TW201510117A - Ultraviolet-curable hard coat resin composition - Google Patents

Abstract

To provide a hard-coating film or base material that is suitable for use in fields that require hardness, optical transparency, resistance to abrasion scratches, and blue-light reduction. A film or base material using a UV-curable hard-coating resin composition that contains the following: a UV-curable polyfunctional (meth)acrylate that has at least two (meth)acryloyl groups per molecule; and a pigment that has a structure that can be represented by formula (1).

Description

Ultraviolet hardening type hard coating resin composition

The present invention relates to an ultraviolet curable hard coating resin composition which imparts scratch resistance and blue light barrier property to a plastic surface. More specifically, it relates to an ultraviolet curing which is suitable for coating on a plastic surface such as polyester, acrylic resin, triacetyl cellulose, polycarbonate, etc., and which is excellent in scratch resistance, chemical resistance, and blue light barrier property. Type hard coating resin composition. In particular, since the film or sheet coated with the hard coating resin composition is suitable for a smart phone or a flat-panel PC using a light-emitting diode (LED) as a backlight, the film is excellent in blue light barrier property (Personal) Computers, personal computers, notebooks, LCD monitors, etc.

Furthermore, the present invention provides a hard coating film which can obtain a molded article having the above-described blue light blocking property even if a crack is formed on the curved surface portion of the surface portion of the molded article by selecting a resin composition having flexibility. In particular, it is suitable for in-mold forming and film forming, and is also suitable for imparting a blue light blocking function to sunglasses.

At present, plastics are widely used in various industries including the automotive industry, home appliance industry, and electronics industry. The reason why such a large amount of plastic is used is that, in addition to workability and transparency, the plastic is also lightweight, inexpensive, and excellent in optical characteristics. However, it has disadvantages such as being softer than glass and easily damaging the surface. In order to improve these disadvantages, it has been conventionally practiced to apply a hard coating agent to the surface. The hard coating agent uses a polyfluorene-based paint, A hard coating type hard curing agent such as an acrylic paint or a melamine paint. Among them, in particular, the polyoxynene-based hard coating agent is used in a large amount because of its high hardness and excellent quality. However, the hardening time is long and expensive, and it is not suitable for a hard coating provided on a film which is continuously processed.

In recent years, a photosensitive acrylic hard coating agent having been developed has been developed and gradually applied (see Patent Document 1). The photosensitive hard coating agent is immediately hardened by irradiation with radiation such as ultraviolet rays to form a hard film, so that it has a high processing speed, excellent hardness and scratch resistance, and becomes a total cost. It is cheap, so it is now becoming the mainstream in the field of hard coating. In particular, it is suitable for continuous processing of films such as polyester. As the film of the plastic, there are a polyester film, an acrylic film, a polycarbonate film, a vinyl chloride film, a triacetyl cellulose film, a polyether ruthenium film, etc., and the polyester film and the triacetyl cellulose film are excellent in various kinds. Features are widely used. The polyester film can be widely used as a glass anti-scattering film, or a car's light-shielding film, a whiteboard surface film, an embedded kitchen surface antifouling film, and can be widely used as a CRT (Cathode-Ray Tube, for electronic materials). Cathode ray tube) A functional film such as a flat panel TV, a touch panel, a liquid crystal display, or a plasma display. Further, the triacetonitrile cellulose film can be used as a protective film for a polarizing plate used in a liquid crystal display. These are all coated with a hard coating without damaging the surface.

Further, in addition to the film of plastic, a hard coating is applied to a sheet or substrate such as polycarbonate or acrylic resin, and it is also used for a liquid crystal related member around a disk or a backlight.

