JP2017178999A - Hard coat coating composition and hard coat film for molding - Google Patents

Abstract

[PROBLEMS] To provide a hard coat film for molding excellent in moldability, scratch resistance, surface feeling, and touch feeling. The molding hard coat film contains, on a base film, 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. It has a hard coat layer formed by coating and forming a hard coat coating composition containing 25 parts by weight or more of oxide fine particles and a leveling agent. [Selection figure] None

Description

  The present invention manufactures a resin molded product whose surface is decorated or protected by printing or concavo-convex shape by an in-mold molding method, a film insert molding method, a three-dimensional laminate molding method, a vacuum molding method, a pressure molding method, or the like. The present invention relates to a hard coat coating composition suitably used for the above, and a molding coating film using the hard coat coating composition.

  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 coating 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, a three-dimensional laminate molding method, a vacuum molding method, a pressure molding method using a decorative film having a high design with a coating layer provided on a printed base film Etc. have been proposed.

  The in-mold molding method is a technique in which a decorative film is laminated on the surface of a resin molding by simultaneously performing vacuum molding and injection in an injection mold. In addition, the film insert molding method is, for example, after a decorative film is preliminarily heated (preliminary heating) and a preform of the decorative film is obtained by a vacuum molding method, a pressure molding method, hot pressing between molds, or the like. In the next process, a decorative film preformed in a mold by injection molding is placed, laminated with a resin molding by injection molding, and integrated.

  The three-dimensional laminate molding is a molding method in which a decorative sheet with an adhesive layer softened by heat is attached to a molded body in a vacuum / pressure state. In addition, the above vacuum forming method heats the decorative film in the mold (preliminary heating), then softens the decorative film, stretches it between the decorative film and closes it to the mold, and molds the mold shape. This is a molding method. In addition, the above-mentioned pressure forming method means that the decorative film is heated (preliminary heating) and softened in the mold as necessary, and then the decorative film is adhered to the mold by pressurization with a gas heated as necessary. And a molding method for shaping the mold shape.

  Conventionally, various configurations have been proposed as a molding hard coat film used in the molding method using the decorative film as described above (see Patent Documents 1 to 4 below).

JP 2009-274378 A JP 2012-81628 A JP 2012-193265 A JP 2012-512247 A

  As hard molding films for molding are used in various fields, sufficient moldability to follow three-dimensional molding (elongation: no cracks occur in the base film layer and coating layer even when stretched) In addition, since the hard coat film for molding on the surface of the resin molded product has many opportunities to come into contact with the human body, not only the moldability but also the strength is regarded as important. For example, in a molding hard coat film applied to a resin molded product such as a mobile phone, in order to prevent damage to the housing in use, in addition to moldability, for example, high scratch resistance that can be replaced with glass or the like Pencil hardness is also required. In addition, in applications such as mobile phones, it is required that the surface feel (tactile feeling) is also good. Therefore, a coating layer with a low friction coefficient is required.

  As a result of intensive studies, the present inventor has found that there is room for improvement in the scratch resistance of the conventional molding hard coat film, and also that there is room for improvement in the feeling of touch.

  Therefore, the present invention uses a hard coat coating composition having good moldability (extension), scratch resistance (strength), surface feeling (visibility) and touch feeling, and the hard coat coating composition. An object of the present invention is to provide a hard coat film for molding.

As a result of intensive studies to solve the above problems, the present inventors have used 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 in combination with an inorganic material. It has been found that by blending oxide fine particles and increasing the blending amount, a molding hard coat film having particularly excellent scratch resistance (strength) and good moldability and feel can be obtained. Further, it has been found that by using a leveling agent, the scratch resistance can be further improved and the touch comfort is also improved.
That is, the present inventor has found that the above problems can be solved by an invention having the following configuration.
The configuration of the present invention is as follows.

  The first invention contains an ionizing radiation curable resin (A) having a weight average molecular weight Mw of 150,000 or more and an ionizing radiation curable resin (B) having a weight average molecular weight Mw of 10,000 or less, and 25 inorganic oxide fine particles. It is a hard coat coating composition characterized by including a weight part or more and a leveling agent.

