JPWO2014208749A1 - UV curable hard coat resin composition - Google Patents

Abstract

The present invention provides a hard coat film or a substrate suitable for fields requiring hardness, transparency, scratch resistance and blue light cut. A film using an ultraviolet curable hard coat resin composition containing an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule and a quinaldine dye, or A base material is used. [Selection figure] None

Description

  The present invention relates to an ultraviolet curable hard coat resin composition that imparts scratch resistance and blue light cutability on a plastic surface. More specifically, the present invention relates to a UV curable hard coat resin composition that is suitable for application to a plastic surface such as polyester, acrylic, triacetyl cellulose, polycarbonate, etc., and has excellent scratch resistance, chemical resistance, and blue light cut property. . The film and sheet coated with this hard coat resin composition are particularly suitable for displays such as smartphones, tablet PCs, notebook computers, and liquid crystal monitors with LED backlights because of their excellent blue light cutting properties. ing.

  Furthermore, the present invention provides a hard coat film capable of obtaining a molded product having the blue light cut characteristics without causing cracks in the curved surface portion of the molded product surface by selecting a flexible resin composition. give. It is particularly suitable for in-mold molding and film integral molding, and is also suitable for imparting a blue light cut function to sunglasses.

  At present, plastics are used in large quantities in various industries including the automobile industry, the home appliance industry, and the electrical and electronic industry. The reason why such a large amount of plastic is used is that, in addition to its processability and transparency, it is lightweight, inexpensive and has excellent optical properties. However, it has disadvantages such as being softer than glass and being easily scratched on the surface. In order to improve these drawbacks, it is a common means to coat the surface with a hard coating agent. As the hard coat agent, thermosetting hard coat agents such as silicone paints, acrylic paints, and melamine paints are used. Of these, silicone hard coat agents are particularly frequently used because of their high hardness and excellent quality. However, it has a long curing time, is expensive, and cannot be said to be suitable for a hard coat layer provided on a continuously processed film.

  In recent years, photosensitive acrylic hard coating agents have been developed and used (see Patent Document 1). The photosensitive hard coat agent is cured immediately upon irradiation with radiation such as ultraviolet rays to form a hard film, so the processing speed is fast, and it has excellent performance in terms of hardness and scratch resistance. Now it has become the mainstream in the hard coat field because it is cheaper. It is particularly suitable for continuous processing of films such as polyester. Examples of plastic films include polyester film, acrylic film, polycarbonate film, vinyl chloride film, triacetyl cellulose film, and polyethersulfone film. Polyester film and triacetyl cellulose film are widely used due to various excellent properties. ing. This polyester film is a glass anti-scattering film, an automobile light-shielding film, a whiteboard surface film, a system kitchen surface antifouling film, and electronic materials such as CRT flat TVs, touch panels, liquid crystal displays, plasma displays, etc. Widely used as a functional film. Moreover, the triacetyl cellulose film is used as a protective film of a polarizing plate used for a liquid crystal display. All of these are coated with a hard coat so as not to scratch the surface.

  In addition to plastic films, polycarbonate and acrylic sheets and substrates that are hard-coated are also used for liquid crystal related members around optical disks and backlights.

  Further, in recent years, a substrate coated with a hard coat agent has been required to have a function other than the performance as a hard coat called scratch resistance. For example, in a display body such as LCD or PDP provided with a film, the display body screen is difficult to see due to reflection, and the eyes are likely to get tired. It is necessary. As a method for preventing surface reflection, a film in which inorganic filler or organic filler is dispersed in a photosensitive resin is coated on the film, and the surface is made uneven to prevent reflection (AG treatment). High refraction on the film A method of preventing reflection by providing a multilayer structure in the order of a refractive index layer and a low refractive index layer and using light interference due to a difference in refractive index (AR processing), or AG / AR processing combining the above two methods (See Patent Document 2).

  In addition, a hard coat having an antistatic function has been developed, and there is a method of using a surfactant or a conductive metal oxide (see Patent Document 3).

  Furthermore, in recent years, with the spread of smartphones and tablet PCs, touch panels that directly touch the display with a finger are rapidly rising. Therefore, there is a demand for imparting so-called fingerprint resistance that fingerprints do not adhere to the surface of the display, are difficult to adhere, difficult to see even if attached, and easy to wipe off.