Further, in the case of a substrate coated with a hard coating agent in recent years, it is required to have a function other than scratch resistance as a function of hard coating. For example, in a display body such as an LCD (Liquid Crystal Display) or a PDP (Plasma Display Panel) in which a film is provided, it is difficult to see a display screen due to reflection, and the eyes are easily fatigued. Therefore, it is necessary to have a hard coating treatment against surface reflection depending on the use. As a method of resisting surface reflection, a method in which an inorganic filler or an organic filler is dispersed in a photosensitive resin is applied to the film, and irregularities are formed on the surface. Anti-reflection method (AG (Anti-Glare) treatment); a multilayer structure is provided in the order of a high refractive index layer and a low refractive index layer on the film, and is prevented by interference of light generated by a difference in refractive index Method of reflection and reflection (AR (Anti-Reflection) processing); or a method of AG/AR processing in which the above two methods are combined (see Patent Document 2).

Further, a hard coating which imparts an antistatic function and a method of using a surfactant or a conductive metal oxide have been developed (see Patent Document 3).

Furthermore, due to the popularity of smart phones or tablet PCs in recent years, touch panels that directly touch the display with fingers are rapidly emerging. Therefore, it is required to impart fingerprint resistance such as that the fingerprint does not adhere to the surface of the display, is not easily adhered, is hard to be seen even if it adheres, and is easy to wipe.

For the method of improving the fingerprint wiping property as the fingerprint resistance, for example, a method in which a fluorine-based material or a polyoxygenated oil or the like is mixed in a coating composition to improve water repellency and oil repellency of the surface may be used; or A component similar to the sebum component is used for coating a composition to fuse the attached fingerprint, is difficult to see, and is easy to wipe (see Patent Document 4).

In recent years, the backlight of a liquid crystal display has been replaced by a CCFL (Cold Cathode Fluorescent Lamp), and the problem of blue light has been controversial. The so-called blue light refers to a short wavelength in the visible light, and light from 380 nm to 495 nm is considered to be emitted from a liquid crystal monitor using a LED from a backlight. This blue light is an important cause of eye fatigue, which in turn is thought to disrupt the biological cycle, leading to sleep disorders, and thus blue light blocking is receiving attention.

At present, a film imparted with a blue light blocking function is flooded in the market, but an ultraviolet curable hard coating resin composition is not known. In particular, when a functional dye having a blue light blocking function is mixed with an acrylate compound as an ultraviolet curable resin, there is a problem that the dye is decomposed without exhibiting a blue light blocking function.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-48934

[Patent Document 2] Japanese Patent Laid-Open No. Hei 9-145903

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-231444

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2008-255301

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

In order to solve the above problems, the inventors of the present invention have found that the ultraviolet curable hard coating resin composition having a specific compound and composition solves the above problems, and has completed the present invention.

In other words, the present invention relates to (1) an ultraviolet curable hard coating resin composition comprising: an ultraviolet curable polyfunctional (meth)acrylic acid having at least two (meth)acrylonium groups in a molecule; An ester, and a pigment having the structure of the formula (1),

(R ₁ represents a halogen atom, R ₂ represents an alkyl group having 1 to 3 carbon atoms, or a sulfonylamino group having a substituent, and n represents an integer of 1 to 4); (2) ultraviolet curing as described in (1) A hard coating resin composition containing a photopolymerization initiator; (3) The ultraviolet curable hard coating resin composition according to (1) or (2), which contains a diluent; (4) as (1) The ultraviolet curable hard coating resin composition according to any one of (3), which contains organic and/or inorganic particles, and (5) a substrate containing the contents (1) to (4). (6) The substrate according to (5), which is a transparent polymer or a film thereof; (7) as described in (5) or (6), the hardened layer of the ultraviolet curable hard coating resin composition described in (5); The substrate has a total light transmittance of 90% or more, and an average transmittance of 440 nm to 480 nm is 1% or more lower than the total light transmittance, and the absolute value of the difference between the transmittances of 440 nm to 480 nm is within 1%. (8) A polarizing plate comprising the hardened layer of the ultraviolet curable hard coating resin composition according to any one of claims 1 to 4; (9) a liquid crystal display device comprising (1) A molded article comprising the ultraviolet ray according to any one of (1) to (4), wherein the cured layer of the ultraviolet curable hard coating resin composition according to any one of (1) to (4) A hardened layer of a hardened hard coating resin composition.

According to the present invention, it is possible to provide an ultraviolet curable hard coating resin composition which has excellent blue light barrier properties, scratch resistance, high hardness, and transparency.

