JP2009001598A - Active energy ray curable type antistatic hard coat resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray curable type antistatic hard coat resin composition for producing a cured material having improved antistatic property, scratch resistance, transparency and light resistance. <P>SOLUTION: The active energy ray curable type antistatic hard coat resin composition contains multifunctional (meta)acrylate(A) having two or more (meta)acryloyl groups in each molecule, zinc oxide particulates (B) obtained by doping gallium, and photoinitiator (C). Herein, the content of the photoinitiator (C) is in a range of 7-40 wt.% based on the zinc oxide particulates (B) which is obtained by doping gallium. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable hard coat resin composition that imparts scratch resistance, antistatic property, and light resistance to a plastic surface. More specifically, an active energy ray that provides a cured product having transparency, scratch resistance, chemical resistance, antistatic property, and light resistance suitable for coating on plastic surfaces such as polyester, acrylic, triacetyl cellulose, and polycarbonate. The present invention relates to a curable antistatic hard coat resin composition.

  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 the plastic film include a polyester film, an acrylic film, a polycarbonate film, a vinyl chloride film, a triacetyl cellulose film, and a polyethersulfone film. The polyester film is most widely used because of various excellent characteristics. This polyester film is a glass shatterproof film, or a light shielding film for automobiles, a whiteboard surface film, a system kitchen surface antifouling film, and electronic materials such as CRT flat TV, touch panel, liquid crystal display (LCD), plasma Widely used as a functional film for displays (PDP), organic EL displays and the like. 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 base material 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 such as a CRT, LCD, or PDP provided with a film, the display screen is difficult to see due to reflection, and the eyes are likely to get tired. Processing is required. 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).

  As the conductive metal oxide, tin oxide, indium oxide, ruthenium oxide, zinc oxide and the like are used. Patent Document 4 discloses a coprecipitate of zinc oxide and gallium, and Patent Document 5 discloses gallium. Zinc oxide to which is added is described respectively.

Further, in Patent Document 6, the ultraviolet curable hard coat resin composition containing polyfunctional urethane acrylate and conductive zinc oxide is used. In Patent Document 7, it is ensured that the conductive zinc oxide fine particles have high transparency, UV curable type. References are made respectively to conductive resin compositions comprising conductive zinc oxide doped with (meth) acrylate and gallium, but examples for compositions comprising conductive zinc oxide doped with polyfunctional urethane acrylate and gallium are as follows: Neither is described.
Further, the present applicant has filed an application that a film having excellent antistatic properties, transparency and hardness can be obtained by a resin composition using polyfunctional urethane acrylate and zinc oxide fine particles doped with gallium ( (See Patent Document 8).

Japanese Patent Laid-Open No. 9-48934 JP-A-9-145903 JP-A-10-231444 JP 2003-54947 A International Publication No. 2004/058645 Pamphlet International Publication No. 2004/044063 Pamphlet JP 2006-160941 A Japanese Patent Application No. 2006-266485

  Among the demands for hard coats with added functionality, there is a demand for materials that are less susceptible to foreign matter such as dust and dirt, particularly in the field of electrical and electronic materials. There is a method of adding an antistatic agent for the purpose of removing generated static electricity. Antistatic agents include cationic, anionic, and nonionic surfactants. However, they are highly environment-dependent and vary in antistatic properties. When a large amount of molecular weight is added, there is a problem that the hard coat performance is lowered. In addition, conductive polymers are also known, but there are problems in that, when mixed with an ultraviolet curable resin, the performance deteriorates or the coloring increases.

  Among these problems, a method using metal oxide conductive fine particles is becoming mainstream in imparting antistatic performance to hard coats. When these metal oxides are used, it is possible to impart permanent antistatic properties while maintaining the properties of the hard coat. Further, by reducing the metal oxide, a film with less haze can be obtained. However, many metal oxides having conductivity are colored, and when a large amount of metal oxide is added to maintain conductivity, the coating film is colored and there is no cloudiness but the transmittance is lowered. There is also a drawback. For metal oxides that are nearly transparent, there is also a problem that antistatic performance cannot be obtained sufficiently.

  Furthermore, some metal oxides have photocatalytic activity, and even if they have excellent initial characteristics, there is a problem that they cannot be put into practical use due to deterioration after a light resistance test.

