KR20150035753A - Energy ray-curable resin composition and weather-resistant hard coat film utilizing same - Google Patents

Abstract

The present invention provides an energy ray curable resin composition which forms a coating film having excellent hardness, scratch resistance, weather resistance and moisture resistance when cured, and a weather resistant hard coating film using the same. (A) an energy ray-curable oligomer; (B) at least one member selected from the group consisting of benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers; (C) a hindered amine light stabilizer; And (D) a photopolymerization initiator, wherein the component (B) is added in an amount of 2 to 12 parts by mass based on 100 parts by mass of the component (A) ) A photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 340 nm to 400 nm in a 0.01% by mass solution dissolved in methanol or acetonitrile, and (D2) a 0.001% by mass solution in methanol or acetonitrile Of at least one photopolymerization initiator having a maximum value of absorbance in a wavelength range of 220 nm to 280 nm of 0.1 or more.

Description

(ENERGY RAY-CURABLE RESIN COMPOSITION AND WEATHER-RESISTANT HARD COAT FILM UTILIZING SAME)

The present invention relates to an energy ray curable resin composition and a weather resistant hard coating film using the same

Hard coating films are widely used in display screens for displays, touch panels, and mobile phones. In particular, mobile products such as mobile phones and smart phones are increasingly used in outdoor applications. In such a hard coat film for outdoor use, excellent weather resistance is required which does not yellow when exposed to ultraviolet rays for a long time and does not peel off between the hard coat layer and the base material film. Therefore, for the purpose of imparting weatherability, it has been proposed to add an ultraviolet absorber or a light stabilizer to the hard coat layer (see, for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 9-157315

However, in the hard coating film proposed in Patent Document 1, curing hindrance is caused by adding an ultraviolet absorber or a light stabilizer, and there arises a problem that coating film hardness, abrasion resistance and substrate adhesion are lowered. This problem is conspicuous when a large amount of ultraviolet absorber or light stabilizer is added to cope with a higher level of weatherability.

On the other hand, in order to suppress the production cost of the mobile product, the production base of each component and the assembly base of the mobile product are often different from each other. Therefore, in the manufacturing and transportation of various components, In consideration of storability, accelerated tests for moisture resistance and weather resistance are usually conducted. Also in such a case, it is necessary to have excellent substrate adhesion property that does not cause peeling between the hard coat layer and the substrate film.

Therefore, even when a large amount of ultraviolet absorber or light stabilizer is added or under accelerated test, a hard coat film excellent in coat film hardness, scratch resistance, weather resistance and moisture resistance is strongly demanded from the industry.

Accordingly, an object of the present invention is to provide an energy ray curable resin composition which is excellent in coating film hardness, scratch resistance, weather resistance and moisture resistance when the above problems are solved and cured, and a weather resistant hard coating film using the same.

As a result of repeated research to solve the above problems, the present inventors have found that a resin composition containing a specific compound in a specific ratio and a hard coating film using the same solve the above problems, and have completed the present invention.

That is, in the energy ray-curable resin composition of the present invention,

[1] (A) an energy ray-curable oligomer; (B) at least one member selected from the group consisting of benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers; (C) a hindered amine light stabilizer; And (D) a photopolymerization initiator, wherein the component (B) is added in an amount of 2 to 12 parts by mass based on 100 parts by mass of the component (A) ) A photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 340 nm to 400 nm in a 0.01% by mass solution dissolved in methanol or acetonitrile; (D2) a photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 220 nm to 280 nm in a 0.001 mass% solution dissolved in methanol or acetonitrile.

[2] The component (A) is an energy ray-curable resin composition comprising a polyfunctional urethane (meth) acrylate oligomer having an energy ray-curable functional group number of 10 to 20.

[3] The energy ray-curable resin composition according to [1], wherein the energy ray-curable monomer is used as the component (E).

[4] The energy ray curable resin composition according to [1], wherein 1 to 15 parts by mass of the component (D) is added to 100 parts by mass of the component (A).

[5] The energy ray-curable resin composition according to [1], wherein the addition amount of (D1) is equal to or less than the addition amount of (D2).

[6] The energy ray curable resin composition according to [1], wherein the addition ratio of the component (D1) to the component (D2) is in the range of 3: 97 to 45:

The hard coat film of the present invention is a hard coat film,

[7] The energy ray-curable resin composition according to [1] is applied and cured on at least one side of the base film to form a hard coat layer.