Hereinafter, the present invention will be described in detail.

The ultraviolet curable polyfunctional (meth) acrylate (A) having at least two or more (meth) acrylonitrile groups in the molecule used in the present invention may, for example, be polyethylene glycol bis(methyl) Manufacture of bis(meth) acrylate of ε-caprolactone adduct of acrylate, tripropylene glycol di(meth) acrylate, neopentyl glycol hydroxypivalate (for example, manufactured by Nippon Kayaku Co., Ltd.) , KAYARAD HX-220, HX-620, etc.), bis (meth) acrylate of EO (ethylene oxide) bisphenol A, 1,4-butanediol diacrylate, 1 ,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxy tri(meth)acrylate , epichlorohydrin (ECH) modified glycerol tri(meth) acrylate, ethylene oxide (EO) modified glycerol tri(meth) acrylate, propylene oxide (PO) modified glycerol tri(methyl) Acrylate, EO modified tris(meth)acrylate, caprolactone modified trimethylolpropane tri(meth)acrylate, EO modified trimethylolpropane tri(meth)acrylate, PO Modified trimethylolpropane tris(A) Acrylate, pentaerythritol tri(meth)acrylate, di-trimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tripentaerythritol Octa(meth)acrylate, tris(propyleneoxyethyl)isocyanurate, caprolactone modified dipentaerythritol hexa(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, poly Hexa hexa(meth) acrylate, as a polyglycidyl compound (bisphenol A type epoxy resin, phenol novolak type epoxy resin, trisphenol methane type epoxy resin, polyethylene glycol diglycidyl ether, Epoxy (meth) acrylate of a reaction product of glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc. with (meth)acrylic acid, diol and polyisocyanate, and (meth) having a hydroxyl group Acrylic urethane acrylate as a reactant of the acrylate, polyfunctional (meth)acrylic acid amide as a reactant of a polyfunctional (meth) acrylate having an active hydrogen (hydroxyl, amine, etc.) and a polyisocyanate compound Acid esters, etc. These may be used singly or in combination of two or more. Preferred are trifunctional or higher polyfunctional (meth) acrylates.

As the polyfunctional (meth) acrylate having active hydrogen described above, for example, Pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra(meth) acrylate, dipentaerythritol tri(meth) acrylate Pentaerythritols such as dipentaerythritol di(meth)acrylate, methylol groups such as trimethylolpropane di(meth)acrylate, and epoxy acrylates such as bisphenol A diepoxy acrylate. Among them, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are preferred. These polyfunctional (meth) acrylates having active hydrogen may be used singly or in combination of two or more.

As the above polyisocyanate, a polyisocyanate containing a chain saturated hydrocarbon, a cyclic saturated hydrocarbon (alicyclic), or an aromatic hydrocarbon can be used. Examples of such a polyisocyanate include chain saturated hydrocarbon polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, and isophor. Cyclic saturated hydrocarbons (alicyclic) such as keto diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate Polyisocyanate, 2,4-methylphenylene diisocyanate, 1,3-benzenedimethyl diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-iso An aromatic polyisocyanate such as propyl-1,3-phenyl diisocyanate or 1,5-naphthalene diisocyanate. Among them, isophorone diisocyanate and hexamethylene diisocyanate are preferred. These polyisocyanates may be used singly or in combination of two or more.

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

It is also possible to add a catalyst in order to shorten the reaction time. As the catalyst, any of an alkaline catalyst or an acidic catalyst can be used. Examples of the basic catalyst include amines such as triethylamine, diethylamine, dibutylamine, and ammonia, phosphines such as tributylphosphine and triphenylphosphine, and pyridine and pyrrole. Examples of the acidic catalyst include metal salts such as copper naphthenate, cobalt naphthenate, zinc naphthenate, aluminum tributoxide, trititanium tetrabutoxide, and zirconium tetrabutoxide, and Lewis such as aluminum chloride. A tin compound such as an acid, 2-ethylhexyltin, octyltin trilaurate, dibutyltin dilaurate or octyltin diacetate. In the case of using these catalysts, the amount thereof is usually from about 0.1 part by weight to about 1 part by weight based on 100 parts by weight of the polyisocyanate.

