TW201510118A - 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 quinaldine-based dye.

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 a blue light barrier property even if a crack is formed on a curved surface portion of a surface portion of a molded article by selecting a resin composition having flexibility. membrane. 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. As the hard coating agent, a hard coating agent such as a thermosetting type such as a polyfluorene-based paint, an acrylic paint, or a melamine paint is used. Among them, especially This is a polyoxo-based hard coating agent which 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 the plastic, the sheet or the substrate such as polycarbonate or acrylic resin is also applied to the liquid crystal related member around the optical disk or the 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. The problem is that it is necessary to have a hard coating treatment that is resistant to surface reflection depending on the application. As a method of resisting surface reflection, there is a method in which an inorganic filler or an organic filler is dispersed in a photosensitive resin, and a film is formed on the surface to provide anti-reflection (AG (Anti-Glare) treatment). High refractive index on the film a layer and a low-refractive-index layer are provided in a multi-layered structure, and a method of preventing reflection and reflection (AR (Anti-Reflection) processing) by interference of light generated by a refractive index difference; or the above two methods A method of combining AG/AR processing or the like (refer to 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 improving the fingerprint wiping property as a fingerprint resistance, for example, a method of mixing a fluorine-based material or a polyoxygenated oil or the like into a coating composition to improve water repellency and oil repellency of the surface; or A component similar to the sebum component is used for coating the composition to fuse the attached fingerprint, making the fingerprint 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 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, so that blue light blocking is receiving attention. Although it is desired to block the light of this wavelength, one of the main light-emitting wavelengths of the 460 nm light-based LED light source It is desirable to block light of 440 nm as another wavelength without substantially blocking the wavelength.

In particular, when a functional dye having a blue light blocking function is mixed with an acrylate compound as an ultraviolet curable resin, the acrylate compound which is decomposed by a pigment or is an ultraviolet curable resin is hardly hardened, and does not exhibit a blue light blocking function. . Due to the above problems, at present, a film imparted with a blue light blocking function is flooded in the market, but an ultraviolet curing type hard coating resin composition is not known.

[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

[Non-patent literature]

[Non-Patent Document 1] General Synthetic Dye, Sakaguchi Bo, Sanxie Publishing Co., Ltd.

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; Ester, and a pigment having any of the structures of formula (1) to formula (3), [Chemical 1]

(R ₁ represents a hydrogen atom, a carbonyl group, an alkyl group having 1 to 3 carbon atoms, a sulfo group having a substituent, and an anthranyl 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 anthranyl group having a substituent, a halogen atom, or a hydroxyl group)

(R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a sulfo group, a sulfo group having a substituent, an amine group having a substituent, a benzamidine group, a nitro group, or a halogen atom) (2) The ultraviolet curable hard coating resin composition according to (1), which comprises a photopolymerization initiator; (3) The ultraviolet curable hard coating resin composition according to (1) or (2) (4) The ultraviolet curable hard coating resin composition according to any one of (1) to (3), which contains organic and/or inorganic particles, and (5) a substrate. The hardened layer containing the ultraviolet curable hard coating resin composition according to any one of (1) to (4), wherein the substrate described in (5) 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 higher than the transmittance at 440 nm by 10% or more; (8) a polarizing plate A hardened layer of the ultraviolet curable hard coating resin composition according to any one of (1) to (4), wherein the liquid crystal display device comprises any one of (1) to (4). Recorded ultraviolet Hardened layer hardening type hard coating of the resin composition; (10) A molded product, which comprises of (1) to (4) according to any one of an ultraviolet hardening layer curing type hard coating of the 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) change Triglyceride (meth) acrylate, ethylene oxide (EO) modified glycerol tri(meth) acrylate, propylene oxide (PO) modified glycerol tri(meth) acrylate, EO modified phosphoric acid (Meth) acrylate, caprolactone modified trimethylolpropane tri(meth) acrylate, EO modified trimethylolpropane tri(meth) acrylate, PO modified trimethylolpropane (Meth) acrylate, pentaerythritol tri(meth) acrylate, di-trimethylolpropane tetra(meth) acrylate, dipentaerythritol hexa(meth) acrylate, dipentaerythritol penta (meth) acrylate , tripentaerythritol octa (meth) acrylate, tris(propylene methoxyethyl) isocyanurate, caprolactone modified dipentaerythritol hexa (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate Ester, polydecane hexa(meth) acrylate, as polyglycidyl compound (bisphenol A type epoxy resin, phenol novolac type epoxy resin, trisphenol methane type epoxy resin, polyethylene glycol condensed water) a reaction of glycerol ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc. with (meth)acrylic acid Epoxy (meth) acrylate, urethane amide as a reactant of a diol with a polyisocyanate and a (meth) acrylate having a hydroxyl group, as a polyfunctional active hydrogen (hydroxyl, amine, etc.) A polyfunctional (meth)acrylic acid urethane or the like which is a reactant of a methyl acrylate and a polyisocyanate compound. These may be used singly or in combination of two or more. Preferred are trifunctional or higher polyfunctional (meth) acrylates.