  According to a second invention, in the first invention, the mixing ratio (parts by weight) of the ionizing radiation curable resin (A) and the ionizing radiation curable resin (B) in the hard coat coating composition is 60. : It is the range of 40-20: 80, It is the hard coat coating composition characterized by the above-mentioned.

  A third invention is the hard coat paint composition according to the first or second invention, wherein the hard coat paint composition contains a reactive fluorine-based leveling agent as the leveling agent. .

  According to a fourth invention, in any one of the first to third inventions, the content of the leveling agent is an ionizing radiation curable resin (the ionizing radiation curable resin (A)) in the hard coat coating composition. And the ionizing radiation curable resin (B)) in a range of 0.3 to 1.0 part by weight per 100 parts by weight.

  A fifth invention is a hard coat coating composition according to any one of the first to fourth inventions, wherein the inorganic oxide fine particles have an average particle size in the range of 5 nm to 50 nm.

  A sixth invention is the hard coat paint composition according to any one of the first to fifth inventions, wherein the hard coat paint composition contains an ester organic solvent and an alcohol organic solvent as a solvent. It is a thing.

  In a seventh aspect based on the sixth aspect, the mixing ratio (parts by weight) of the ester organic solvent and the alcohol organic solvent in the hard coat coating composition is in the range of 80:20 to 40:60. It is a hard coat coating composition characterized by these.

  8th invention has a hard-coat layer formed by apply | coating the hard-coat-coating composition of any one of said 1st thru | or 7th invention on a base film, and forming it, It is a film.

  A ninth invention is the hard coat film for molding according to the eighth invention, wherein the hard coat layer has a thickness in the range of 0.5 μm to 3 μm.

  A tenth invention is the hard coat film for molding according to the eighth or ninth invention, wherein an acrylic film or a laminated film of acrylic and polycarbonate is used as the substrate film.

  By using the hard coat coating composition of the present invention, a molding hard coat film having good moldability (extension), scratch resistance (strength), surface feeling (visibility) and touch feeling is provided. be able to.

  In the hard coat coating composition, the mixing ratio (parts by weight) of the ionizing radiation curable resin (A) and the ionizing radiation curable resin (B) is in the range of 60:40 to 20:80. This is suitable for enhancing the effect of the present invention.

In the present invention, it is important for the hard coat coating composition to contain a leveling agent in order to further improve the effects of the present invention. As the leveling agent, it is particularly preferable to contain a reactive fluorine-based leveling agent.
Moreover, the content of the leveling agent is 100 parts by weight of the ionizing radiation curable resin (the sum of the ionizing radiation curable resin (A) and the ionizing radiation curable resin (B)) in the hard coat coating composition. The range of 0.3 to 1.0 part by weight is particularly suitable.

  Moreover, in this invention, it is suitable for the average particle diameter of the said inorganic oxide microparticles | fine-particles to be the range of 5 nm-50 nm.

In the present invention, it is preferable that the hard coat coating composition contains an ester organic solvent and an alcohol organic solvent as solvents in order to enhance the effects of the present invention.
In order to enhance the effect of the present invention, the mixing ratio (parts by weight) of the ester organic solvent and the alcohol organic solvent in the hard coat coating composition is in the range of 80:20 to 40:60. Is preferred.

Moreover, the hard coat film for molding having a hard coat layer formed by applying the hard coat paint composition according to the present invention on a base film has a thickness of 0.5 μm to 3 μm. A range is preferred.
Moreover, as said base film, it is suitable to use a polyethylene terephthalate (PET) film, an acrylic film, or a laminated (for example, two-layer) film of acrylic and polycarbonate, and a laminated film of acrylic film or acrylic and polycarbonate. A film is more preferable.

Hereinafter, although the form for implementing this invention is demonstrated in detail, this invention is not necessarily limited to the following embodiment.
In the description of the specification and the like, unless otherwise specified, “XX to ΔΔ” means “from XX to ΔΔ”.

The hard coat film for molding according to the present invention has a hard coat layer formed by applying the hard coat paint composition according to the present invention on a base film.
The hard coat coating composition according to the present invention contains an ionizing radiation curable resin (A) having a weight average molecular weight Mw of 150,000 or more and an ionizing radiation curable resin (B) having a weight average molecular weight Mw of 10,000 or less, The inorganic oxide fine particles (C) are contained in an amount of 25 parts by weight or more and a leveling agent.