[8] A hard coating film according to [7], wherein the yellowing degree (? B) after 12 cycles of the weather resistance test according to ASTM G-154 is less than 1.0.

[9] The hard coat film according to [7], wherein the substrate adhesion as defined in JIS K-5400 after 12 cycles of weather resistance test according to ASTM G-154 is 90/100 or more.

[10] The hard coating film according to [7], wherein the substrate has a substrate adhesion of 90/100 or more as defined in JIS K-5400 after 500 hours in an environment of a temperature of 60 ° C and a humidity of 90%.

According to the present invention, it is possible to provide an energy ray curable resin composition excellent in coating film hardness, scratch resistance, weather resistance and moisture resistance when cured, and a weather resistant hard coating film using the same.

Each of the energy ray-curable resin composition and weather-resistant hard coat film of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments, It is also within the scope of the present invention that modifications, improvements and the like are appropriately applied to the following embodiments based on the common knowledge of the present invention.

[Energy ray curable resin composition]

The energy ray-curable resin composition of the present invention comprises (A) an energy ray-curable oligomer; (B) at least one member selected from the group consisting of benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers; (C) a hindered amine light stabilizer; And (D) a photopolymerization initiator. Each component will be described in detail below.

[Component (A)] [

The component (A) used in the present invention is an energy ray-curable oligomer.

As the energy ray-curable oligomer, a (meth) acrylic oligomer having a three-dimensional network structure having two or more acryloyl groups in one molecule and being crosslinked and cured is particularly preferably used. Examples of the (meth) acrylic oligomer include urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate and melamine (meth) acrylate. These may be used alone, or two or more of them may be used in combination. And, (meth) acryl refers to acryl or methacryl, and (meth) acrylate refers to acrylate or methacrylate.

The energy ray-curable oligomer used in the component (A) preferably has a mass average molecular weight of 1,000 to 20,000. This is because when the weight average molecular weight is less than 1,000, flexibility is insufficient, and when it exceeds 20,000, the hardness of the coating film is insufficient. From the viewpoints of flexibility and coating film hardness, the mass average molecular weight is more preferably 1,000 to 10,000.

The energy ray-curable oligomer used in the component (A) preferably comprises a polyfunctional urethane (meth) acrylate oligomer having an energy ray-curable functional group number of 10 to 20. By using this oligomer, it is possible to maintain the flexibility while maintaining the hardness of the coating film. This is because when the number of energy ray-curable functional groups is less than 10, the hardness of the coating film is insufficient, and when it is more than 20, flexibility is insufficient. The energy ray-curable functional group number is more preferably in the range of 10 to 16 from the viewpoints of coating film hardness and flexibility.

[Component (E)] [

In the energy ray-curable resin composition of the present invention, in addition to the component (A), an energy ray curable monomer may be further used as the component (E). In this case, it is preferable that the proportion of the component (E) is less than 40 mass% with respect to the total of the components (A) and (E). By setting such a range, the adhesion of the substrate in the moisture resistance test described later can be further improved. Examples of the component (E) include dipentaerythritol hexa (meth) acrylate, trimethylolpropane (meth) acrylate, pentaerythritol tri (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol divinyl (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, and tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate. These may be used alone, or two or more of them may be used in combination.

In addition to the above component (E), it is also possible to use, as the component (E), dipentaerythritol polyacrylate, dipentaerythritol hexaacrylate, tricyclodecane dimethanol diacrylate, pentaerythritol triacrylate, It is also preferable to use a hydrophobic bifunctional or higher (meth) acrylate monomer such as acrylate, trimethylolpropane triacrylate or ditrimethylolpropane tetraacrylate. This is because, by using these monomers, the adhesion of the base material in the moisture resistance test described later can be further improved.

[Component (B)] [

The component (B) used in the present invention is at least one selected from a benzotriazole-based ultraviolet absorber and a triazine-based ultraviolet absorber. Since these have absorption in the region of UVA (wavelength: 320 to 400 nm), good results can be obtained in the weather resistance test using a UVA340 lamp described later. Since the absorption of the UVA region in the benzotriazole ultraviolet absorber is large, good results can be obtained in the weather resistance test. And,

Examples of the benzotriazole-based compound include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'- - (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5 '- (2- (octyloxycarbonyl) ethyl) (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole Benzotriazole, 2- (2'-hydroxy-3 ', 5'-di (dimethylbenzyl) phenyl) benzotriazole, 2- - (2'-hydroxy-5'-octyloxyphenyl) benzotriazole, 2,2'-methylene-bis (2- 2- (2'-hydroxy-3 '- (3,4,5,6-tetrahydrophthalimidylmethyl) -5'-methylbenzyl) ) And the like benzotriazole. These may be used alone, or two or more of them may be used in combination.