  As a method for improving fingerprint wiping as a fingerprint resistance, for example, a fluorine material or silicone oil is mixed in the coating composition to improve the surface water / oil repellency, or similar to sebum components. There is also a method in which the component is used in the coating composition so that the attached fingerprint becomes familiar, difficult to see, and easy to wipe (see Patent Document 4).

  In recent years, the backlight of a liquid crystal display has been replaced by an LED from CCFL, and the problem of blue light has been discussed. Blue light refers to light with a short wavelength of 380 nm to 495 nm among visible light, and is said to be emitted from a liquid crystal monitor that uses LEDs as a backlight. This blue light is a major cause of eye strain, and it is also said that it disturbs the biological rhythm and causes sleep disturbance. However, 460 nm light is one of the main emission wavelengths of the LED light source, and there has been a demand to cut light of 440 nm, which is the other wavelength, without largely cutting the wavelength.

  In particular, when a functional dye having a blue light cut function and an acrylate compound that is an ultraviolet curable resin are mixed, the dye is decomposed, or the acrylate compound that is an ultraviolet curable resin is hard to be cured, and the blue light cut function is not exhibited. There were problems such as. Because of these problems, films with a blue light cut function are currently on the market, but no ultraviolet curable hard coat resin composition is known.

Japanese Patent Laid-Open No. 9-48934 JP-A-9-145903 JP-A-10-231444 JP 2008-255301 A

Review Synthetic dyes, by Horiguchi Hiroshi, Sankyo Publishing Co., Ltd.

  An object of the present invention is to provide an ultraviolet curable hard coat resin composition having high transparency, high hardness, and excellent blue light cut function by stably dissolving a dye having a specific structure. And

  As a result of intensive studies to solve the above problems, the present inventors have found that an ultraviolet curable hard coat resin composition having a specific compound and composition can solve the above problems, and have reached the present invention.

（Ｒ_１は水素原子、カルボニル基、炭素数が１乃至３のアルキル基、置換基を有するスルホ基、置換基を有するアミド基を示す。）

（Ｒ_２、Ｒ_３はそれぞれ独立に水素原子、カルボニル基、炭素数が１乃至３のアルキル基、置換基を有するスルホ基、置換基を有するアミド基、ハロゲン原子、ヒドロキシル基を示す。）

（Ｒ_４、Ｒ_５はそれぞれ独立に水素原子、炭素数が１乃至３のアルキル基、スルホ基、置換基を有するスルホ基、置換基を有するアミノ基、ベンゾイル基、ニトロ基、ハロゲン原子を示す。）
（２）光重合開始剤を含有することを特徴とする（１）に記載の紫外線硬化型ハードコート樹脂組成物、
（３）希釈剤を含有することを特徴とする（１）または（２）に記載の紫外線硬化型ハードコート樹脂組成物、
（４）有機及び／又は無機粒子を含有することを特徴とする（１）乃至（３）のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物。
（５）（１）乃至（４）のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物よりなる硬化層を有する基材、
（６）透明ポリマーまたはそのフィルムである、（５）に記載の基材、
（７）全光線透過率が９０％以上であって、かつ、４４０ｎｍの透過率に対して４６０ｎｍの透過率が１０％以上高いことを特徴とする（５）または（６）に記載の基材、
（８）（１）乃至（４）のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物の硬化層を含む偏光板、
（９）（１）乃至（４）のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物の硬化層を含む液晶表示装置、

（１０）（１）乃至（４）のいずれか一項に記載の紫外線硬化型ハードコート樹脂組成物の硬化層を有する成型物。」、に関する。That is, the present invention
“(1) Contains a UV-curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule and a dye having any one of formulas (1) to (3)” UV curable hard coat resin composition,

(R ₁ represents a hydrogen atom, a carbonyl group, an alkyl group having 1 to 3 carbon atoms, a sulfo group having a substituent, or an amide group having a substituent.)

(R ₂ and R ₃ each independently represent a hydrogen atom, a carbonyl group, an alkyl group having 1 to 3 carbon atoms, a sulfo group having a substituent, an amide group having a substituent, a halogen atom, or a hydroxyl group.)