[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, a laminated (for example, two-layer) film of acrylic and polycarbonate is preferably used. Can do. 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. Moreover, since the said acrylic film is excellent in the texture, it can be used especially suitably.
As the base film of the present invention, it is particularly preferable to use a polyethylene terephthalate (PET) film, an acrylic film, or a laminated film of acrylic and polycarbonate, and an acrylic film or a laminated film of acrylic and polycarbonate is used. More preferred.

  Although there is no restriction | limiting in particular about the thickness of the said base film, It should be the range of about 25 micrometers-150 micrometers from the relationship of the processing conditions of a hard-coat layer, and economical efficiency of a base film, mechanical strength, handling property, etc. Is preferred.

  Thermoplastic resin during surface treatment such as corona treatment or low-temperature plasma treatment, addition of a lubricant for the purpose of improving the running property of the film, or after film formation on the surface of the substrate film Alternatively, easy adhesion treatment using a thermosetting resin can be performed. In addition, for the purpose of imparting antistatic properties, antistatic treatment and the like can also be performed.

[Hard coat layer]
Next, the hard coat layer will be described.
In the present invention, the hard coat layer is formed by applying the hard coat coating composition according to the present invention on a base film.
As described above, the hard coat coating composition according to the present invention comprises an ionizing radiation curable resin (A) having a weight average molecular weight Mw of 150,000 or more and an ionizing radiation curable resin (B) having a weight average molecular weight Mw of 10,000 or less. It contains 25 parts by weight or more of inorganic oxide fine particles and a leveling agent.

  The resin contained in the hard coat coating composition according to the present invention can be used without particular limitation as long as it is a resin that forms a film. In particular, hardness (scratch resistance, pencil hardness) is imparted to the hard coat layer surface. In addition, it is possible to adjust the degree of cross-linking by the exposure amount of ultraviolet rays and the like, and it is possible to adjust the extensibility of the hard coat layer and the surface hardness (abrasion resistance, pencil hardness). It is preferable to use a mold 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, Polyol polyacrylates 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. Polyoxy (meth) acrylate, polyester (meth) acrylate, polyhydric alcohol, polyisocyanate and hydroxyl group-containing, which can be obtained by esterifying 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.

As described above, the characteristic constitutions of the hard coat coating composition of the present invention include an ionizing radiation curable resin (A) 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 ( B) is used together.
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 coating composition, an ionizing radiation curable resin (A) having a weight average molecular weight Mw of 150,000 or more and an ionizing radiation curable resin (B) having a weight average molecular weight Mw of 10,000 or less are mixed. As a result, it is possible to improve both the moldability (extension) and scratch resistance (strength) characteristics of the hard coat film for molding.

Among the ionizing radiation curable resins (A) having a weight average molecular weight Mw of 150,000 or more, an ionizing radiation curable resin having a pencil hardness of B to H as defined in JIS K 5600 is preferable.
Among the ionizing radiation curable resins (B) having a weight average molecular weight Mw of 10,000 or less, an ionizing radiation curable resin having a pencil hardness of H to 4H is preferable. Examples of such an ionizing radiation curable resin (B) include, as a commercial product, UN-3320HS (manufactured by Negami Kogyo Co., Ltd.), UN-904 (manufactured by Negami Kogyo Co., Ltd.), and the like.

  In the present invention, the mixing ratio (parts by weight) of the ionizing radiation curable resin (A) and the ionizing radiation curable resin (B) is preferably in the range of 60:40 to 20:80. If the mixing ratio is outside this range, the effect of using the ionizing radiation curable resin (A) and the ionizing radiation curable resin (B) in combination is difficult to obtain, and the moldability (extensibility) and scratch resistance ( It is difficult to improve any of the properties.

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

  The ionizing radiation curable resin used in the hard coat coating composition of the present invention is a phenol resin, a urea resin, a range that does not impair the effects of the present invention, that is, the moldability and scratch resistance, and the effects of surface feeling and touch. Thermosetting resins such as unsaturated polyester, epoxy, and silicon resin, and thermoplastic resins such as polyethylene, polypropylene, polystyrene, polycarbonate, and polyester can be used in combination.