Representative examples of triazine compounds include 2- (4-hexyloxy-2-hydroxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- Hydroxyphenyl) -4,6-di (2,5-dimethylphenyl) -1,3,5-triazine, 2- (4-butoxy- Butoxyphenyl) -1,3,5-triazine, 2- (4-butoxy-2-hydroxyphenyl) -4,6-di (2,4- dibutoxyphenyl) Hydroxyphenyl) -4,6-di (2,4-dimethylphenyl) -1, 2-dihydroxyphenyl) , 3,5-triazine, 2- (4- (3-dodecyloxy-2-hydroxypropoxy) -2-hydroxyphenyl) , 3,5-triazine, 2,4-di (4-butoxy-2-hydroxyphenyl) -6- (4-butoxyphenyl) (4-butoxy-2-hydroxyphenyl) -6- (2,4-dibutoxyphenyl) -1,3,5-triazine. These may be used alone, or two or more of them may be used in combination.

The addition amount of the component (B) should be in the range of 2 to 12 parts by mass with respect to 100 parts by mass of the component (A). This is because when the amount is less than 2 parts by mass, weatherability is poor, and when the amount is more than 12 parts by mass, the coating film hardness and substrate adhesion are poor. Is preferably in the range of 2.5 to 10 parts by mass, more preferably 3 to 8 parts by mass from the viewpoints of weatherability, film hardness and substrate adhesion. When the energy ray-curable monomer is used as the component (A) in addition to the component (A), the amount of the component (B) Refers to an addition amount per 100 mass parts of the total amount of monomers.

[Component (C)] [

Component (C) used in the present invention is a hindered amine compound. By adding such a radical, radicals generated by ultraviolet irradiation can be efficiently captured, and weather resistance can be improved. As the component (C), for example, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-hexanoyloxy-2,2,6,6-tetramethylpiperidine, 4 - octanoyloxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, succinic acid-bis (2,2,6,6- Tetramethylpiperidine), sebacic acid-bis (2,2,6,6-tetramethylpiperidine), sebacic acid-bis (1,2,2,6,6-pentamethyl-4- 3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4,5] decane-2,4-dione, N-methyl- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, N-acetyl-3-dodecyl- , 6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione, phthalic acid-bis (1,2,2,6,6-pentamethyl- And tris (2,2,6,6-tetramethyl-4-piperidyl). These may be used alone, or two or more of them may be used in combination.

The amount of the component (C) to be added is preferably in the range of 0.05 to 5 parts by mass based on 100 parts by mass of the component (A). This is because when the amount is less than 0.05 part by mass, weatherability is poor, and when it is more than 5 parts by mass, the scratch resistance is poor. It is preferably in the range of 0.5 to 3 parts by mass from the viewpoint of weatherability and scratch resistance. When the energy ray-curable monomer is used as the component (E) in addition to the component (A), the amount of the component (C) Refers to an addition amount per 100 mass parts of the total amount of monomers.

[Component (D)] [

Component (D) used in the present invention is a photopolymerization initiator having a maximum value of absorbance at a wavelength of 340 nm to 400 nm in a 0.01% by mass solution in (D1) methanol or acetonitrile of 0.1 or more, (D2) And at least one photopolymerization initiator each having a maximum value of absorbance of 0.1 or more in a wavelength range of 220 nm to 280 nm in a 0.001 mass% solution dissolved in methanol or acetonitrile. It is one of the characteristics of the present invention that by adding these two types of photopolymerizable absorbents, a considerable synergistic effect can be obtained with respect to moisture resistance than when they are used alone.

The amount of the component (D) to be used in the present invention is preferably in the range of 1 to 15 parts by mass per 100 parts by mass of the total amount of the component (A). This is because when the amount is less than 1 part by mass, the coating film hardness and the substrate adhesion property are insufficient. When the amount is more than 15 parts by mass, adhesion of the substrate is insufficient due to inhibition of curing due to recombination of these components. More preferably in the range of 3 to 12 parts by mass in view of coating film hardness and substrate adhesion. When the energy ray-curable monomer is used as the component (A) in addition to the component (A), the amount of the component (D) Refers to an addition amount per 100 mass parts of the total amount of monomers.