(R ₄ and R ₅ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a sulfo group, a sulfo group having a substituent, an amino group having a substituent, a benzoyl group, a nitro group, or a halogen atom. .)
(2) The ultraviolet curable hard coat resin composition according to (1), which contains a photopolymerization initiator,
(3) The ultraviolet curable hard coat resin composition according to (1) or (2), comprising a diluent,
(4) The ultraviolet curable hard coat resin composition according to any one of (1) to (3), comprising organic and / or inorganic particles.
(5) A substrate having a cured layer made of the ultraviolet curable hard coat resin composition according to any one of (1) to (4),
(6) The base material according to (5), which is a transparent polymer or a film thereof,
(7) The substrate according to (5) or (6), wherein the total light transmittance is 90% or more and the transmittance at 460 nm is 10% or more higher than the transmittance at 440 nm. ,
(8) A polarizing plate comprising a cured layer of the ultraviolet curable hard coat resin composition according to any one of (1) to (4),
(9) A liquid crystal display device comprising a cured layer of the ultraviolet curable hard coat resin composition according to any one of (1) to (4),

(10) A molded article having a cured layer of the ultraviolet curable hard coat resin composition according to any one of (1) to (4). ".

  According to the present invention, an ultraviolet curable hard coat resin composition having excellent blue light cut property, scratch resistance, high hardness and transparency can be provided.

  Hereinafter, the present invention will be described in detail.

  Examples of the ultraviolet curable polyfunctional (meth) acrylate (A) having at least two (meth) acryloyl groups in the molecule used in the present invention include polyethylene glycol di (meth) acrylate, tripropylene glycol di ( Di (meth) acrylate (e.g., KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), EO addition product of bisphenol A Di (meth) acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri ( Meta ) Acrylate, epichlorohydrin (ECH) modified glycerol tri (meth) acrylate, ethylene oxide (EO) modified glycerol tri (meth) acrylate, propylene oxide (PO) modified glycerol tri (meth) acrylate, EO modified phosphate tri (meth) acrylate, Caprolactone-modified trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (Meth) acrylate, tris (acryloxyethyl) isocyanurate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxytetra (meth) acrylate, silicone hexa (meth) acrylate, polyglycidyl compound (bisphenol A type epoxy) Resin, phenol novolac type epoxy resin, trisphenol methane type epoxy resin, polyethylene glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc.) and epoxy (meth) acrylate which is a reaction product of (meth) acrylic acid , Urethane acrylate which is a reaction product of diol, polyisocyanate and (meth) acrylate having a hydroxyl group, active hydrogen (hydric acid) And polyfunctional (meth) acrylate and a polyfunctional urethane (meth) acrylate which is a reaction product of a polyisocyanate compound having an amine and the like). You may use these individually or in mixture of 2 or more types. Preferred is a trifunctional or higher polyfunctional (meth) acrylate.

  Examples of the polyfunctional (meth) acrylate having active hydrogen include pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol tetra (meth). Pentaerythritols such as acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, methylols such as trimethylolpropane di (meth) acrylate, epoxy acrylates such as bisphenol A diepoxy acrylate, etc. Can be mentioned. Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferable. These polyfunctional (meth) acrylates having active hydrogen may be used alone or in admixture of two or more.

  As said polyisocyanate, the polyisocyanate comprised by a chain | strand-shaped saturated hydrocarbon, cyclic saturated hydrocarbon (alicyclic), and aromatic hydrocarbon can be used. Examples of such polyisocyanates include chain saturated hydrocarbon polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexyl). Isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, etc., cyclic saturated hydrocarbon (alicyclic) polyisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene Diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate Aromatic polyisocyanates such as 1,5-naphthalene diisocyanate. Of these, isophorone diisocyanate and hexamethylene diisocyanate are preferable. These polyisocyanates may be used alone or in combination of two or more.

  The polyfunctional urethane (meth) acrylate is obtained by reacting the polyfunctional (meth) acrylate having active hydrogen with a polyisocyanate. The polyisocyanate is usually in the range of 0.1 to 50 equivalents, preferably in the range of 0.1 to 10 equivalents as the isocyanate group equivalent, relative to 1 equivalent of the active hydrogen group in the polyfunctional (meth) acrylate having active hydrogen. is there. The reaction temperature is usually 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is the time when the polyisocyanate calculated by the method of reacting residual isocyanate with excess n-butylamine and back titrating with 1N hydrochloric acid is 0.5% by weight or less.