  The present invention improves the above-mentioned drawbacks, and the resulting cured product has good antistatic performance, no dependency on the environment, high transparency, high hardness, and good light resistance. An object is to provide a preventive hard coat resin composition.

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

That is, the present invention
(1) A polyfunctional (meth) acrylate (A) having at least two (meth) acryloyl groups in the molecule, zinc oxide fine particles (B) doped with gallium, and a photopolymerization initiator (C). And the content of the photopolymerization initiator (C) is in the range of 7 to 40% by weight with respect to the zinc oxide fine particles (B) doped with gallium. Coat resin composition,
(2) An active energy ray in which a polyfunctional (meth) acrylate (A) having at least two (meth) acryloyl groups in the molecule has at least two (meth) acryloyl groups and active hydrogen in the molecule The active energy ray-curable antistatic hard coat resin composition according to the above (1), which is a polyfunctional urethane (meth) acrylate obtained by reacting a curable polyfunctional (meth) acrylate and a polyisocyanate,
(3) The active energy according to (1) or (2), wherein the content of zinc oxide fine particles (B) doped with gallium is in the range of 10 to 95% by weight with respect to the solid content of the resin composition Wire curable antistatic hard coat resin composition,
(4) Any one of the above (1) to (3), wherein the photopolymerization initiator (C) is 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one Active energy ray-curable antistatic hard coat resin composition according to
(5) The active energy ray-curable antistatic hard coat resin composition according to any one of (1) to (4), which contains a diluent (D),
(6) A film or substrate having a cured layer of the active energy ray-curable antistatic hard coat resin composition according to any one of (1) to (5),
About.

  The present invention can provide an active energy ray-curable antistatic hard coat resin composition that imparts a cured product having excellent antistatic properties, scratch resistance, transparency, and light resistance.

  Hereinafter, the present invention will be described in detail.

  The active energy ray-curable antistatic hard coat resin composition of the present invention is a zinc oxide fine particle doped with polyfunctional (meth) acrylate (A) having at least two (meth) acryloyl groups in the molecule and gallium. (B) and the photopolymerization initiator (C), and the content of the photopolymerization initiator (C) is in the range of 7 to 40% by weight with respect to the zinc oxide fine particles (B) doped with gallium. is there.

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 and tripropylene glycol di (meth). Di (meth) acrylate of an acrylate, ε-caprolactone adduct of hydroxypentyl glycol neopentyl glycol (for example, KAYARAD HX-220, HX-620, etc., manufactured by Nippon Kayaku Co., Ltd.), di of EO adduct of bisphenol A (Meth) acrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meta ) Polyester acrylates such as acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, polyglycidyl compounds (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 Polyfunctional urethane (meth) acrylate obtained by reacting polyfunctional (meth) acrylate with active hydrogen and polyisocyanate Rate and the like. You may use these individually or in mixture of 2 or more types.
Among these polyfunctional (meth) acrylates, it is particularly preferable to use a polyfunctional urethane (meth) acrylate obtained by reacting a polyfunctional (meth) acrylate having active hydrogen with a polyisocyanate.

  Examples of the polyfunctional (meth) acrylate having active hydrogen include pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, di Mention may be made of pentaerythritols such as pentaerythritol di (meth) acrylate, methylols such as trimethylolpropane di (meth) acrylate, and epoxy acrylates such as bisphenol A diepoxy acrylate. Preferable examples include pentaerythritol triacrylate and dipentaerythritol pentaacrylate. These (meth) acrylates may be used alone or in combination of two or more.

  As the polyisocyanate, polyisocyanates composed of chain saturated hydrocarbons, cyclic saturated hydrocarbons, and aromatic hydrocarbons can be used. Examples of such polyisocyanates include chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexylisocyanate). , Hydrogenated diphenylmethane diisocyanate, hydrogenated xylene diisocyanate, cyclic saturated hydrocarbon isocyanate such as hydrogenated toluene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, p-phenylene diisocyanate, 3,3′-dimethyl- 4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate, 1,5-naphthalene And aromatic polyisocyanates such as isocyanate. Preferable examples include isophorone diisocyanate and hexamethylene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

  The polyfunctional urethane (meth) acrylate is obtained by reacting the ultraviolet curable polyfunctional (meth) acrylate having active hydrogen with a polyisocyanate. The polyisocyanate is usually in the range of 0.1 to 50 as the isocyanate group equivalent, preferably 0.1 to 10 with respect to 1 equivalent of the active hydrogen group in the ultraviolet curable polyfunctional (meth) acrylate having active hydrogen. Range. The reaction temperature is usually in the range of 30 to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is calculated by a method in which the amount of residual isocyanate is reacted with an excess of n-butylamine and back titrated with 1N hydrochloric acid, and ends when the isocyanate is 0.5 wt% or less.

