JP2003306561A - Antistatic hard coating film and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic hard coating film excellent in antistatic performance, transparency, reflectance, and scuff resistance, and exceeding 3H in pencil hardness when applied onto a polyester film, and to provide a method for manufacturing the same. <P>SOLUTION: The method for manufacturing the antistatic hard coating film comprises: a process of applying an antistatic hard coat agent containing (A) a compound having two or more ethylenic unsaturated groups in its molecule, (B) a photopolymerization initiator, and (C) a conductive metal oxide having a primary particle diameter of 1-200 nm, onto a base film; and a process of hardening the hard coat agent. The method is characterized in that the hardening process is preceded by a process wherein the base film coated by the hard coat agent is humidified in an atmosphere of a relative humidity of 35-70%. The antistatic hard coating film is obtained by using this method. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an antistatic hard coat film, a method for producing the same, and an antistatic hard coat agent.

[0002]

2. Description of the Related Art At present, plastics are used in large quantities in various industries including the automobile industry, home electric appliances industry, electric and electronic industries. In this way, plastic is used in large quantities, in addition to its workability and transparency, it is lightweight, inexpensive,
Due to reasons such as optical characteristics. However, the plastics used in such fields have drawbacks such as being softer than glass or the like and being easily scratched on the surface. In order to improve these drawbacks, it is a common practice to coat the surface with a hard coat agent. This hard coat agent contains silicone paint,
Thermosetting hard coating agents such as acrylic paints and melamine paints are used. Among them, particularly, the silicon-based hard coating agent has been widely used because of its high hardness and excellent quality. This type of coating agent is mostly used for high value-added products such as glasses and lenses. However, the curing time is long, the cost is high, and it is not suitable for a hard coat of a film which is continuously processed.

In recent years, photosensitive acrylic hard coating agents have been developed and used. The photosensitive hard coat agent cures quickly to form a hard film when exposed to radiation such as ultraviolet rays, so it has a high processing speed, and has excellent performance in terms of hardness, scratch resistance, etc. Because it will be cheaper in cost,
It is now the mainstream in the hard coat field. In particular, it is suitable for continuous processing of films such as polyester. Plastic films include polyester films, polyacrylate films, acrylic films, polycarbonate films, vinyl chloride films, triacetyl cellulose films, polyether sulfone films, etc., but polyester films are the most widely used because of their excellent characteristics. Is a type of film. This polyester film is used as a functional film for glass shatterproof film, automobile light-shielding film, whiteboard surface film, system kitchen surface antifouling film, and electronic materials such as touch panels, liquid crystal displays, and CRT flat TVs. Widely used. The surface of each of these is not scratched, so a hard coat is applied.

Further, in recent years, in a display body such as a CRT or LCD provided with a film coated with a hard coat agent, the screen of the display body becomes difficult to see due to reflection, causing a problem that eyes are easily tired. A hard coat treatment that has the ability to prevent surface reflection is required. As a method of preventing surface reflection, a method in which a film in which a filler of inorganic filler or organic fine particles is dispersed in a photosensitive resin is coated, and the surface is made uneven to prevent reflection (AG treatment), film A method of providing a multilayer structure in the order of a high-refractive index layer and a low-refractive index layer to prevent reflection due to a difference in refractive index (AR processing), or an AG / AR processing method combining the above two methods and so on.

[0005]

In recent years, while hard coats having functionality have been demanded, especially in the field of electronic materials, materials to which foreign matters such as dust and dust are unlikely to adhere are demanded. In order to avoid such a phenomenon, a method of adding an antistatic agent has been adopted for the purpose of eliminating static electricity generated. Antistatic agents include cations, anions,
Nonionic surfactants are known, but they are highly environmentally dependent and the antistatic performance varies depending on the situation.Blends with low molecular weight, which are highly effective, bleed, and hardness of the film when a large amount of high molecular weight is added. There is a problem that In addition, conductive polymers and the like are also known, but since they are conjugated systems because of their structure, there is a problem that they are colored when mixed with a photosensitive resin. Amid such problems, the method of using conductive fine particles of metal oxides is becoming mainstream.
It becomes possible to impart antistatic performance while maintaining the transparency of the coating film to some extent.

However, in order to impart sufficient antistatic performance, it is necessary to add a considerable amount of a conductive metal oxide, which lowers the total light transmittance and increases the refractive index of the film. Therefore, there is a problem that the reflectance also becomes high. In addition, when the coating film thickness is reduced to solve the above problem, there is a problem that scratch resistance and pencil hardness deteriorate.

An object of the present invention is to provide an antistatic hard coat film having excellent antistatic properties, transparency, reflectance, scratch resistance, and a pencil hardness of more than 3H on a polyester film, and a method for producing the same. To do.