[Component (D1)] [

The component (D1) used in the present invention refers to a photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 340 nm to 400 nm in a 0.01% by mass solution dissolved in methanol or acetonitrile. For example, 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, bis (2,4,6-trimethylbenzoyl) (2-benzyl-2-dimethylamino) -1- (4-morpholinophenyl) -butanone-1, bis (eta 5--2,4-cyclopentadien- 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholinophenyl) butanone, diphenyl ( 2,4,6-trimethylbenzoyl) phosphine oxide and the like. These may be used alone, or two or more of them may be used in combination.

(D1) may be commercially available, for example, IRGACURE 651, 907, 819, 369, 379, 1800, 784, DAROCURE 4265, Lucirin TPO (manufactured by BASF).

[Component (D2)] [

The component (D2) used in the present invention refers to a photopolymerization initiator having a maximum absorbance of 0.1 or more in a wavelength range of 220 nm to 280 nm in a 0.001 mass% solution dissolved in methanol or acetonitrile. Methyl-1- [4- (methylthio) phenyl] -2-methylpolinopropane-1-one, 2,2-dimethoxy-1,2-diphenylethane- Hydroxy-2-methyl-1-phenyl-propane-l- [2- (2-hydroxy- Methyl 2-methyl- [1- (4-methylvinyl) phenyl] propanone, and the like. These may be used alone, or two or more of them may be used in combination.

(D2) may be commercially available, for example, IRGACURE 184, 651, 500, 2959, 127, 754, 907, 1800, DARACURE 1173, MBF , KIP100F, ONE (manufactured by Lamberti), and the like.

The component (D) is preferably added in an amount equal to or less than the addition amount of the photopolymerization initiator having the component (D2), in terms of improving moisture resistance. The addition ratio of the component (D1) to the component (D2) is particularly preferably in the range of 3: 97 to 45: 55 in mass ratio. Although the component (D) is one type of photopolymerization initiator and has a photopolymerization initiation wavelength region of the component (D1) and the component (D2), in the present invention, at least the component (D1) It is necessary to use two kinds of them. Therefore, even when one kind of photopolymerization initiator having the components (D1) and (D2) is used, another kind of another photopolymerization initiator must be used. By containing two kinds of photopolymerization initiators in this manner, even an energy ray curable resin composition having an ultraviolet ray absorbing ability can provide a coating film excellent in scratch resistance and excellent in moisture resistance when cured.

The energy ray curable resin composition of the present invention may contain other resins, solvents, photopolymerization initiators, leveling agents, antifoaming agents, antioxidants, polymerization inhibitors, crosslinking agents, pigments, Additives such as antifouling agents, fine particles, lubricants, fluorescent whitening agents, antistatic agents, flame retardants, antibacterial agents, antifungal agents, plasticizers, flow regulators, dispersants and mold release agents, Function may be given.

Examples of the photopolymerization initiator include amine compounds, carboxylic acid compounds, and polyfunctional thiol compounds. These may be used alone, or two or more of them may be used in combination. The solvent is not particularly limited, but any solvent that does not contain a functional group capable of reacting with the component (A) can be preferably used.

Preferred examples of the solvent include aromatic solvents such as toluene and xylene; Ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, and methoxypropyl acetate; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ether solvents such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether and diethylene glycol ethyl methyl ether ; And other known organic solvents.

The kind of the organic solvent to be used is determined in consideration of the solubility with the above components (A), (B), (C) and (D) added at the same time. However, Ketone, methyl isobutyl ketone, tetrahydrofuran and the like is preferably an organic solvent having a boiling point of 120 ° C or lower. These may be used alone, or two or more of them may be used in combination. The amount of the solvent to be used is not particularly limited, but it is preferable to adjust the viscosity of the composition so as to be a viscosity suitable for the coating system employed. The amount to be used is preferably 5 to 90 mass%, more preferably 10 to 85 mass%, and still more preferably 20 to 80 mass% of the entire composition.