  A catalyst may be added for the purpose of shortening the reaction time. As this catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphine such as tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, zirconium tetrabutoxide and the like, Lewis acids such as aluminum chloride, and 2-ethylhexanetin. , Tin compounds such as octyltin trilaurate, dibutyltin dilaurate, and octyltin diacetate. The addition amount of these catalysts is 0.1-1 weight% normally with respect to 100 weight% of polyisocyanate.

  In addition to the component (A), a (meth) acrylate monomer having a (meth) acryloyl group can be used in the resin composition of the present invention as necessary. For example, alicyclic (meth) acrylates such as tricyclodecane (meth) acrylate, dicyclopentadieneoxyethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantane (meth) acrylate, (Meth) acrylates having aromatic rings such as phenylglycidyl (meth) acrylate and benzyl (meth) acrylate, heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and morpholine (meth) acrylate, 2- (Meth) acrylates having a hydroxyl group such as hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, etc. It is below. You may use these individually or in mixture of 2 or more types.

  In the resin composition of the present invention, the amount of the component (A) used is usually 10 to 80% by weight, preferably 20 to 70% by weight when the solid content of the resin composition of the present invention is 100% by weight. %.

  The gallium-doped zinc oxide fine particles (B) used in the present invention are preferably dispersed in an organic solvent. Conductivity can be imparted by doping gallium. Examples of the zinc oxide fine particles doped with gallium include a passette series manufactured by Hakusui Tech Co., Ltd.

  In the resin composition of the present invention, the amount of the component (B) used is 10 to 95% by weight, preferably 30 to 80% by weight when the solid content of the resin composition of the present invention is 100% by weight. It is.

  In mixing and dispersing the component (B) in the resin, a dispersant may be used to stabilize the dispersion. Examples of the dispersant that can be used for this purpose include cationic, anionic, nonionic, and amphoteric surfactants. The amount added is 0.5 to 30% by weight, preferably 1 to 20% by weight, when the component (B) is 100% by weight.

Examples of the photopolymerization initiator (C) 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-phenyl Acetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl]- Acetophenones such as 2-morpholinopropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-t-butylanthraquinone, 2-chloroanthraquinone and 2-amylanthraquinone; 2,4-die Thioxanthones such as luthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylamino Benzophenones such as benzophenone; phosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc., preferably 2-methyl- 1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one.
Specifically, from the market, Irgacure 184 (1-hydroxycyclohexyl phenyl ketone) and Irgacure 907 (2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane manufactured by Ciba Specialty Chemicals, Inc. -1-one), Lucylin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide) manufactured by BASF, etc. can be easily obtained. Moreover, you may use these individually or in mixture of 2 or more types.

  In the composition of the present invention, the amount of the photopolymerization initiator (C) used is 7 to 40% by weight, preferably 10 to 30% by weight, based on the zinc oxide fine particles (B) doped with gallium. is there.

  When the ratio of the component (C) to the component (B) is small, the light resistance test is bad.

  Moreover, said photoinitiator (C) can also be used together with a hardening accelerator. Examples of curing accelerators 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 (D) 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; 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 ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl Ethers such as ethers; carbonates such as ethylene carbonate and propylene carbonate Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone; phenols such as phenol, cresol, xylenol; ethyl acetate, butyl acetate, ethyl lactate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene Esters such as glycol monomethyl ether acetate; Hydrocarbons such as toluene, xylene, diethylbenzene, cyclohexane; Halogenated hydrocarbons such as trichloroethane, tetrachloroethane, and monochlorobenzene, and petroleum solvents such as petroleum ether and petroleum naphtha Organic solvents, fluorinated alcohols such as 2H, 3H-tetrafluoropropanol, perfluorobutyl methyl ether, perf Hydrofluoroethers such as Oro butyl 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 of the component (D) used is in the range of 0 to 90% by weight, preferably 30 to 80% by weight, based on the total amount of the resin composition of the present invention.