[0008]

Means for Solving the Problems As a result of intensive research to solve the above problems, the present inventors have found that a photosensitive resin composition having a specific composition solves the above problems, and Completed

That is, the present invention provides (1) a compound (A) having at least two ethylenically unsaturated groups in the molecule.
And a photopolymerization initiator (B), an antistatic hard coating agent containing a conductive metal oxide (C) having a primary particle size of 1 to 200 nm is coated on a base film, and then the hard coating agent A method for producing an antistatic hard coat film, comprising: curing an integrated body of a base film and a hard coat agent in an atmosphere having a relative humidity of 35 to 70% before the curing step. The method for producing a protective hard coat film, (2) wherein the compound (A) having at least two ethylenically unsaturated groups in the molecule is a reaction product of a hydroxyl group-containing polyfunctional (meth) acrylate and a polyisocyanate compound. (1) The method according to (1) or (3), wherein the conductive metal oxide (C) having a primary particle size of 1 to 200 nm is zinc antimonate. ) The method of manufacturing described, (4) the antistatic hard coat agent contains a diluent (D) (1)
(5) The manufacturing method according to any one of (1) to (3),
An antistatic hard coat film obtained by the method according to any one of (1) to (4) above,
(6) The antistatic hard coat film according to (5) above, which has a reflectance of 5% or less, a total line transmittance of 85% or more, and a haze value of 0.5 or less per 1 μm of film thickness, (7) in the molecule Compound (A) having at least two or more ethylenically unsaturated groups, photopolymerization initiator (B), and primary particle size of 1 to 1
An antistatic hard coating agent containing a conductive metal oxide (C) of 200 nm, wherein the proportion of the component (C) in the solid content of the hard coating agent is 15 to 35% by weight. Hard coat agent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The antistatic hard coating agent used in the present invention uses a compound (A) having at least two ethylenically unsaturated groups in the molecule. Specific examples of the component (A) include polyethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, ditrimethylolpropane. Tetra (meth) acrylate, glycene polypropoxy tri (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopentyl hydroxybivalate (for example, KAYARA manufactured by Nippon Kayaku Co., Ltd.)
D HX-220, HX-620, etc.), pentaerythritol tetra (meth) acrylate, poly (meth) a reaction product of dipentaerythritol and ε-caprolactone.
Acrylate, dipentaerythritol hexa (meth)
Acrylate, dipentaerythritol penta (meth)
Acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, polyglycidyl compound (polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hexahydrophthalic acid Diglycidyl ester, glycerin polyglycidyl ether, glycerin polyethoxyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolpropane polyethoxypolyglycidyl ether, etc.) and (meth) epoxy (meth) acrylate which is a reaction product of acrylic acid, Polyfunctional urethane acryl which is a reaction product of hydroxyl group-containing polyfunctional (meth) acrylate and polyisocyanate compound Etc. The. They are,
You may use it individually or in mixture of 2 or more types. Of these compounds (A), trifunctional or higher functional (meth) acrylates are preferable.

Further, among the compounds (A) having at least two ethylenically unsaturated groups in the molecule, a poly (isocyanate) compound obtained by reacting a polyfunctional (meth) acrylate having a hydroxyl group is particularly preferable. Functional urethane (meth) acrylates are preferred. The polyfunctional urethane (meth) acrylate is effective in preventing curling of the film and improving the hardness of the cured film.

Examples of the above-mentioned hydroxyl group-containing polyfunctional (meth) acrylates include pentaerythritol tri (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate. Acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol di (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol Tetra (meta)
Acrylate, tripentaerythritol tri (meth)
Acrylates, tripentaerythritol di (meth) acrylate, trimethylolpropane di (meth) acrylate, obtained by reacting an epoxy resin having two or more epoxy groups in one molecule with an ethylenically unsaturated group-containing monocarboxylic acid. Examples thereof include epoxy (meth) acrylates. These hydroxyl group-containing polyfunctional (meth) acrylates may be used alone or in combination of two or more.

The epoxy resin having two or more epoxy groups in one molecule used for the epoxy (meth) acrylate is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol. Glycidyl ethers such as novolac type epoxy resin, trisphenol methane type epoxy resin, brominated epoxy resin, biquinol type epoxy resin and biphenol type epoxy resin;
4-epoxy-6-methylcyclohexylmethyl-3,
4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4
Alicyclic epoxy resins such as epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; tetraglycidyl Glycidylamines such as diaminophenylmethane; Heterocyclic epoxy resins such as triglycidyl isocyanurate; Epicoat series (Epicoat 100
9, 1031: manufactured by Yuka Shell Epoxy Co., Ltd., and the like.

