, and decorating with a coating thickness of 20 μm A layer (solid print layer) was formed to prepare Sample No. 2 for an adhesion test between the primer layer and the decorative layer.
2. For the transparency, pencil hardness, and winding applicability tests, the primer layer coating was applied to one side of the polymethyl methacrylate film with a bar coater, dried in hot air at 90 ° C. for 1 minute, and the coating thickness was 0.3 μm. A primer layer is formed, and then the hard coat layer paint is applied to the back surface with a bar coater, dried with hot air at 80 ° C. for 1 minute, and then cured with an ultraviolet light quantity of 450 mJ / m ² , and a coating thickness of 3. A 0 μm hard coat layer was formed.
3. For the elongation test, the primer layer paint described above was applied to one side of a 125 μm-thick biaxially stretched polyethylene terephthalate film film “Lumirror U463 (trade name)” (manufactured by Toray Industries Inc.) with a bar coater. Dry with hot air for a minute to form a primer layer with a coating thickness of 0.3 μm, then apply the above hard coat layer paint on the back with a bar coater, dry with hot air at 80 ° C. for 1 minute, and then apply an ultraviolet light quantity of 450 mJ / M ² to form a hard coat layer having a coating thickness of 3.0 μm.

[Example 2]
For molding in the same manner as in Example 1 except that the blending ratio of the urethane-modified acrylic resin “Acryt 8UA-347A” and the urethane-modified polyester resin “Byron UR-3200” used for the primer layer coating was changed to 98/2. A hard coat film was produced.
[Example 3]
For molding in the same manner as in Example 1 except that the blending ratio of the urethane-modified acrylic resin “Acryt 8UA-347A” and the urethane-modified polyester resin “Byron UR-3200” used for the primer layer coating was changed to 80/20. A hard coat film was produced.

[Example 4]
A molding hard coat film was produced in the same manner as in Example 1 except that the coating thickness of the primer layer was changed to 0.1 μm.
[Example 5]
A molding hard coat film was produced in the same manner as in Example 1 except that the thickness of the primer layer was changed to 7.0 μm.

[Example 6]
Instead of the urethane-modified acrylic resin “Acryt 8UA-347A” used for the primer layer coating, “Acryt 8UA-301 (trade name)” (made by Taisei Fine Chemicals, glass transition temperature 60 ° C.), which is a polyester urethane resin. A hard coat film for molding was produced in the same manner as in Example 1 except that the above was changed.
[Example 7]
Example 1 except that it was changed to “Byron UR-8300 (trade name)” (manufactured by Toyobo, glass transition temperature 23 ° C.) instead of the urethane-modified polyester resin “Byron UR-3200” used for the primer layer coating. A molding hard coat film was produced in the same manner.

[Example 8]
Spherical silica “MEK-ST-ZL (trade name)” (solid content 30%, particle size 0.10 μm, manufactured by Nissan Chemical Co., Ltd.), which is inorganic fine particles, is added to the primer layer coating material in 0.2 part of the total solid content. A molding hard coat film was produced in the same manner as in Example 1 except for the addition.
[Example 9]
10 parts of spherical silica “MEK-ST-ZL (trade name)” (solid content 30%, particle size 0.10 μm, manufactured by Nissan Chemical Co., Ltd.), which is inorganic fine particles, was added to the primer layer coating. Except for the above, a molding hard coat film was produced in the same manner as in Example 1.

[Example 10]
Spherical silica “MEK-ST-ZL (trade name)” (solid content 30%, particle size 0.10 μm, manufactured by Nissan Chemical Co., Ltd.) as inorganic fine particles was added to the primer layer coating 20 parts in the total solid content. Except for the above, a molding hard coat film was produced in the same manner as in Example 1.
[Example 11]
For molding in the same manner as in Example 1, except that the blending ratio of the urethane-modified acrylic resin “Acryt 8UA-347A” and the urethane-modified polyester resin “Byron UR-3200” used for the primer layer coating was changed to 90/10. A hard coat film was produced.

[Example 12]
A hard coat film for molding in the same manner as in Example 1 except that a 75 μm thick polyethylene terephthalate film “Diafoil O300E (trade name)” (manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) was used instead of the polymethyl methacrylate film. Was made.
[Example 13]
Hard coating for molding in the same manner as in Example 1 except that a 125 μm thick polycarbonate film “Panlite PC-2151 (trade name)” (manufactured by Teijin DuPont Films Ltd.) was used instead of the polymethyl methacrylate film. A film was prepared.