  A catalyst may be added for the purpose of shortening the reaction time. As the catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as triethylamine, diethylamine, dibutylamine, and ammonia, phosphines such as tributylphosphine and triphenylphosphine, pyridine, pyrrole, and the like. Examples of the acidic catalyst include metal salts such as copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide, Lewis acids such as aluminum chloride, 2-ethylhexanetin, Examples thereof include tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. When these catalysts are used, the amount added is usually about 0.1 to 1 part by weight per 100 parts by weight of the polyisocyanate.

  Further, in the reaction, it is preferable to use a polymerization inhibitor (for example, methoquinone, hydroquinone, methylhydroquinone, phenothiazine, etc.) in order to prevent polymerization during the reaction, and the amount used is 0.01 weight with respect to the reaction mixture. % To about 1% by weight, preferably about 0.05% to 0.5% by weight. The reaction temperature is 60 to 150 ° C, preferably 80 to 120 ° C.

  In the resin composition of the present invention, the amount of the ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule is 100% by weight based on the solid content of the resin composition of the present invention. In this case, it is usually 80 to 95% by weight, preferably 90 to 95% by weight.

  In the resin composition of the present invention, a (meth) acrylate compound other than the ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule is optionally used as necessary. Can do. Examples of (meth) acrylate compounds include (meth) acrylate monomers.

  Examples of the (meth) acrylate monomer include tricyclodecane (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate, benzyl ( (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, phenylglycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( And meth) acrylate and ethyl carbitol (meth) acrylate.

  In the present invention, it further contains an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule and a dye having a structure of formulas (1) to (3). The ultraviolet curable hard coat resin composition, which is a feature and contains the pigment, can provide an ultraviolet curable hard coat resin composition having high transparency, high hardness, and excellent blue light cut function. When a dye other than that described in Formula (1) is used, not only the blue light cut function is lowered, but also transparency is lowered, hardness is lowered, and the ultraviolet curable resin is not yet treated after the polymerization reaction. Problems such as an increase in reactive residual monomers occur.

（Ｒ_１は水素原子、カルボニル基、炭素数が１乃至３のアルキル基、置換基を有するスルホ基、置換基を有するアミド基を示す。）

(R ₁ represents a hydrogen atom, a carbonyl group, an alkyl group having 1 to 3 carbon atoms, a sulfo group having a substituent, or an amide group having a substituent.)

（Ｒ_２、Ｒ_３はそれぞれ独立に水素原子、カルボニル基、炭素数が１乃至３のアルキル基、置換基を有するスルホ基、置換基を有するアミド基、ハロゲン原子、ヒドロキシル基を示す。）

(R ₂ and R ₃ each independently represent a hydrogen atom, a carbonyl group, an alkyl group having 1 to 3 carbon atoms, a sulfo group having a substituent, an amide group having a substituent, a halogen atom, or a hydroxyl group.)

（Ｒ_４、Ｒ_５はそれぞれ独立に水素原子、炭素数が１乃至３のアルキル基、スルホ基、置換基を有するスルホ基、置換基を有するアミノ基、ベンゾイル基、ニトロ基、ハロゲン原子を示す。）

(R ₄ and R ₅ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a sulfo group, a sulfo group having a substituent, an amino group having a substituent, a benzoyl group, a nitro group, or a halogen atom. .)

  By using the dye represented by the formulas (1) to (3), the total light transmittance is 90% or more, and the transmittance at 460 nm is 10% or more higher than the transmittance at 440 nm. A characteristic film or substrate can be produced, and a film or substrate having a high surface hardness can be obtained. Moreover, since the transmittance | permeability of 460 nm is higher than 440 nm, the blue light cut film or base material which can cut light of 440 nm can be implement | achieved, suppressing the fall of the luminous efficiency of LED.

  As a method for synthesizing such a dye, for example, it can be produced by the method described in Non-Patent Document 1. In particular, it can be manufactured in accordance with the Quinoline Yellow manufacturing method described on page 309.

  Examples of the alkyl group having 1 to 3 carbon atoms in the formula (1) include a methyl group, an ethyl group, and a propyl group, and examples of the sulfo group having a substituent include sulfophenyl, sulfomethyl, and sulfoethyl. Examples of the amide group include a dimethylamide group. Examples of the alkyl group having 1 to 3 carbon atoms in the formula (2) include a methyl group, an ethyl group, and a propyl group. Examples of the sulfo group having a substituent include sulfophenyl, sulfomethyl, and sulfoethyl. Examples of the amide group possessed include a dimethylamide group. Examples of the alkyl group having 1 to 3 carbon atoms in the formula (3) include a methyl group, an ethyl group, and a propyl group, and examples of the sulfo group having a substituent include sulfophenyl, sulfomethyl, and sulfoethyl. Examples of the amide group include a dimethylamide group.