  The hard coat coating composition of the present invention contains the ionizing radiation curable resin (A) having a weight average molecular weight Mw of 150,000 or more and the ionizing radiation curable resin (B) having a weight average molecular weight Mw of 10,000 or less. In addition, it is important to contain inorganic oxide fine particles and a leveling agent. In this way, the ionizing radiation curable resin (A) and the ionizing radiation curable resin (B) are used in combination, and the inorganic oxide fine particles are blended, and the blending amount is increased, so that particularly scratch resistance (strength) ), And a molding hard coat film having good moldability and surface feeling can be obtained.

In this case, the average particle size of the inorganic oxide fine particles is preferably 5 nm to 50 nm, more preferably 5 nm to 40 nm, and still more preferably the average particle size 10 nm to 40 nm. When the average particle size of the inorganic oxide fine particles is less than 5 nm, it is difficult to further improve the scratch resistance (strength). On the other hand, when the average particle size exceeds 50 nm, the transmittance and haze of the molding hard coat film are likely to be affected.
The average particle diameter of the inorganic oxide fine particles can be measured using, for example, a particle size distribution meter (manufactured by Nikkiso Co., Ltd., apparatus name: Nanotrac 150) using a dynamic light scattering method.

The inorganic oxide fine particles may be a single particle having an average particle diameter in the above range or a granulated product formed by granulating finer primary particles. Such primary particles preferably have an average primary particle size of 1 nm to 25 nm, more preferably 1 nm to 20 nm. In addition, an average primary particle diameter measures a specific surface area by BET method, for example using the specific surface area measuring apparatus ASAP-2010 (made by Shimadzu Corporation), and average primary particle diameter (nm) = 6 * 10 < ³ > / It can be calculated according to the equation (density (g / cm ³ ) × specific surface area (m ² / g)).

  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 needs to be 25 parts by weight or more in the hard coat coating composition. When the content of the inorganic oxide fine particles is less than 25 parts by weight, it is difficult to obtain a sufficient effect of improving scratch resistance. On the other hand, if the content of the inorganic oxide fine particles exceeds 50 parts by weight, the effect of improving the scratch resistance will reach its peak, and the elongation rate, surface feeling and touch feeling of the hard coat layer will decrease, and haze will increase. Therefore, the visibility of the molded body using the molding hard coat film may be impaired. Accordingly, the content of the inorganic oxide fine particles is desirably 50 parts by weight or less.
In the present invention, the content of the inorganic oxide fine particles is particularly preferably in the range of 30 to 45 parts by weight.

In the present invention, it is important that the hard coat coating composition further contains a leveling agent. By using the leveling agent, the scratch resistance can be further improved, and the surface feeling and the touch feeling are also improved.
The leveling agent used in the present invention is not particularly limited as long as the surface tension can be adjusted by blending in a small amount in the coating composition, but it is particularly preferable to contain a reactive fluorine-based leveling agent. .

  The reactive fluorine-based leveling agent has a fluorine group in which at least one hydrogen atom of an alkyl group such as a perfluoroalkyl group is substituted in the molecule and performs a polymerization reaction with an ionizing radiation curable resin. It is a leveling agent having a polymerizable group. Examples of such leveling agents include MegaFuck RS series (for example, MegaFac RS-90 and MegaFac RS-55) (manufactured by DIC Corporation), and Footgent 610AD (manufactured by Neos Corporation).

  By using a reactive fluorine-based leveling agent as the leveling agent, the effects of the present invention can be obtained more easily. By using such a reactive fluorine-based leveling agent, a higher-strength hard coat layer can be obtained after irradiation with ultraviolet rays or the like, and the scratch resistance can be further improved. Further, since it contains a fluorine group, even in a system in which inorganic oxide fine particles are blended in a high blending amount, the friction coefficient on the surface of the hard coat layer is lowered, and a good surface feeling and touch feeling can be obtained.

  In the present invention, the content of the leveling agent is 100 parts by weight of an ionizing radiation curable resin (the total of the ionizing radiation curable resin (A) and the ionizing radiation curable resin (B)) in the hard coat coating composition. It is preferable that it exists in the range of 0.3-1.0 weight part with respect to, Especially preferably, it exists in the range of 0.3-0.5 weight part. When the content of the leveling agent is less than 0.3 parts by weight, the effect of improving the scratch resistance, surface feeling and touch feeling cannot be sufficiently obtained. On the other hand, when the content of the leveling agent exceeds 1.0 part by weight, the non-hardening component is increased in the surface layer, so that the scratch resistance is lowered.