Examples of the leveling agent include an acrylic compound, a high boiling point solvent, a fluorine-based compound, and a silicone-based compound, but fluorine-based compounds and silicone-based compounds are preferable in terms of finishing the surface to a mirror surface. Examples of the antioxidant include a phenol compound and the polymerization inhibitor includes methoquinone, methylhydroquinone and hydroquinone. Examples of the crosslinking agent include the isocyanates and the melamine compounds. Examples of the fine particles include inorganic fine particles such as silica and calcium carbonate, and organic fine particles such as polymethyl methacrylate and polystyrene. The antifouling agent may be a fluorine-based compound, a silicon-based compound or a mixture thereof, and a fluorine-based compound is preferable in view of the antifouling performance.

The energy ray-curable resin composition of the present invention can be obtained by adding the components (A), (B), (C) and (D) described above and further optionally the component (E), the solvent and the additives in an arbitrary order Can be obtained. Hereinafter, in the present invention, the solution to which various components are added may be referred to as a hard coating liquid.

[Hard Coating Film]

The hard coating film of the present invention can be obtained by a process comprising a step of applying the energy ray curable resin composition of the present invention to at least one surface of a base film. Therefore, the hard coating film of the present invention includes a hard coat layer coated on both sides, a substrate film surface on which a hard coat layer is not coated, and a pressure-sensitive adhesive layer and a print layer coated.

Examples of the base film include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene film, polypropylene film, salopan, diacetylcellulose film, triacetylcellulose film, acetylcellulose butyrate film, A polyvinylidene chloride film, an ethylene-vinyl acetate copolymer film, a polystyrene film, a polycarbonate film, a polymethylpentene film, a polysulfone film, a polyetheretherketone film, a polyether sulfone film, a poly An ether imide film, a polyimide film, a fluororesin film, a nylon film, an acrylic resin film and the like can be used. For the purpose of improving the adhesion with the energy ray curable resin composition, the surface treatment of the surface by the application of the adhesive layer (easy adhesion layer), the sand blast method or the solvent treatment method, or the corona discharge Surface treatment such as treatment, chromic acid treatment, flame treatment, hot air treatment, plasma treatment, ozone / ultraviolet ray irradiation treatment, and the like may be performed. The base film may be provided with a pressure-sensitive adhesive layer or a printing or coating for imparting design properties to one or both sides before applying the energy ray curable resin composition.

The application may be carried out by a known method such as a gravure coating method, a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, a spin coating method, a flow coating method, A spray coating method, a screen printing method, an oval coating, or the like can be used.

If the viscosity of the energy ray-curable resin composition is higher than the viscosity suitable for application, the viscosity may be adjusted using a solvent. The usable solvents are as described above.

When a solvent is contained in the energy-curable resin composition, it is necessary to perform drying after application. The drying temperature may be determined in consideration of the length of the drying line, the line speed, the application amount, the amount of the residual solvent, the kind of the substrate, and the like. If the base material is a polyethylene terephthalate film, the general drying temperature is 50 to 100 占 폚. When there are a plurality of dryers in one line, the respective dryers may be set to different temperatures and wind speeds. In order to obtain a coating film having a good coating appearance, it is preferable to mild the drying conditions on the inlet side. The coating thickness is not particularly limited, but it is preferable that coating is performed so that the film thickness after drying becomes 1 to 20 m. More preferably 1 to 15 占 퐉, and still more preferably 1 to 10 占 퐉.

Examples of the active energy ray for curing the energy ray curable resin composition of the present invention include ultraviolet rays and electron beams. In the case of curing by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp or the like is used as a light source, and the amount of light and the arrangement of the light source are adjusted as necessary. When a high-pressure mercury lamp is used, it is preferable to cure the lamp 1 having an energy of 80 to 160 W / cm ^{2 at} a conveying speed of 5 to 60 m / min. In the case of curing by electron beam, it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.

The hard coat layer of the hard coat film of the present invention is preferably such that the pencil hardness specified in JIS K-5400 is adjusted to 2H or more, and further to 3H or more. If the pencil hardness is adjusted to a predetermined value or more, damage to the surface of the hard coat layer can be effectively prevented.

Such a hard coating layer is obtained by winding a steel wool of # 0000 on a 3 cm ² cylindrical jig and winding it in a state of 500 g in a dry state, 30 reciprocations, more preferably 50 reciprocations, particularly preferably 70 reciprocations, It is preferable to adjust it so as not to cause a defect when it is made abnormal. By adjusting in this manner, it is possible to secure the necessary scratch resistance.