  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 can be obtained by mixing the component (A), the component (B), the component (C) and, if necessary, the component (D) and other components in any order.

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

  The antistatic hard coat film of the present invention has the above active energy ray-curable antistatic hard coat resin composition on a substrate, and the thickness of the resin composition after drying is usually 0.1 to 50 μm, Preferably, it can be obtained by coating to 1 to 20 μm and irradiating an active energy ray after drying to form a cured film.

  When a film is used as a substrate on which the resin composition of the present invention is applied, examples of the substrate film include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetylcellulose, polyethersulfone, and cycloolefin polymer. Is mentioned. 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.

  Examples of the active energy rays irradiated for curing include ultraviolet rays and electron beams. 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 a conveying speed of 5 to 60 m / min for one lamp having an energy of 80 to 120 W / cm. On the other hand, when curing with an electron beam, it is preferable to use an electron beam accelerator having an energy of 100 to 500 eV.

  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 a weight part.

Synthesis Example 1 Synthesis of polyfunctional urethane acrylate In a dry container, 939.7 parts by weight of dipentaerythritol pentaacrylate, 0.47 parts by weight of dibutyltin dilaurate, and 0.3 parts by weight of methoquinone were added and heated to 80 ° C. with stirring. 60.3 parts by weight of hexamethylene diisocyanate was added dropwise thereto over 1 hour, and the proportion of isocyanate after stirring for 2 hours was 0.1% by weight or less, indicating that the reaction was almost quantitatively completed.

Examples 1-2 and Comparative Examples 1-3
A resin composition containing the materials shown in Table 1 was coated on an easy-adhesion-treated PET film (125 μm) with a bar coater and dried at about 80 to 100 ° C. / Min × 1 pass) to obtain an antistatic hard coat film having a thickness of 3 to 5 μm. In Table 1, the unit represents “part”.
In order to demonstrate that the amount of the initiator used in Examples 1 and 2 is effective, in the comparative example, the amount of the initiator is reduced, and an ultraviolet absorber is added and compared with the example. I did it.

Table 1
Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3
DPHA 7.12
Compounds from Synthesis Examples 7.12 8.80 7.12 8.80
THFA 0.88 0.88 1.10 0.88 1.10
Irg. 184 0.33 0.33
Irg. 907 3.00 3.00 0.33 0.33 1.10
Lucilin TPO 0.44 0.44
Tinuvin PS 1.90
Conductive zinc oxide dispersion 63.30 63.30 63.30 63.30 63.30
PGM 25.70 25.70 25.70 25.70 25.70
Total 100.00 100.00 100.00 100.00 100.00

(note)
DPHA: (Multifunctional acrylate (A) component; mixture of dipentaerythritol pentaacrylate and hexaacrylate)
Compound from synthesis example: (polyfunctional urethane acrylate (A) component)
THFA: Tetrahydrofurfuryl acrylate Irg. 184: Ciba Specialty Chemicals Co., Ltd., 1-hydroxycyclohexyl phenyl ketone (component (C))
Irg. 907: Ciba Specialty Chemicals Co., Ltd., 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one (component (C))
Lucillin TPO: manufactured by BASF, 2,4,6-trimethylbezoyldiphenylphosphine oxide (component (C))
Tinuvin PS: manufactured by Ciba Specialty Chemicals Co., Ltd., UV absorber conductive zinc oxide dispersion: gallium-doped zinc oxide pastette GK-40 manufactured by Hakusuitec Co., Ltd., 30% solid content, PGM dispersion (component (B) )
PGM: Propylene glycol monomethyl ether (component (D))

  The following items were evaluated for the antistatic hard coat films obtained in Examples 1-2 and Comparative Examples 1-3, and the results are shown in Table 2.

(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 a polyester film having a cured film to be measured, a pencil is applied at a 45 degree angle, and a 1 kg load is applied from above, and the pencil is scratched about 5 mm. expressed.

(Total light transmittance)
Measured using TC-H3DPK, manufactured by Tokyo Denshoku Co., Ltd.