Examples of the polyfunctional (meth)acrylate having active hydrogen include pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol. Pentaerythritol such as tetrakis(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol di(meth)acrylate, or hydroxymethyl group such as trimethylolpropane di(meth)acrylate, double Epoxy acrylate such as phenol 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 chain saturated hydrocarbon or a cyclic saturated hydrocarbon can be used. (alicyclic), polyisocyanate of aromatic hydrocarbon. 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 hydrocarbon (alicyclic) polymerization such as keto diisocyanate, dicyclohexylmethane diisocyanate, methylene bis(4-cyclohexyl isocyanate), hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate Isocyanate, 2,4-methylphenylene diisocyanate, 1,3-benzenedimethyl diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl An aromatic polyisocyanate such as 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 by comprising an ultraviolet curable polyfunctional (meth) acrylate having at least two or more (meth) acrylonitrile groups in a molecule, and a structure having the formula (1) to formula (3) By the ultraviolet curable hard coating resin composition containing the pigment, the dye can provide an ultraviolet curable hard coating resin composition having 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.

[Chemical 4]

(R ₁ represents a hydrogen atom, a carbonyl group, an alkyl group having 1 to 3 carbon atoms, a sulfo group having a substituent, and an anthranyl 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, a mercapto group having a substituent, a halogen atom, or a hydroxyl group).

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

By using the dyes represented by the formulas (1) to (3), a film or a substrate which is characterized in that the total light transmittance is 90% or more and is transmitted with respect to 440 nm can be produced. The rate, the transmittance at 460 nm is higher than 10%, and a film or substrate having a high surface hardness can be obtained. Moreover, since the transmittance at 460 nm is higher than 440 nm, it is possible to suppress The reduction in luminous efficiency of the LED is a blue blocking film or substrate that blocks light of 440 nm on one side.

As a method of 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 according to the method of Quinoline Yellow described on page 309.

The alkyl group having a carbon number of 1 to 3 in the formula (1) may, for example, be a methyl group, an ethyl group or a propyl group, and the sulfo group having a substituent may be a sulfophenyl group, a sulfomethyl group or a sulfoethyl group, having a substituent. The guanamine group may, for example, be a dimethylammonium group. The alkyl group having a carbon number of 1 to 3 in the formula (2) may, for example, be a methyl group, an ethyl group or a propyl group, and the sulfo group having a substituent may be a sulfophenyl group, a sulfomethyl group or a sulfoethyl group, having a substituent. The guanamine group may, for example, be a dimethylammonium group. The alkyl group having a carbon number of 1 to 3 in the formula (3) may, for example, be a methyl group, an ethyl group or a propyl group, and the sulfo group having a substituent may be a sulfophenyl group, a sulfomethyl group or a sulfoethyl group, having a substituent. The guanamine group may, for example, be a dimethylammonium group.

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

[Chemistry 9]

Next, a specific example of the coloring matter represented by the formula (2) is shown below.

[Chemistry 13]

Next, a specific example of the coloring matter represented by the formula (3) is shown below.