  Further, as other additives to be added to the hard coat coating composition, as long as the effects of the present invention are not impaired, an antifoaming agent, a surface tension adjusting agent (other than the leveling agent), an antifouling agent, an antioxidant, You may contain an antistatic agent, a ultraviolet absorber, a light stabilizer etc. as needed.

  The hard coat layer in the hard coat film for molding of the present invention is formed by coating and drying a paint obtained by dissolving and dispersing the hard coat paint composition in an appropriate solvent on the base film. The solvent can be appropriately selected according to the solubility of the ionizing radiation curable resin contained therein, and can be any solvent that can uniformly dissolve or disperse at least solids (resin, leveling agent, polymerization initiator, other additives). That's fine. Examples of such solvents include esters (methyl acetate, ethyl acetate, butyl acetate, etc.), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol, etc.), 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.), 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.

  In the present invention, it is particularly preferable that the hard coat coating composition contains the ester organic solvent and the alcohol organic solvent as solvents. In this way, by using a mixed solvent of an ester organic solvent and an alcohol organic solvent, it is possible to obtain appropriate erosion properties with respect to the base film, so that whitening can be prevented, and between the base film and the coating layer can be prevented. Strong adhesion and high visibility can be obtained.

  In this case, the mixing ratio (parts by weight) of the ester organic solvent and the alcohol organic solvent is preferably in the range of 80:20 to 40:60. When the mixing ratio is outside this range, it is difficult to obtain an appropriate effect of using the ester organic solvent and the alcohol organic solvent in combination. In addition, since the balance between the volatility and solubility of the solvent changes, the coating state of the coating layer deteriorates (generation of repelling, etc.).

  The hard coat layer coating method is not particularly limited, but it is easy to adjust the coating thickness, such as gravure coating, micro gravure coating, fountain bar coating, slide die coating, slot die coating, etc. It is possible to apply by a simple method. In addition, the coating film thickness of the coated hard coat layer can be measured by actually measuring with a micrometer.

  In the present invention, the film thickness (coating film thickness) of the hard coat layer is not particularly limited, but is preferably in the range of, for example, 0.5 μm to 3 μm, more preferably 1 to 3 μm. It is. When the thickness of the hard coat layer is thinner than 0.5 μm, it becomes difficult to obtain sufficient scratch resistance. Moreover, when the film thickness is thicker than 3 μm, it becomes difficult to obtain good extensibility.

In the hard coat film for molding of the present invention, the paint containing the hard coat paint composition is applied to a base film (acrylic film) with a dry coating thickness of 1 to 3 μm, and then cured by irradiation with ultraviolet rays or electron beams. When a test piece having a width of 15 mm and a length of 150 mm is prepared and pulled at a temperature of 120 ° C. and a tensile speed of 50 mm / min and a distance between chucks of 40 mm, a coating layer comprising the hard coat paint composition It is preferable that the elongation rate until cracks occur is 15% or more (based on the test method specified in JIS K5600-5-4).
As described above, if the elongation is 15% or more, sufficient moldability can be provided in many applications that require a combination of scratch resistance (strength) such as resin molded products such as mobile phones.

  Moreover, in the hard coat film for molding of the present invention, a decorative layer such as a printing layer or a coloring layer directly or via an appropriate primer layer on the side opposite to the side on which the hard coat layer of the base film is provided, or coloring -An adhesive film or the like may be provided. Further, an overcoat layer or the like can be further provided on the hard coat layer.

  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. Moreover, the said metal vapor deposition layer can be formed into a film by methods, such as sputtering.

  As described above, according to the present invention, the ionizing radiation curable resin (A) having a weight average molecular weight Mw of 150,000 or more and the ionizing radiation curable resin (B) having a weight average molecular weight Mw of 10,000 or less are contained. By using a hard coat coating composition containing 25 parts by weight or more of inorganic oxide fine particles and a leveling agent, moldability (extensibility) is good, scratch resistance (strength), surface feeling (visibility) and touch It is possible to provide a hard coat film for molding that is excellent in comfort.