Further, in the reaction, in order to prevent polymerization in the reaction, it is preferred to use a polymerization inhibitor (for example, p-methoxyphenol, hydroquinone, methyl hydroquinone, or thiophene The amount used is from about 0.01% by weight to about 1% by weight, preferably from about 0.05% by weight to about 0.5% by weight, based on the reaction mixture. The reaction temperature is 60 to 150 ° C, preferably 80 to 120 ° C.

In the resin composition of the present invention, when the solid content component of the resin composition of the present invention is 100% by weight, the ultraviolet curable type having at least two (meth)acryl fluorenyl groups in the molecule is more The functional (meth) acrylate is usually used in an amount of from 80 to 95% by weight, preferably from 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) acrylonitrile groups in the molecule may be optionally used as needed. . As a (meth)acrylate compound, a (meth)acrylate monomer is mentioned.

Examples of the (meth) acrylate monomer include tricyclodecane (meth) acrylate, dicyclopentadienyloxyethyl (meth) acrylate, and dicyclopentanyl (meth) acrylate. (meth)acrylic acid Ester, adamantane (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, phenyl glycidyl (meth) acrylate, ( 2-hydroxyethyl methacrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, and the like.

The present invention is characterized in that it contains an ultraviolet curable polyfunctional (meth) acrylate having at least two or more (meth) acrylonitrile groups in a molecule, and a dye having a structure of the formula (1), The ultraviolet curable hard coating resin composition of the dye provides an ultraviolet curable hard coating resin composition which has high transparency, high hardness, and excellent blue light blocking function. When a dye other than the one described in the formula (1) is used, there is a problem that not only the blue light blocking function is lowered, but also the transparency is lowered, the hardness is lowered, or the residual monomer which is not reacted by the ultraviolet curable resin after the polymerization reaction is increased.

(R ₁ represents a halogen atom, R ₂ represents an alkyl group having 1 to 3 carbon atoms, or a sulfonylamino group having a substituent, and n represents an integer of 1 to 4).

By using the dye represented by the formula (1), the following film or substrate can be obtained: although the total light transmittance is 90% or more, the average transmittance of 440 nm to 480 nm is 1% or more lower than the total light transmittance. Preferably, it is 3% or less, further preferably 6% or less, and further, the absolute value of the difference between the transmittances of 440 nm to 480 nm is within 1%. That is, a film obtained from a composition of the dye represented by the formula (1) and a combination of an ultraviolet curable polyfunctional (meth) acrylate having at least two or more (meth) acrylonitrile groups in the molecule, or a substrate The transmittance of 440 nm to 480 nm has a substantially fixed transmittance, and a stable blue light barrier can be achieved in the range of 440 nm to 480 nm.

As a method for synthesizing such a dye, for example, o-dichlorobenzene is used as a solvent, and a phthalic anhydride having a substituent represented by the formula (2) and a substituent having the substituent represented by the formula (3) are used. Although it is obtained by dehydration condensation of 8-naphthalenediamine, it is not limited to this. Further, R ₁ , R ₂ and n of the formulas (2) and (3) represent the same.

Next, a more specific example of the coloring matter represented by the formula (1) is shown below.

[Chemical 5]

[化8]

The photopolymerization initiator used in the present invention may, for example, be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether or the like; acetophenone, 2,2-diethoxy group -2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexylbenzene Acetones such as ketone and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one; 2-ethyl hydrazine, 2-tributyl Anthraquinones such as hydrazine, 2-chloroindole and 2-pentylhydrazine; 2,4-diethyl 9-oxosulfur 2-isopropyl 9-oxosulfur 2-chloro 9-oxosulfur 9-oxosulfur a ketal such as acetophenone dimethyl ketal or benzoin dimethyl ketal; benzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 4,4' - benzophenones such as dimethylaminobenzophenone; 2,4,6-trimethylbenzimidyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene) ) - phosphine oxides such as phenylphosphine oxide, and the like. Further, specifically, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1-(4-(methylthio)phenyl) manufactured by BASF Corporation can be easily obtained from the market. -2-(4-morpholinyl)-1-propanone), Lucirin TPO (2,4,6-trimethylbenzimidyldiphenylphosphine oxide), and the like. Further, these may be used singly or in combination of two or more.