It is more preferable that the hard coating film of the present invention has a yellowing degree (? B) of less than 1.0 and less than 0.5 after 12 cycles of the weather resistance test specified in ASTM G-154. The yellowing degree (? B) represents a value obtained by subtracting the b value (b0) before the test from the b value (b1) after the weathering test. Further, it is preferable that the adhesion of the base material after 12 cycles of the weather resistance test specified in ASTM G-154 is 90/100 or more based on JIS K-5400. By adjusting the yellowing degree (? B) and the substrate adhesion property in this way, it is possible to obtain a hard coat film having good weather resistance.

The hard coating film of the present invention preferably has a substrate adhesion of 90/100 or more, more preferably 100/100, as measured in JIS K-5400 after 500 hours in an environment of a temperature of 60 캜 and a humidity of 90%. By such adjustment, a hard coating film having good moisture resistance can be obtained.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples. In the examples, "part" means "part by mass" unless otherwise specified.

(Film hardness)

According to JIS K-5400, the pencil hardness of the hard coat film was measured using a pencil scratch tester. Specifically, a pencil was set at an angle of 45 degrees on a polyester film having a cured coating film to be measured, and a load of 1000 g was applied thereon and scratched about 5 mm, so that scratches were not formed more than 4 times in 5 times It is expressed by the hardness of the pencil.

(Scratch resistance)

As the steel resistance test, a steel wool of # 0000 was wound on a 3 cm ² cylindrical jig and wound thereon was placed on the hard coat layer of the present invention, and the weight of 500 g was reciprocated in a dry state. The number of times immediately before the scratch occurred was recorded.

(Weatherability)

UV rays were irradiated using a UVA340 lamp under an environment of 60 DEG C for 8 hours using a QUV ultraviolet fluorescent accelerator (manufactured by Q-LAB) according to ASTM G-154, and condensation was observed for 4 hours under an environment of 50 DEG C, . This cycle was performed for 12 cycles. The weatherability (? B) in the following Tables 1 to 4 was measured by using a spectrophotometric colorimeter (trade name: CM-5, manufactured by Konica Minolta Sensing Co., Ltd.) after 12 cycles. (Hereinafter referred to as weather resistance (adhesion) in Tables 1 to 4 described later) was evaluated based on JIS K-5400.

(Moisture resistance)

The substrate adhesion after 500 hours in an environment of a temperature of 60 占 폚 and a humidity of 90% RH (relative humidity) was evaluated based on JIS K-5400.

The components (A) to (E) used in the respective Examples and Comparative Examples are as follows.

(A1) Component: Aliphatic urethane acrylate oligomer (trade name: Art Resin UN-904, manufactured by Negami Chemical Industry Co., Ltd., energy radiation-curable functional group number: 10, mass average molecular weight: 4900).

(A2) Component: Aliphatic urethane acrylate oligomer (trade name: Art Resin UN-3320HS, manufactured by Negami Industrial Co., Ltd., energy radiation-curable functional groups: 15, mass average molecular weight: 4900).

(B1) Component: A benzotriazole-based ultraviolet absorber (trade name: ULS-1933D, manufactured by Ippona Kogyo Co., Ltd.).

Component (B2): Triazine-based ultraviolet absorber (trade name: Tinuvin 477, manufactured by BASF).

Component (C): Hindered amine light stabilizer (trade name: TINUVIN 765, manufactured by BASF).

Component (D1): bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, BASF).

(D2) Component: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (trade name: Irgacure 907, BASF).

Component (E): dipentaerythritol hexaacrylate monomer (trade name: A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd., number of energy ray-curable functional groups: 6, mass average molecular weight: 578).

Other ultraviolet absorbers: benzophenone-based ultraviolet absorbers (trade name: LS-907, manufactured by Ipponasha Kogyo Co., Ltd.).

Leveling agent: polyether-modified polydimethylsiloxane (trade name: BYK-331, manufactured by Big Chem Japan Co., Ltd.)

Example 1

0.25 parts by mass of a leveling agent and 75 parts by mass of methyl ethyl ketone (MEK) were added to 100 parts by mass of (A1), 5 parts by mass of (B1), 1 part by mass of (C), 3 parts by mass of (D1) and 4 parts by mass of (D2) , And 75 parts by mass of propylene glycol monomethyl ether (PGM) were added, stirred, and added to prepare a hard coating liquid having a solid content of 43%. Next, this coating liquid was applied to the surface of a PET film (trade name: Cosmo Shine A4300, manufactured by Toyobo Co., Ltd.) having a thickness of 188 占 퐉 using a wire bar, dried at 80 占 폚 for 2 minutes, cm < ² > to form a hard coat layer having a thickness of 6 mu m. The physical properties thereof are shown in Table 1.