Examples of the ethylenically unsaturated group-containing monocarboxylic acid include acrylic acids, crotonic acid, α-cyanocinnamic acid, cinnamic acid, or a reaction of a saturated or unsaturated dibasic acid with an unsaturated group-containing monoglycidyl compound. Things can be mentioned. Examples of acrylic acids include a dimer of acrylic acid, methacrylic acid, β-styryl acrylic acid, β-furfuryl acrylic acid, saturated or unsaturated dibasic acid anhydride, and one hydroxyl group in one molecule. Examples thereof include half-esters which are equimolar reaction products with (meth) acrylate derivatives, and half-esters which are equimolar reaction products of saturated or unsaturated dibasic acids and monoglycidyl (meth) acrylate derivatives.

The epoxy resin is reacted with the ethylenically unsaturated group-containing monocarboxylic acid compound to obtain an epoxy (meth) acrylate compound. The usage of both is
It is 0.3 to 1.2 equivalents, preferably 0.9 to 1.05 equivalents, of the total amount of ethylenically unsaturated group-containing monocarboxylic acid carboxyl groups to 1 equivalent of epoxy groups of the epoxy resin. Further, at least one of the below-mentioned diluents (D) can be used during or after the reaction.

In addition, a catalyst can be used to accelerate the reaction. Examples of the catalyst include triethylamine, benzylmethylamine, methyltriethylammonium chloride, triphenylstilbine, triphenylphosphine and the like. The amount used is usually 0.1 to 10% by weight, preferably 0.3 to 5% by weight, based on the reaction raw material mixture.

During the reaction, it is preferable to use a polymerization inhibitor in order to prevent the polymerization of the ethylenically unsaturated group. Examples of the polymerization inhibitor include metoquinone, hydroquinone, methylhydroquinone, phenothiazine and the like. The amount used is preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% by weight, based on the reaction raw material mixture. The reaction temperature is 60 to 150 ° C, and further 8
0-120 degreeC is preferable. The reaction time is preferably 5 to 60 hours.

Examples of the polyisocyanate compound include chain saturated hydrocarbon isocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate and methylenebis (4-cyclohexyl isocyanate. ), Hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and other cyclic saturated hydrocarbon isocyanates, 2,4-tolylene diisocyanate, 1,3
-Aromatic isocyanates such as xylylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'-diisocyanate, 6-isopropyl-1,3-phenyl diisocyanate and 1,5-naphthalene diisocyanate. You can You may use these polyisocyanate compounds individually or in mixture of 2 or more types.

The polyfunctional urethane (meth) acrylate is
It can be obtained by reacting the hydroxyl group-containing polyfunctional (meth) acrylate with the polyisocyanate compound. The amount of both used is generally 0.1 to 50, preferably 0.1 to 10, in terms of the isocyanate group equivalent of the polyisocyanate compound, relative to 1 equivalent of the hydroxyl group of the hydroxyl group-containing polyfunctional (meth) acrylate. The reaction temperature is usually in the range of room temperature to 150 ° C, preferably 50 to 100 ° C. The end point of the reaction is confirmed by a decrease in the amount of isocyanate.

A catalyst may be added for the purpose of shortening the reaction time. As the catalyst, either a basic catalyst or an acidic catalyst is used. Examples of the basic catalyst include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine and ammonia, and phosphines such as tributylphosphine and triphenylphosphine. Examples of the acidic catalyst include copper naphthenate, cobalt naphthenate, zinc naphthenate, tributoxyaluminum, trititanium tetrabutoxide, metal alkoxides such as zirconium tetrabutoxide, Lewis acids such as aluminum chloride,
Examples thereof include tin compounds such as 2-ethylhexanetin, octyltin trilaurate, dibutyltin dilaurate and octyltin diacetate. Of these, acidic catalysts are preferable, and tin compounds are particularly preferable. The addition amount is 0.1 to 1% by weight with respect to the polyisocyanate compound. Further, one kind or two or more kinds of the below-mentioned diluent (D) can be mixed and used during or after the reaction. However, a diluent containing a hydroxyl group cannot be used during the reaction because it may react with the polyisocyanate compound.

In the antistatic hard coat agent used in the present invention, the photopolymerization initiator (B) is used. Examples of the component (B) include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2. -Phenylacetophenone, 1,1-dichloroacetophenone,
2-hydroxy-2-methyl-phenylpropane-1-
On, diethoxy acetophenone, 1-hydroxy chlorohexyl phenyl ketone, 2-methyl-1- [4-
(Methylthio) phenyl] -2-morpholinopropane-
Acetophenones such as 1-one; 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-
Anthraquinones such as chloroanthraquinone and 2-amylanthraquinone; thioxanthones such as 2,4-diethylthioxanthone, 2-isopropylthioxanthone and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4 -Benzoyl-4'-methyldiphenyl sulfide, benzophenones such as 4,4'-bismethylaminobenzophenone; 2,4,6
Examples include phosphine oxides such as -trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

These can be used alone or as a mixture of two or more kinds, and further, tertiary amines such as triethanolamine and methyldiethanolamine, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid. It can be used in combination with a promoter such as a benzoic acid derivative such as acid isoamyl ester.