In the case where the solid content component of the resin composition of the present invention is 100% by weight in the resin composition of the present invention, the amount of the photopolymerization initiator component used is 0.5 to 10% by weight. Preferably, it is 1 to 7% by weight.

Further, the photopolymerization initiator may be used in combination with a curing accelerator. Examples of the hardening accelerator which can be used together include triethanolamine, diethanolamine, N-methyldiethanolamine, 2-methylaminoethyl benzoate, dimethylaminoacetophenone, and p-dimethylaminobenzene. Hydrogen donors such as isoamyl formate, amines such as EPA, and 2-mercaptobenzothiazole. When the solid content component of the resin composition of the present invention is 100% by weight, the curing accelerator is used in an amount of 0 to 5% by weight.

Examples of the diluent which can be used in the present invention include γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone, α-ethinyl-γ-butyrolactone, and the like. Ε-caprolactone and the like lactones; Alkane, 1,2-dimethoxymethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, triethylene glycol dimethyl Ethers such as ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether; carbonates such as ethylene carbonate and propylene carbonate; methyl ethyl ketone, methyl iso Ketones such as butyl ketone, cyclopentanone, cyclohexanone, acetophenone; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, Esters such as butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate; hydrocarbons such as toluene, xylene, diethylbenzene, cyclohexane; Halogenated hydrocarbons such as ethyl chloride, tetrachloroethane, and monochlorobenzene, petroleum solvents such as petroleum ether and petroleum spirit, and fluorine-based alcohols such as 2H, 3H-tetrafluoropropanol, and perfluorobutylmethyl Hydrofluoroethers such as ether and perfluorobutyl ethyl ether; alcohols such as methanol, ethanol, isopropanol and n-propanol; diacetone alcohol having both ketone and alcohol properties. These may be used singly or in combination of two or more.

In the resin composition of the present invention, the amount of the diluent component 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.

Further, in the resin composition of the present invention, organic and/or inorganic particles may be added to impart an antiglare property and an antireflection function. Examples of the organic particles include melamine beads of plastic beads, acrylic resin beads, acrylic-styrene beads, polycarbonate beads, polyethylene beads, and polystyrene beads. Examples of the inorganic particles include amorphous particles of cerium oxide as cerium oxide, true spherical particles, tin oxide as a metal oxide, zinc oxide, titanium oxide, and aluminum oxide. The particle size or amount of the particles can be adjusted according to the target haze or other characteristics.

Further, in the resin composition of the present invention, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a polymerization inhibitor or the like may be added to the photosensitive resin composition of the present invention as needed. And give the functionality of the target separately. Examples of the leveling agent include a fluorine-based compound, a polyfluorene-based compound, and an acrylic compound. Examples of the ultraviolet absorber include a benzotriazole-based compound, a benzophenone-based compound, and the like. Examples of the light stabilizer include a hindered amine compound and a benzoate compound. Examples of the antioxidant include a phenol compound, and examples of the polymerization inhibitor include p-methoxyphenol and methyl. Hydroquinone, hydroquinone, and the like.

The resin composition of the present invention can be obtained by containing the above-mentioned ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acrylonitrile groups, the dye exemplified in the formula (1), and photopolymerization initiation. The agent and the diluent are obtained by mixing other components as needed.

The resin composition of the present invention obtained in the above manner is stable over time.

The ultraviolet curable hard coating resin composition of the present invention is applied to 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, after drying. The cured film is formed by irradiation with ultraviolet rays, whereby it can be obtained as a hard coat film.

In the case where a film is used for the substrate, examples of the substrate film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetyl cellulose, polyether oxime, and cycloolefin polymer. Wait. The film may also be a sheet having a certain thickness. The film to be used may also be a surface treatment provided with a pattern or an easy-to-layer layer, such as corona treatment.