[Comparative Example 1]
A molding hard coat film was prepared in the same manner as in Example 1 except that the urethane-modified acrylic resin “Acryt 8UA-347A” was used alone as the primer layer coating resin.
[Comparative Example 2]
A molding hard coat film was prepared in the same manner as in Example 1 except that the urethane-modified polyester resin “Byron UR-3200” was used alone as the primer layer coating resin.

[Comparative Example 3]
For molding in the same manner as in Example 1 except that the blending ratio of the urethane-modified acrylic resin “Acryt 8UA-347A” and the urethane-modified polyester resin “Byron UR-3200” used for the primer layer coating was changed to 75/25. A hard coat film was produced.
[Comparative Example 4]
Instead of the urethane-modified acrylic resin “Acryt 8UA-347A” used for the primer layer coating, “Acryt 8UA-239H (trade name)” (made by Taisei Fine Chemical, glass transition temperature 75 ° C.), which is a urethane urethane resin. A hard coat film for molding was produced in the same manner as in Example 1 except that the change was changed to “)”.

  The urethane-modified acrylic resin “Acryt 8UA-347A (trade name)” contained in the primer layer of Example 1 has a urethane resin grafting amount of 80/20 with respect to the acrylic resin. Further, in the urethane-modified polyester resin “Byron UR-3200 (trade name)”, the modification amount of the urethane resin with respect to the polyester resin is 75/25. The urethane-modified acrylic resin “Acryt 8UA-301 (trade name)” contained in the primer layer of Example 6 has a urethane resin graft amount of 60/40 with respect to the acrylic resin. Further, in the urethane-modified polyester resin “Byron UR-8300 (trade name)” contained in the primer layer of Example 7 above, the modification amount of the urethane resin with respect to the polyester resin is 85/15. The urethane-modified acrylic resin “Acryt 8UA-239H (trade name)” contained in the primer layer of Comparative Example 4 has a graft amount of the urethane resin to the acrylic resin of 80/20.

The following items were evaluated for the molding hard coat films of Examples and Comparative Examples produced as described above, and the results are summarized in Table 1 below. In Table 1, the polymethyl methacrylate film used as the base material is represented as “PMMA”, the polyethylene terephthalate film as “PET”, and the polycarbonate film as “PC”. Moreover, the urethane-modified acrylic resin used for the primer layer was described as “UA”, and the urethane-modified polyester resin as “UP”.
(1) Compatibility In preparing the primer layer coating material, the urethane-modified acrylic resin and the urethane-modified polyester resin were mixed and stirred in the diluent solvent, and then the transparency of the coating material was visually evaluated. The evaluation criteria are as follows. The ◎ and ○ evaluation products were judged to be compatible.
Evaluation standard ◎: Excellent transparency without turbidity of paint ○: Slight turbidity of paint but high transparency △: Slightly strong turbidity of paint and poor transparency ×: Strong turbidity of paint and no transparency at all (2) Heat resistance Using a film on which a primer layer is formed, folded so that the primer layers face each other, and with a thermal gradient tester HG-100-2 “manufactured by Toyo Seiki Co., Ltd.”, pressure 3 kg / cm ² , time 10 seconds After crimping, the crimp surface was peeled off, and the temperature without surface roughness was expressed as the heat resistant temperature. In addition, the heat-resistant temperature of 70 degreeC or more was determined to be acceptable.

(3) Adhesiveness For the primer layer of sample No.1 for adhesion test and the decorative layer of No.2 under constant temperature and humidity conditions (23 ° C, 53% RH), 1 mm using a cross-cut peel test jig 100 crosscuts of No. ² were prepared, adhesive tape No. 252 made by Sekisui Chemical Co., Ltd. was applied on it, pressed uniformly with a spatula, then peeled in the direction of 90 degrees, and the remaining number of each layer was divided into 4 levels. evaluated. The evaluation criteria are as follows, and ◎ and ○ evaluation products were judged to have passed. In addition, the item “PR layer” in Table 1 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 △: 94 to 50 pieces ×: 49 to 0 pieces