  Next, specific examples of the dye represented by the formula (1) are shown below.

  Next, specific examples of the dye represented by the formula (2) are shown below.

Next, specific examples of the dye represented by the formula (3) are shown below.

  Examples of the photopolymerization initiator used in the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 1, 1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane Acetophenones such as -1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-diethylthio Thioxanthones such as sandone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone And phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Specifically, from the market, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1- (4- (methylthio) phenyl) -2- (4-morpholinyl)-produced by BASF Corporation are available. 1-propanone), lucillin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) and the like can be easily obtained. Moreover, you may use these individually or in mixture of 2 or more types.

  In the resin composition of the present invention, the amount used when the photopolymerization initiator component is used is 0.5 to 10% by weight when the solid content of the resin composition of the present invention is 100% by weight. The amount is preferably 1 to 7% by weight.

  Moreover, said photoinitiator can also be used together with a hardening accelerator. Examples of the curing accelerator that can be used in combination include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethylbenzoate, dimethylaminoacetophenone, p-dimethylaminobenzoic acid isoamino ester, amines such as EPA, 2- And hydrogen donors such as mercaptobenzothiazole. The usage-amount of these hardening accelerators is 0 to 5 weight% when solid content of the resin composition of this invention is 100 weight%.

  Examples of the diluent that can be used in the present invention include lactones such as γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptalactone, α-acetyl-γ-butyrolactone, and ε-caprolactone; 2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, etc. Ethers; carbonates such as ethylene carbonate and propylene carbonate; Ketones such as ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and acetophenone; phenols such as phenol, cresol and xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butylcarbi Esters such as tall acetate and propylene glycol monomethyl ether acetate; Hydrocarbons such as toluene, xylene, diethylbenzene and cyclohexane; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane and monochlorobenzene; Petroleum such as petroleum ether and petroleum naphtha Organic solvents such as organic solvents, fluorinated alcohols such as 2H, 3H-tetrafluoropropanol, and perfluorobutyl methyl ether Le, hydrofluoroethers such as perfluorobutyl ethyl ether; methyl alcohol, ethyl alcohol, isopropyl alcohol, and n- propyl alcohol; and diacetone alcohol combines ketone and both alcohol performance thereof. You may use these individually or in mixture of 2 or more types.

  In the resin composition of the present invention, the amount used when the diluent component is used is in the range of 20 to 80% by weight, preferably 30 to 70% by weight, based on the total amount of the resin composition of the present invention. It is.

  Furthermore, in the resin composition of the present invention, organic and / or inorganic particles can be added to impart antiglare properties and antireflection functions. Examples of the organic particles include plastic melamine beads, acrylic beads, acrylic-styrene beads, polycarbonate beads, polyethylene beads, polystyrene beads, and the like. Examples of the inorganic particles include amorphous particles of silicon dioxide as silica, true spherical particles, and metal oxides such as tin oxide, zinc oxide, titanium oxide, and alumina. The particle size and addition amount of these particles can be adjusted according to the target haze and other characteristics.

  Furthermore, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor and the like are added to the photosensitive resin composition of the present invention as necessary. However, it is also possible to provide each intended functionality. Fluorine compounds, silicone compounds, acrylic compounds, etc. as leveling agents, benzotriazole compounds, benzophenone compounds, triazine compounds, etc. as UV absorbers, hindered amine compounds, benzoate compounds as light stabilizers Compounds, etc., antioxidants include phenolic compounds, and polymerization inhibitors include methoquinone, methylhydroquinone, hydroquinone, and the like.

  The resin composition of the present invention comprises the above-mentioned ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups, a dye exemplified by formula (1), a photopolymerization initiator, and a diluent. It can be obtained by mixing and mixing other components as required.

  The resin composition of the present invention thus obtained is stable over time.

  The UV curable hard coat resin composition of the present invention is applied onto a substrate so that the film thickness after drying of the resin composition is usually 0.1 to 20 μm, preferably 1 to 10 μm, and dried. It can obtain as a hard coat film by irradiating back ultraviolet rays and forming a cured film.