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

Ultraviolet rays are irradiated for hardening, but an electron beam or the like can also be used. In the case of curing by ultraviolet light, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, a metal halide lamp or the like is used as the light source, and the amount of light, the arrangement of the light source, and the like are adjusted as needed. In the case of using a high-pressure mercury lamp, it is preferable to perform hardening at 100 to 1000 mJ/cm ² at a conveying speed of 5 to 60 m/min with respect to one lamp having an energy of 80 to 160 W/cm ² . On the other hand, in the case of hardening by an electron beam, a photopolymerization initiator may not be added, and an electron beam acceleration device having an energy of 100 to 500 eV is preferably used.

As the substrate obtained in the above manner, a transparent polymer or a film thereof is preferred. As the transparent polymer or film to be formed, a transparent polymer or film having high mechanical strength and good thermal stability is preferred. The substance used as the transparent protective layer is, for example, a cellulose acetate resin such as triacetonitrile cellulose or diacetyl cellulose or a film thereof, an acrylic resin or a film thereof, a polyvinyl chloride resin or a film thereof, Nylon resin or film thereof, polyester resin or film thereof, polyarylate resin or film thereof, a cyclic olefin such as a olefin is a monomeric cyclic polyolefin resin or a film thereof, polyethylene, polypropylene, ring system or has a drop The polyolefin of the olefin skeleton or a copolymer thereof, a main chain or a branch of a resin or polymer of ruthenium and/or decylamine or a film thereof.

The obtained substrate may be bonded to a polarizing element including a polyvinyl alcohol resin film or a polarizing plate obtained by laminating the polarizing element with triacetyl cellulose or the like, for example, via an adhesive or the like. When the film obtained in the above manner is provided in the liquid crystal cell, it becomes a hard coating film or a substrate suitable for the field of hardness, transparency, scratch resistance, and blue light barrier in addition to the necessary polarizing function.

Further, the resin composition resin of the present invention can be molded into a film, a lens or the like. Therefore, the resin composition of the present invention can also be used in the production of such a molded component or a molded article.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention should not be construed as limited. Further, in the examples, the parts represent % by weight unless otherwise specified.

Modulation example 1

60 parts of a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.) in a 500 mL flask, polyfunctional urethane urethane (trade name: KAYARAD) UX-5000, manufactured by Nippon Kayaku Co., Ltd., 40 parts, 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF), and 66.7 parts of toluene were mixed and dissolved at room temperature. And a mother liquid 1 in which 60% of the solid content is produced.

Modulation example 2

The compound represented by the formula (4) and the compound represented by the formula (5) are added to o-dichlorobenzene. The solution was heated while stirring, and a solution containing the compound shown in the compound example 1 was obtained. The obtained solution was filtered, and the residual component was dried to obtain a pigment of the compound example 1 having a maximum absorption wavelength at 450 nm. 0.1 part of the obtained pigment and 19.9 parts of toluene were mixed and dissolved to prepare a mother liquid 2.

Comparative example 1

The mother liquid 1 was applied onto an 80 μm triethylene fluorene cellulose film by a bar coater, and dried in a dryer at 80 ° C for 2 minutes, and then an ultraviolet ray irradiation apparatus provided with a 160 W high pressure mercury lamp was used to accumulate a light amount of 250 mJ/ The cm ² was hardened to obtain a hard coating film having a film thickness of 4 to 5 μm.

Examples 1 to 3

The resin composition prepared with the material shown in the following Table 1 was applied onto an 80 μm triethylene fluorene cellulose film by a bar coater, and dried in a dryer at 80 ° C for 2 minutes, and then a 160 W high pressure was set. The ultraviolet irradiation device of the mercury lamp was hardened with a cumulative light amount of 250 mJ/cm ² to obtain a blue light-barrier hard coating film having a film thickness of 4 to 5 μm. Furthermore, in Table 1, the unit indicates "parts".