[化17]

[Chem. 21]

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 use amount of the photopolymerization initiator component 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 (Eicosapentaenoic Acid), 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 ethyl carbonate and propyl carbonate; methyl ethyl ketone and methyl Ketones such as butyl ketone, cyclopentanone, cyclohexanone, and acetophenone; phenols such as phenol, cresol, and 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 film thickness of the ultraviolet curable hard coating resin composition of the present invention after drying the resin composition is usually 0.1 to 20 μm, preferably 1 to 10 μm. The coating is applied to a substrate, and after drying, it is irradiated with ultraviolet rays to form a cured film, whereby it can be obtained as a hard coating 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 necessary. 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 is 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

In a 500 cc flask, a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate (trade name: KAYARAD PET-30, manufactured by Nippon Kayaku Co., Ltd.), 60 parts, polyfunctional urethane amide (trade name: KAYARAD) UX-5000, manufactured by Nippon Kayaku Co., Ltd., 40 parts, 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, manufactured by BASF), 5 parts, and 66.7 parts of toluene were mixed and dissolved at room temperature to prepare Mother material 1 of 60% solids.

Modulation example 2

The pigment obtained in the formulation of Non-Patent Document 1 and the dye having the highest absorbance at 448 nm, and the dye having the highest absorbance at 424 nm, the compound of Example 5, were mixed in the same amount, 0.1 part by weight, and 19.9 parts by weight of toluene. The mother liquor 2 was prepared by mixing and dissolving.

Modulation example 3

0.1 part of the dye of the compound example 15 which is the highest in absorbance at 431 nm, and the mixture of 19.9 parts of toluene obtained by using the formulation described in Non-Patent Document 1 was mixed and dissolved to prepare a mother liquid. 3.

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 6

The resin composition prepared with the material shown in the following Table 1 was applied onto an 80 μm triethylene cellulose film by bar coating, and dried in a dryer at 80 ° C for 2 minutes, and then a 160 W high pressure mercury lamp was provided. The ultraviolet irradiation device was hardened with an integrated 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 pigment used in Examples 1 to 3 was changed to a yellow pigment Flavine FG manufactured by Nippon Kayaku Co., Ltd. having a maximum absorption wavelength at 420 nm, which does not have the structure of the formulas (1) to (3) described in the present application. Except for this, Comparative Examples 2 to 4 were produced in the same manner.

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 that the total light transmittance was 90% or more. And the transmittance at 440 nm is adjusted to a transmittance of 460 nm in the case of 65% to 70%.

(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)

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

(scratch resistance)

Using steel wool #0000, the load was reciprocated 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

(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 contact, ×: peeling occurs

In Examples 1 to 6, 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 has been found that a film or a substrate having a transmittance lower than 440 nm but having a transmittance of 460 nm higher by 10% or more can be obtained. It is understood that by using the film or substrate obtained by the present invention, a film or a base which imparts a blue light blocking function without causing deterioration of the dye and which has less luminous efficiency of the LED can be obtained, although the transparency and the hardness are high. material.

[Industrial availability]

The hard coating film obtained from the resin composition of the present invention is excellent in blue light barrier property, and is transparent. High brightness and good hardness, especially for smart phones, tablet PCs, notebook PCs, plastic optical parts, etc. with hard touch panels, hardness, transparency, scratch resistance, and blue light barrier. Coating film.

Claims (10)

An ultraviolet curable hard coating resin composition containing an ultraviolet curable polyfunctional (meth) acrylate having at least two (meth) acrylonitrile groups in a molecule, and having the formula (1) to (3) a pigment of any structure, (R ₁ represents a hydrogen atom, a carbonyl group, an alkyl group having 1 to 3 carbon atoms, a sulfo group having a substituent, and an anthranyl 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 anthranyl group having a substituent, a halogen atom, or a hydroxyl group) (R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a sulfo group, a sulfo group having a substituent, an amine group having a substituent, a benzamidine group, a nitro group, or a halogen atom) . 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 a transmittance of 460 nm is higher than a transmittance of 440 nm by 10% or more. 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.