  When using a film for the substrate, examples of the substrate film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetylcellulose, polyethersulfone, and cycloolefin polymer. The film may be a thick sheet. The film to be used may be one provided with a handle or an easy-adhesion layer, or one subjected to surface treatment such as corona treatment.

  Examples of the coating method of the resin composition include bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, micro gravure coating, micro reverse gravure coater, and die coater. Examples include coating, dip coating, spin coating, and spray coating.

Although ultraviolet rays are irradiated for curing, an electron beam or the like can also be used. In the case of curing with 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 light amount, the arrangement of the light source, etc. are adjusted as necessary. When using a high-pressure mercury lamp, it is preferable to cure at 100 to 1000 mJ / cm ² at a conveyance speed of 5 to 60 m / min with respect to one lamp having energy of 80 to 160 W / cm ² . On the other hand, in the case of curing with an electron beam, it is not necessary to add a photopolymerization initiator, and it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.

  As a base material obtained by the above, a transparent polymer or its film is preferable. The transparent polymer or film to be formed is preferably a transparent polymer or film having high mechanical strength and good thermal stability. As a substance used as a transparent protective layer, for example, cellulose acetate resin such as triacetyl cellulose or diacetyl cellulose or film thereof, acrylic resin or film thereof, polyvinyl chloride resin or film thereof, nylon resin or film thereof, polyester resin or film thereof A film, a polyarylate resin or a film thereof, a cyclic polyolefin resin having a cyclic olefin such as norbornene or a film thereof, polyethylene, polypropylene, a polyolefin having a cyclo or norbornene skeleton or a copolymer thereof, a main chain or a side chain Examples include imide and / or amide resins or polymers or films thereof.

  The obtained base material can be bonded through a polarizing element made of a polyvinyl alcohol resin film, or a polarizing plate in which the polarizing element is laminated with triacetyl cellulose, an adhesive, or the like, for example. The film thus obtained becomes a hard coat film or substrate suitable for fields requiring hardness, transparency, scratch resistance and blue light cut in addition to the polarizing function when provided in a liquid crystal cell.

  Moreover, since a film, a lens, etc. can be resin-molded using the resin composition of the present invention, the resin composition of the present invention can be used even when such a molded part or molded body is produced.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited by these Examples. Moreover, unless otherwise indicated in an Example, a part shows weight%.

Formulation Example 1
500 cc Kolben, 60 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.), polyfunctional urethane acrylate (trade name: KAYARAD UX-5000, Japan 40 parts of Kayaku Co., Ltd.), 5 parts of 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF) and 66.7 parts of toluene are mixed and dissolved at room temperature to obtain a master solution having a solid content of 60%. 1 was produced.

Formulation Example 2
A mixture of the same amount of 0.1 wt% of the dye of Compound Example 1 having the highest absorbance at 448 nm and the dye of Compound Example 5 having the highest absorbance at 424 nm obtained using the formulation described in Non-Patent Document 1 was used. Part and 19.9 parts of toluene were mixed and dissolved to prepare a master liquid 2.

Formulation Example 3
A master solution 3 was prepared by mixing and dissolving 0.1 part of the dye of Compound Example 15 having the highest absorbance at 431 nm obtained using the formulation described in Non-Patent Document 1 and 19.9 parts of toluene.

Comparative Example 1
The master liquid 1 was applied onto an 80 μm triacetylcellulose film with a bar coater, dried for 2 minutes in an 80 ° C. dryer, and then cured with an ultraviolet light irradiation apparatus equipped with a 160 W high-pressure mercury lamp at an integrated light amount of 250 mJ / cm ² A hard coat film having a thickness of 4 to 5 μm was obtained.

Examples 1 to 6
The resin composition containing the materials shown in Table 1 below was coated on an 80 μm triacetylcellulose film with a bar coater, dried in an 80 ° C. dryer for 2 minutes, and then integrated with a UV irradiation device equipped with a 160 W high-pressure mercury lamp. It hardened | cured at 250 mJ / cm < ² > and obtained the blue light cut hard coat film with a film thickness of 4-5 micrometers. In Table 1, the unit indicates “part”.

Comparative Examples 2 to 4
Except for changing the dye used in Examples 1 to 3 to Yellow Dye Flavine FG manufactured by Nippon Kayaku Co., Ltd. having a maximum absorption wavelength at 420 nm that does not have the structure of the formulas (1) to (3) described in the present application. It implemented similarly and it was set as Comparative Examples 2-4.