  Moreover, since the effect of this invention can be further improved by making the said hard-coat coating material composition contain a reactive fluorine-type leveling agent as a leveling agent, it is an especially preferable embodiment.

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 coating layer paint>
60 parts of urethane acrylate UV curable resin “UN-3320HS (manufactured by Negami Kogyo Co., Ltd., weight average molecular weight 5000)” and 40 parts of urethane acrylate UV curable resin “8BR-500 (manufactured by Taisei Fine Chemical Co., Ltd., weight average molecular weight 250,000)” 5 parts of Irgacure 184 (photopolymerization initiator, manufactured by BASF), fine particles “ALPGM 30 wt% -H01 (average particle size 39 nm (average primary particle size 15 nm), CIK Nanotech) ) ", 0.5 part of Tinuvin 292 (BASF) as a UV absorber, and 0.4 part of MegaFac RS-90 (reactive fluorosiloxane leveling agent, DIC) as a leveling agent , Butyl acetate / n-propyl alcohol (NPA) = 50/50 (parts by weight) Solid content of the coating composition for external curable resin to prepare a coating layer coating was sufficiently stirred diluted to 20%.
<Production of hard coat film for molding>
The above coating layer coating is applied to one side of a 75 μm thick acrylic film with a bar coater, dried with hot air at 80 ° C. for 1 minute, and then cured with an ultraviolet light amount of 450 mJ / m ² to form a coating layer having a thickness of 2 μm ( Hard coat layer) was formed, and a molding hard coat film of this example was produced.

[Example 2]
Except that the main agent was changed to 80 parts of urethane acrylate UV curable resin “UN-3320HS (manufactured by Negami Kogyo Co., Ltd.)” and 20 parts of urethane acrylate UV curable resin “8BR-500 (manufactured by Taisei Fine Chemical Co., Ltd.)” In the same manner as in Example 1, a coating layer coating material and a molding hard coat film were prepared.

[Example 3]
Except that the main ingredients were changed to 40 parts of urethane acrylate UV curable resin “UN-3320HS (manufactured by Negami Kogyo Co., Ltd.)” and 60 parts of urethane acrylate UV curable resin “8BR-500 (manufactured by Taisei Fine Chemical Co., Ltd.)” In the same manner as in Example 1, a coating layer coating material and a molding hard coat film were prepared.

[Example 4]
A coating layer coating and a molding hard coat film were produced in the same manner as in Example 1 except that the base film was changed to an acrylic (15 μm) / polycarbonate (60 μm) bilayer film.

[Example 5]
A coating layer coating material and a molding hard coat film were produced in the same manner as in Example 1 except that the blending part of the leveling agent RS-90 was 0.3 part.

[Example 6]
Except that the main agent was changed to 85 parts of urethane acrylate UV curable resin “UN-3320HS (manufactured by Negami Kogyo)” and 15 parts of urethane acrylate UV curable resin “8BR-500 (manufactured by Taisei Fine Chemical)” In the same manner as in Example 1, a coating layer coating material and a molding hard coat film were prepared.

[Example 7]
Except that the main ingredients were changed to 35 parts of urethane acrylate UV curable resin “UN-3320HS (manufactured by Negami Kogyo)” and 65 parts of urethane acrylate UV curable resin “8BR-500 (manufactured by Taisei Fine Chemical)” In the same manner as in Example 1, a coating layer coating material and a molding hard coat film were prepared.

[Example 8]
A coating layer coating and a molding hard coat film were prepared in the same manner as in Example 1 except that the amount of the fine particles “ALPGM 30 wt% -H01” containing aluminum oxide as a main component was 25 parts.

[Example 9]
A coating layer coating and a molding hard coat film were prepared in the same manner as in Example 1 except that the amount of the fine particles “ALPGM 30 wt% -H01” containing aluminum oxide as a main component was 45 parts.

[Example 10]
The coating material for coating layers and moldings are the same as in Example 1 except that the leveling agent is changed from Megafac RS-90 to Megafac RS-55 (reactive fluorosiloxane leveling agent, manufactured by DIC). A hard coat film was produced.