Comparative Examples 2 to 4

The dyes used in Examples 1 to 3 were changed to the yellow pigment Flacine FG manufactured by Nippon Chemical Co., Ltd., which has a maximum absorption wavelength at 420 nm, and the same procedure was carried out to prepare Comparative Examples 2 to 4.

The following items were evaluated for the blue light-blocking hard coat films obtained in Examples 1 to 3 and Comparative Examples, and the results are shown in Table 2 and Table 3. Table 4 shows the transmittances of 440 nm to 480 nm obtained by measuring the transmittance, and Table 5 shows the transmittances of the wavelengths of 440 nm to 480 nm.

(pencil hardness)

The pencil hardness of the coating film of the above composition was measured in accordance with JIS K 5400 using a pencil scratch tester. Specifically, on the polyester film having the hardened film to be measured, a load of 750 g was applied from the top, and the pencil was drawn at an angle of 45 degrees to about 5 mm, and the hardness of the pencil which was not damaged more than four times in five times was expressed. Pencil hardness.

(total light transmittance)

The measurement was carried out using HM-150 manufactured by Murakami Color Research Institute Co., Ltd.

(haze)

The measurement was carried out using HM-150 manufactured by Murakami Color Research Institute Co., Ltd.

(chroma)

The U-4100 manufactured by Hitachi, Ltd. was used to measure L*, a*, and b* under a halogen lamp.

(scratch resistance)

Using steel wool # 0000, the load was repeated once at a load of 250 g/cm ² , and after rubbing for 10 times, the friction surface was observed, and the following evaluation was performed.

Evaluation...○: no damage, ×: damage occurred

(adhesiveness)

Using a cutter, 100 squares were formed at intervals of 1 mm in the hard coat layer of the example, and the transparent tape was firmly adhered, and then peeled off instantaneously in the direction of 90 degrees, and the following evaluation was performed.

Evaluation...○: 100/100 is in good adhesion, ×: peeling occurs

In Examples 1 to 3, although the total light transmittance was maintained at 90% or more, the transmittance at 440 nm as a blue light blocking region was blocked. Moreover, it was confirmed that the characteristics as a hard coating film were maintained in comparison with the comparative example. That is, the characteristics of the previous hard coating film can be maintained, and the blue light blocking function can be imparted without causing deterioration of the dye. Further, it is understood that a film or a substrate having a substantially uniform transmittance of 440 nm to 480 nm can be obtained.

[Industrial availability]

The hard coating film obtained from the resin composition of the present invention is excellent in blue light barrier property, high in transparency, and good in hardness, and is particularly suitable for a smart phone, a tablet PC, a notebook PC, a plastic optical component equipped with a touch panel. A hard coating film in the field of hardness, transparency, scratch resistance, and blue light barrier.

Claims (10)

An ultraviolet curable hard coating resin composition comprising: an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acrylonitrile groups in a molecule, and a structure having the formula (1) Pigment, (R ₁ represents a halogen atom, R ₂ represents an alkyl group having 1 to 3 carbon atoms, or a sulfonylamino group having a substituent, and n represents an integer of 1 to 4). The ultraviolet curable hard coating resin composition of claim 1, which comprises a photopolymerization initiator. The ultraviolet curable hard coating resin composition according to claim 1 or 2, which contains a diluent. The ultraviolet curable hard coating resin composition according to any one of claims 1 to 3, which contains organic and/or inorganic particles. A substrate comprising a hardened layer comprising the ultraviolet curable hard coating resin composition according to any one of claims 1 to 4. A substrate according to claim 5 which is a transparent polymer or a film thereof. The substrate of claim 5 or 6 has a total light transmittance of 90% or more, and an average transmittance of 440 nm to 480 nm is lower than a total light transmittance by 1% or more, and further, a difference in transmittance between 440 nm and 480 nm. The absolute value is less than 1%. A polarizing plate comprising the hardened layer of the ultraviolet curable hard coating resin composition according to any one of claims 1 to 4. A liquid crystal display device comprising the hardened layer of the ultraviolet curable hard coating resin composition according to any one of claims 1 to 4. A molded article comprising the hardened layer of the ultraviolet curable hard coating resin composition according to any one of claims 1 to 4.