  The following items were evaluated for the blue light cut hard coat films obtained in Examples 1 to 3 and Comparative Example, and the results are shown in Tables 2 and 3. Table 4 shows that the total light transmittance is 90% or more. The relationship between the transmittance at 460 nm when the transmittance at 440 nm is adjusted to 65% to 70% is shown.

(Pencil hardness)
According to JIS K 5400, the pencil hardness of the coated film having the above composition was measured using a pencil scratch tester. Specifically, on the polyester film having the cured film to be measured, the pencil is applied with a load of 750 g from the top at a 45 degree angle, and is scratched for about 5 mm. expressed.

(Total light transmittance)
Measurement was performed using HM-150 manufactured by Murakami Color Research Laboratory.

(Haze)
Measurement was performed using HM-150 manufactured by Murakami Color Research Laboratory.

(Chromaticity)
Hitachi, Ltd. U-4100 was used and L *, a *, and b * were measured with a halogen lamp.

(Abrasion resistance)
Steel wool # 0000 was used, and after 10 reciprocating wears at 1 reciprocation / load at 250 g / cm ² , the wear surface was observed and the following evaluation was performed.
Evaluation: ○: No scratch, ×: Scratch occurrence

(Adhesion)
100 squares were produced on the hard coat layer of the example at intervals of 1 mm with a cutter, and after the cellophane was firmly adhered, it was peeled off at a 90 degree direction, and the following evaluation was performed.
Evaluation: ○: 100/100 good adhesion, x: peeling occurred

  In Examples 1 to 6, it was possible to cut the transmittance at 440 nm, which is the blue light cut region, while maintaining the total light transmittance at 90% or more. Moreover, it was confirmed by the comparison with a comparative example that the characteristic as a hard coat film is maintained. That is, the blue light cut function could be imparted without causing deterioration of the pigment while maintaining the characteristics of the conventional hard coat film. Moreover, it turns out that the film film or base material whose transmittance | permeability of 460 nm is 10% or more high is obtained, reducing the transmittance | permeability of 440 nm. By using the film or base material obtained by the invention of the present application, the blue light cut function can be imparted without causing deterioration of the pigment despite the high transparency and hardness, and the light emission of the LED It can be seen that a film or a substrate with little reduction in efficiency can be obtained.

  The hard coat film obtained with the resin composition of the present invention has excellent blue light cutability, high transparency, and good hardness, especially a smartphone equipped with a touch panel, a tablet PC, a notebook PC, a plastic optical component, etc. It is a hard coat film suitable for fields requiring hardness, transparency, scratch resistance and blue light cut.

Claims (10)

UV-curable polyfunctional (meth) acrylate having at least two (meth) acryloyl groups in the molecule, and a dye having a structure of any one of formulas (1) to (3) Hard coat resin composition.

(R ₁ represents a hydrogen atom, a carbonyl group, an alkyl group having 1 to 3 carbon atoms, a sulfo group having a substituent, or an amide group having a substituent.)

(R ₂ and R ₃ each independently represent a hydrogen atom, a carbonyl group, an alkyl group having 1 to 3 carbon atoms, a sulfo group having a substituent, an amide group having a substituent, a halogen atom, or a hydroxyl group.)

(R ₄ and R ₅ each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a sulfo group, a sulfo group having a substituent, an amino group having a substituent, a benzoyl group, a nitro group, or a halogen atom. .) The ultraviolet curable hard coat resin composition according to claim 1, further comprising a photopolymerization initiator. The ultraviolet curable hard coat resin composition according to claim 1 or 2, further comprising a diluent. The ultraviolet curable hard coat resin composition according to any one of claims 1 to 3, comprising organic and / or inorganic particles. The base material which has a hardened layer which consists of an ultraviolet curable hard coat resin composition as described in any one of Claims 1 thru | or 4. The substrate according to claim 5, which is a transparent polymer or a film thereof. The substrate according to claim 5 or 6, wherein the total light transmittance is 90% or more, and the transmittance at 460 nm is 10% or more higher than the transmittance at 440 nm. A polarizing plate comprising a cured layer of the ultraviolet curable hard coat resin composition according to any one of claims 1 to 4. A liquid crystal display device comprising a cured layer of the ultraviolet curable hard coat resin composition according to claim 1. The molding which has a hardened layer of the ultraviolet curable hard coat resin composition as described in any one of Claims 1 thru | or 4.