[Example 11]
Coating layer coating and molding hard coat in the same manner as in Example 1 except that the leveling agent is changed to Surflon S-611 (fluorine leveling agent, manufactured by AGC Seimi Chemical Co.) which has no reactivity. A film was prepared.

[Example 12]
A coating layer paint and a molding hard coat film were prepared in the same manner as in Example 1 except that butyl acetate / n-propyl alcohol was changed to 80/20 (parts by weight).

[Example 13]
A coating layer paint and a molding hard coat film were prepared in the same manner as in Example 1 except that butyl acetate / n-propyl alcohol was changed to 40/60 (parts by weight).

[Comparative Example 1]
A coating layer coating and a molding hard coat film were prepared in the same manner as in Example 1 except that the leveling agent was not added.

[Comparative Example 2]
A coating layer coating and a molding hard coat film were prepared in the same manner as in Example 1 except that the amount of fine particles “ALPGM 30 wt% -H01” mainly composed of aluminum oxide was 20 parts.

[Comparative Example 3]
Except for using urethane acrylate UV curable resin “UN-3320HS (manufactured by Negami Kogyo Co., Ltd.)” as the main ingredient and 100 parts urethane acrylate UV curable resin “8BR-500 (manufactured by Taisei Fine Chemical Co., Ltd.)” as the main component. In the same manner as in Example 1, a coating layer paint and a molding hard coat film were prepared.

[Comparative Example 4]
Except for 100 parts of urethane acrylate UV curable resin “UN-3320HS (manufactured by Negami Kogyo Co., Ltd.)” as the main agent and urethane acrylate UV curable resin “8BR-500 (manufactured by Taisei Fine Chemical Co., Ltd.)” In the same manner as in Example 1, a coating layer coating material and a molding hard coat film were prepared.

  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.

(1) Elongation rate Each hard coat film for molding was used as a test piece having a sample size width of 15 mm × length of 150 mm, and the test piece was pulled at a temperature of 120 ° C. at a pulling speed of 50 mm / min and a distance between chucks of 40 mm. The tensile elongation (%) until cracks occurred in the coating layer was measured.
The evaluation criteria are as follows.
A: Elongation rate is 20% or more B: Elongation rate is 15% or more and less than 20%.
Δ: Elongation is 10% or more and less than 15%.
X: Elongation rate is less than 10%.

(2) Pencil hardness The pencil hardness was measured at a load of 1000 g in accordance with the test method shown in JIS K5600. The evaluation criteria are as follows.
◎: Pencil hardness 4H or more ○: Pencil hardness 3H
Δ: Pencil hardness 2H
X: Pencil hardness less than 2H

(3) Scratch resistance A fastness test against abrasion and friction of the coating layer was performed by a fastness tester (manufactured by Tester Sangyo Co., Ltd.). The hard coat surface of each molding hard coat film and steel wool # 0000 were rubbed against each other by 200 reciprocations at a load of 1,000 g / cm ² , and the surface of the hard coat layer was visually confirmed. The evaluation criteria are as follows.
(Double-circle): There is no generation | occurrence | production of a crack.
○: 5 or less scratches occur, but there is no practical problem.
(Triangle | delta): Although 6-10 scratches generate | occur | produce, it is in a practical range.
X: Innumerable scratches occur.

(4) Touch comfort Using Peeling / Slipping / Scratching TESTER HEIDON-14 manufactured by Shinto Kagaku Co., Ltd., the hard coat surface of each molding hard coat film and Bengot TF-30 are overlapped, load 500 g, speed 100 mm / min. The dynamic friction coefficient was measured by the above, and the tactile sensation (touch feeling) when the finger was slid was evaluated according to the following criteria.
A: The coefficient of dynamic friction is less than 0.20, and it is difficult to feel resistance when the finger is slid, and the tactile feeling (feeling to touch) is good.
○: The coefficient of dynamic friction is 0.20 or more and less than 0.30, and there is a slight resistance when the finger is slid, but the tactile sensation is not significantly affected.
(Triangle | delta): A dynamic friction coefficient is 0.30 or more and less than 0.5, a feeling of resistance is felt when a finger is slid, and it is inferior to touch.
X: The coefficient of dynamic friction is 0.5 or more, and when the finger is slid, the resistance is greatly felt and the tactile sensation is inferior.