(Haze: Haze value)
Measured using TC-H3DPK, manufactured by Tokyo Denshoku Co., Ltd.

(Surface resistivity: Antistatic property)
Resistivity meter Measured using HIRESTA IP manufactured by Mitsubishi Chemical Corporation.

(Light resistance test)
EYE SUPER UV TESTER made by Iwasaki Electric
After irradiation for 10 hours, adhesion and reflectance were measured, and before and after the light resistance test was compared.

(Adhesion)
The film surface after the light resistance test is scratched on the cloth with a cutter, and a cellophane tape is affixed thereon and peeled at an angle of 90 degrees.
○: No peeling ×: Peeling occurred

(Reflectance)
Measured with a spectrophotometer UV-3150 (reflection angle 5 °) manufactured by Shimadzu Corporation.
The reflection curve between 360 and 760 nm was compared before and after the light resistance test.
○: No change (no decrease in reflectivity)
×: Changed (Reflectance decreased)

Table 2
Pencil hardness Total light transmittance Haze Surface resistivity Adhesion Reflectance
(%) (%) (Ω / □)
Example 1 2H 89 0.7 5E + 10 ○ ○
Example 2 2H 89 0.9 4E + 12 ○ ○
Comparative Example 1 2H 89 0.8 3E + 10 × ×
Comparative Example 2 2H 89 1.5 7E + 10 × ×
Comparative Example 3 2H 89 0.8 3E + 10 ○ ×

  In the antistatic hard coat films of Examples 1 and 2, Irg. 907 (2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one) is used in an amount of 15.8% with respect to zinc oxide fine particles doped with gallium. Similarly to the above, Comparative Example 1 uses 1.7% and Comparative Example 2 uses 1.7% in addition to an ultraviolet absorber for the purpose of improving light resistance. Similarly, Comparative Example 3 uses 5.8%.

  The antistatic hard coat film of Example 1 showed good results with respect to pencil hardness, total light transmittance, haze, surface resistivity, adhesion after light resistance test, and reflectance characteristics. Also in Example 2, the surface resistivity (antistatic performance) and other performance showed good results. Comparative Example 1 is a component of (C) component Irg. When the amount of 907 (2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one) is decreased, pencil hardness, total light transmittance, haze, surface resistivity, etc. The initial characteristics were good, but the adhesion and reflectance after the light resistance test were poor. In Comparative Example 2, an ultraviolet absorber was added for the purpose of improving the light resistance, but the initial haze slightly increased, and the adhesion and reflectance after the light resistance test were poor. For Comparative Example 3, the reflectance after the light resistance test was insufficient.

  The antistatic hard coat film obtained with the resin composition of the present invention has excellent antistatic properties, high transparency, hardness, adhesion after light resistance test, and good optical characteristics, especially plastic optical parts It is a hard coat film suitable for fields that do not like dust, require hardness and transparency, such as optical disks, touch panels, flat panel displays, mobile phones, and film liquid crystal elements.

Claims (6)

A polyfunctional (meth) acrylate (A) having at least two (meth) acryloyl groups in the molecule, zinc oxide fine particles (B) doped with gallium, and a photopolymerization initiator (C); The active energy ray-curable antistatic hard coat resin composition, wherein the content of the polymerization initiator (C) is in the range of 7 to 40% by weight with respect to the zinc oxide fine particles (B) doped with gallium. object. The polyfunctional (meth) acrylate (A) having at least two (meth) acryloyl groups in the molecule has at least two (meth) acryloyl groups and active hydrogen in the molecule. 2. The active energy ray-curable antistatic hard coat resin composition according to claim 1, which is a polyfunctional urethane (meth) acrylate obtained by reacting a functional (meth) acrylate with a polyisocyanate. The active energy ray-curable charging according to claim 1 or 2, wherein the content of the zinc oxide fine particles (B) doped with gallium is in the range of 10 to 95 wt% with respect to the solid content of the resin composition. Prevention hard coat resin composition. The photopolymerization initiator (C) is 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, according to any one of claims 1 to 3. An active energy ray-curable antistatic hard coat resin composition. The active energy ray-curable antistatic hard coat resin composition according to any one of claims 1 to 4, further comprising a diluent (D). A film or a substrate having a cured layer of the active energy ray-curable antistatic hard coat resin composition according to any one of claims 1 to 5.