(4) Transparency The total light transmittance of each molding hard coat film prepared in each Example and Comparative Example 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 A: 92% or more B: 91% or more and less than 92% X: less than 91% (5) Elongation Using the above-described film for elongation test, a test piece having a size of 15 mm and a length of 150 mm is prepared. 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 and Comparative Example, pencil hardness was measured by the test method shown in JIS K5600. The hardness without scratches on the surface was indicated.
(7) Winding suitability About each molding hard coat film produced in each example and comparative example, each sample was cut into 10 cm squares, and two sets of samples were prepared by superimposing the primer layer surface and the hard coat layer surface, After storage for 48 hours in an environment at a temperature of 40 ° C., the sample was taken out, and evaluated according to four levels based on 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 were as follows, and ◎ and ○ evaluation products were judged to be acceptable for winding.
Evaluation criteria ◎: Crimping, no surface roughness ○: Crimping is somewhat, but there is no surface roughness
Δ: Strong crimping, no surface roughness ×: Strong crimping, large surface roughness

  As is apparent from the results of Table 1 above, according to the examples of the present invention, the primer layer is excellent in adhesion between the base film and the decorative layer, and the moldability (elongation), hardness ( In addition to (pencil hardness) and winding ability, a molding hard coat film excellent in heat resistance and transparency can be obtained. In Example 10 where the amount of fine particles added to the primer layer was 20 parts, the transparency deteriorated.

On the other hand, in Comparative Examples 1 and 2 in which any one of the urethane-modified acrylic resin and the urethane-modified polyester resin is used alone as the resin component of the primer layer, the adhesion with the decorative layer is particularly bad. Also, good characteristics cannot be obtained with respect to the heat resistance and winding property of the primer layer.
In addition, a urethane-modified acrylic resin and a urethane-modified polyester resin are used in combination as the resin component of the primer layer. In Comparative Example 3 in which the blending ratio is outside the scope of the present invention, the phase of the urethane-modified acrylic resin and the urethane-modified polyester resin is used. Since the solubility was poor and the paint was cloudy (evaluation x), no other performance evaluation was performed.
Further, in Comparative Example 4 in which the urethane resin of the urethane-modified acrylic resin is a polyether-based urethane resin other than the polyester-based urethane resin or the polycarbonate-based urethane resin, the adhesion with the decorative layer is particularly poor.

DESCRIPTION OF SYMBOLS 1 Base film 2 Primer layer 3 Decorating layer 4 Hard coat layer 5 Hard coat film for molding

Claims (5)

In the hard coat film for molding, in which a decorative layer is formed on one surface of a base film via a primer layer and a hard coat layer is formed on the other surface, the primer layer includes a urethane-modified acrylic resin and urethane Contains a modified polyester resin,
The urethane-modified acrylic resin is a resin obtained by graft polymerization of an acrylic resin and a urethane resin, and the urethane resin graft-polymerized to the acrylic resin is a polyester-based urethane resin or a polycarbonate-based urethane resin,
The mixing ratio of the urethane-modified acrylic resin and the urethane-modified polyester resin (parts by weight) is molded for a hard coat film, which is a range of 98 / 2-80 / 20. The hard coat film for molding according to claim 1, wherein the primer layer contains inorganic fine particles or organic fine particles. The hard coat film for molding according to claim 1 or 2 , wherein the hard coat layer contains an ionizing radiation curable resin. The hard coat film for molding according to any one of claims 1 to 3 , wherein the base film is a polyethylene terephthalate film, a polycarbonate film, or a polymethyl methacrylate film. One surface of the base film contains a urethane-modified acrylic resin and a urethane-modified polyester resin, and the urethane-modified acrylic resin is a resin obtained by graft polymerization of an acrylic resin and a urethane resin. urethane resin is a polyester urethane resin or a polycarbonate-based urethane resin, the urethane-modified polyester resin and the urethane-modified acrylic resin, the blending ratio (parts by weight) is contained in a range of 98 / 2-80 / 20 primer After coating and drying the layer coating, the other surface is coated with a hard coating layer coating containing an ionizing radiation curable resin and dried, and the ionizing radiation curable resin is cured with ionizing radiation. And then forming a decorative layer on the primer layer. Method of manufacturing over Tofirumu.

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