(5) Feeling Each hard coating film for molding was cut into an area of 10 cm × 15 cm to prepare a sample film. A black glossy tape is bonded to the opposite surface of the sample film to the hard coat layer, the hard coat surface is the upper surface, and a three-wavelength daylight white fluorescent lamp (National Palook, F.L15EX-N15W) is illuminated as a light source. The reflected light was visually observed from above and evaluated for visibility. The evaluation criteria are as follows.
A: Good surface shape and excellent visibility.
○: The uniformity of the surface shape is slightly inferior, but the visibility is practically no problem.
(Triangle | delta): Although it is inferior to the uniformity of the surface, visibility can be used practically.
X: The surface uniformity is greatly inferior and the visibility is inferior.

As is clear from the results of Table 1 above, according to the examples of the present invention, high pencil hardness, scratch resistance, good surface feeling, and touch feeling are obtained while securing the elongation. Therefore, according to the Example of this invention, the hard coat film for shaping | molding which is excellent in all the characteristics of a moldability, surface strength, a surface feeling, and a touch feeling is obtained.
The mixing ratio (parts by weight) of the high molecular weight urethane acrylate UV curable resin “8BR-500” and the low molecular weight urethane acrylate UV curable resin “UN-3320HS” is in the range of 60:40 to 20:80. It is preferable to increase the effect of the present invention.
In addition, it is preferable to use a reactive fluorine leveling agent as the leveling agent in order to enhance the effect of the present invention.

  On the other hand, in Comparative Example 1 in which the leveling agent was not added to the hard coat paint, the evaluation was generally poor except for the elongation, and particularly the scratch resistance was inferior. Further, in Comparative Example 2 where the blending amount of the aluminum oxide fine particles was small, the strength of the hard coat surface was low, and particularly the scratch resistance was poor. In Comparative Example 3 using only the high molecular weight urethane acrylate UV curable resin “8BR-500” as the main agent, the evaluation of the elongation rate and surface feeling is good, but the pencil hardness and scratch resistance are very poor. It was. On the other hand, in Comparative Example 4 in which only the low molecular weight urethane acrylate UV curable resin “UN-3320HS” was used as the main agent, the evaluation of the elongation rate was particularly bad. In short, in the comparative example, it is not possible to obtain a molding hard coat film excellent in all of moldability, surface strength, surface feeling, and touch feeling.

Claims (10)

  Contains an ionizing radiation curable resin (A) having a weight average molecular weight Mw of 150,000 or more and an ionizing radiation curable resin (B) having a weight average molecular weight Mw of 10,000 or less, and 25 parts by weight or more of inorganic oxide fine particles and leveling A hard coat paint composition comprising an agent.   The mixing ratio (parts by weight) of the ionizing radiation curable resin (A) and the ionizing radiation curable resin (B) in the hard coat coating composition is in the range of 60:40 to 20:80. The hard coat paint composition according to claim 1.   The hard coat paint composition according to claim 1, wherein the hard coat paint composition contains a reactive fluorine leveling agent as the leveling agent.   Content of the leveling agent is 100 parts by weight of the ionizing radiation curable resin (total of the ionizing radiation curable resin (A) and the ionizing radiation curable resin (B)) in the hard coat coating composition. The hard coat coating composition according to any one of claims 1 to 3, wherein the hard coating composition is in a range of 0.3 to 1.0 part by weight.   The hard coat coating composition according to any one of claims 1 to 4, wherein an average particle diameter of the inorganic oxide fine particles is in a range of 5 nm to 50 nm.   The hard coat paint composition according to any one of claims 1 to 5, wherein the hard coat paint composition contains an ester organic solvent and an alcohol organic solvent as a solvent.   The mixing ratio (parts by weight) of the ester organic solvent and the alcohol organic solvent in the hard coat coating composition is in the range of 80:20 to 40:60. Hard coat paint composition.   A hard coat film for molding, comprising a hard coat layer formed by applying the hard coat paint composition according to claim 1 onto a base film.   The hard coat film for molding according to claim 8, wherein a film thickness of the hard coat layer is in a range of 0.5 μm to 3 μm.   The hard film for molding according to claim 8 or 9, wherein an acrylic film or a laminated film of acrylic and polycarbonate is used as the base film.