Examples 2 to 17

A hard coat film was produced in the same manner as in Example 1 by using the energy ray curable resin compositions having the compositions shown in Tables 1 to 3, respectively. The physical properties of these hard coating films are shown in Tables 1 to 3.

Comparative Examples 1 to 6

A hard coating film was prepared in the same manner as in Example 1, using each of the hard coating solutions having the compositions shown in Table 4 below. The physical properties of these hard coating films are shown in Table 4.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

(evaluation)

From Tables 1 to 3, it can be understood that the pencil hardness is 3H in all of Examples 1 to 17 and the coating film hardness is excellent. Also, in the evaluation of the scratch resistance, all of them exceed 30 times, and it is understood that the scratch resistance is excellent. In Example 4, since the amount of the component (C) to be added was small, it was slightly inferior in weather resistance as compared with the other examples. In Example 8, it is understood that the moisture resistance is slightly insufficient because the amount of the component (D1) is larger than that of the component (D2). From Examples 8 and 17, it can be understood that moisture resistance is improved by changing a part of the component (A1) to the component (E).

On the other hand, in Table 4, it is understood that Comparative Example 1 is poor in weatherability because the amount of the component (B1) is small. In Comparative Example 2, it is understood that since the blending amount of the component (B1) is large, the abrasion resistance, the weather resistance, the substrate adhesion and the moisture resistance are inferior. In Comparative Example 3, since the component (C) is not added, it can be understood that the evaluation of the yellowing degree (? B) of the weatherability is poor. It can be understood that the components (D1) and (D2) are not used together in Comparative Examples 4 and 5, so that moisture resistance and scratch resistance are remarkably poor. Comparing Comparative Examples 4 and 5 with Example 1, it is understood that Example 1 significantly improves scratch resistance and moisture resistance by using the components (D1) and (D2) in combination. In Comparative Example 6, it is understood that the use of another ultraviolet absorber is inferior in weatherability and moisture resistance.

Claims (10)

(A) an energy ray-curable oligomer;
(B) at least one member selected from the group consisting of benzotriazole ultraviolet absorbers and triazine ultraviolet absorbers;
(C) a hindered amine light stabilizer; And
(D) a photopolymerization initiator
Wherein the energy ray-curable resin composition comprises:
The component (D) is added in an amount of from 2 to 12 parts by mass based on 100 parts by mass of the component (A), and the component (D) is dissolved in the solution of the component (D1) in methanol or acetonitrile, (D2) a maximum value of absorbance in a wavelength range of 220 nm to 280 nm in a 0.001 mass% solution dissolved in methanol or acetonitrile is 0.1 Or more of a photopolymerization initiator and at least one photopolymerization initiator. The method according to claim 1,
Wherein the component (A) is a polyfunctional urethane (meth) acrylate oligomer having an energy ray-curable functional group number in the range of 10 to 20. The method according to claim 1,
Further, as the component (E), an energy radiation curable monomer is used. The method according to claim 1,
Wherein the component (D) is added in an amount of 1 to 15 parts by mass based on 100 parts by mass of the component (A). The method according to claim 1,
Wherein the addition amount of (D1) is equal to or smaller than the addition amount of (D2). The method according to claim 1,
Wherein the addition ratio of the component (D1) to the component (D2) is in the range of 3: 97 to 45: 55 in mass ratio. A hard coating film formed by applying and curing the energy ray-curable resin composition according to claim 1 on at least one surface of a base film to form a hard coat layer. 8. The method of claim 7,
A weather-hardening test according to ASTM G-154, wherein the yellowing degree (? B) after 12 cycles is less than 1.0. 8. The method of claim 7,
A hard coat film having a base material adhesion of 90/100 or more as defined in JIS K-5400 after 12 cycles of weather resistance test according to ASTM G-154. 8. The method of claim 7,
Wherein the substrate has an adhesion to the substrate specified in JIS K-5400 after 500 hours in an environment of a temperature of 60 占 폚 and a humidity of 90% of 90/100 or more.