In the antistatic hard coat agent used in the present invention, a conductive metal oxide (C) having a primary particle size of 1 to 200 nm is used. As the component (C),
For example, tin oxide, antimony-doped tin oxide (ATO)
(For example, Ishihara Sangyo Co., Ltd., FSS-10M, SNS
-10M), indium tin oxide (ITO) (for example, CI Kasei Co., Ltd., ITO dispersion liquid), zinc antimonate (for example, Nissan Chemical Industries, Ltd., Cellunax CX)
-Z600M-3, Cellunax CX-Z600M-3
F, Cellnax CX-Z600M-3F2) and the like. These can be easily obtained as an organosol dispersed in an organic solvent. Further, a powdery conductive metal oxide can also be used by dispersing it in a resin.

Among the above conductive metal oxides (C), zinc antimonate is preferable from the viewpoints of transparency, haze value and cost, and in consideration of workability, organosol of zinc antimonate is particularly preferable. The primary particle size is 1 to 200
There is no particular limitation as long as it is within the range of nanometers, but when the conductive metal oxide is in powder form, it is preferable that the particle diameter by the BET method calculated by the vapor phase adsorption method is 25 nanometers or less. When the conductive metal oxide is in the form of an organosol, the average particle size by dynamic light scattering method is 200.
It is preferably nanometer or less. The conductive metal oxide (C) is used in an amount of 15 to 15 in the solid content of the hard coat agent.
35% by weight. The antistatic hard coating agent of the present invention is one in which the content of the component (C) in the antistatic hard coating agent used in the production method of the present invention is within this range, and the optical characteristics (reflectance, total line transmittance, , Bayes value) is improved, and thus it can be preferably used. When the antistatic hard coat agent of the present invention is applied to the production method of the present invention, the antistatic hard coat film obtained has a reflectance of 5%.
Hereafter, the total ray transmittance is 85% or more, and the haze value per 1 μm of film thickness is 0.5 or less.

When the conductive metal oxide (C) is mixed and dispersed in the resin, a dispersant may be used to stabilize the dispersion. As the dispersant, a cationic dispersant,
Examples thereof include anionic dispersants, nonionic dispersants and double-sided surfactants. Preferably, a surfactant having an alkylamine, particularly Sols Perth 20000 (manufactured by Zeneca, PO modified by alkylamine, PO or EO), TAMNO-15 (manufactured by Nikko Chemical Co., Ltd., modified by EO of alkylamine), or the like. Is effective. The amount of the dispersant added is usually 0.5 to 30% by weight, preferably 1 to 20% by weight, based on the fine particles used.

As the antistatic hard coating agent in the present invention, a diluent (D) can be used. Examples of the diluent (D) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, phenoxyethyl (meth) acrylate,
Isoboronyl (meth) acrylate, tetrafurfuryl (meth) acrylate, acryloylmorpholine, dicyclopentanyloxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, 1,4-butanediol mono (meth) acrylate, polyethylene glycol Di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane polyethoxytri (meth) acrylate, di-caprolactone adduct of neopentyl glycol hydroxybivalate (Meth) acrylate (for example, manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, HX-62)
0), pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate and other reactive diluents (D-1), γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-
Heptalactone, α-acetyl-γ-butyrolactone,
Lactones such as ε-caprolactone; dioxane, 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 ether, etc. Ethers; carbonates such as ethylene carbonate and propylene carbonate; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and acetophenone;
Phenols such as phenol, cresol, xylenol; esters such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether; toluene, Hydrocarbons such as xylene, diethylbenzene, cyclohexane; trichloroethane, tetrachloroethane,
Organic solvents such as halogenated hydrocarbons such as monochlorobenzene, petroleum ethers such as petroleum ether and petroleum naphtha (D
-2) can be mentioned. The diluent may be used alone or in combination of two or more.

In the antistatic hard coat agent,
If necessary, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, various inorganic or organic fillers, polymers and the like may be added to impart functionality.

The antistatic hard coating agent used in the present invention is prepared by mixing the above-mentioned components (A), (B), (C) and, if necessary, component (D) and other components in any order. Obtainable. In addition, the amount used is 30-80% by weight of the component (A) in terms of solid content, (B)
The components are 0.5 to 32% by weight, the component (C) is 15 to 35% by weight, and the component (D-1) is 0 to 20% by weight. (D-2)
The components are 0 to 90% by weight, preferably 20 to 90% by weight in the antistatic hard coating agent. The antistatic hard coating agent thus obtained is stable over time.

The film of the present invention comprises the above-mentioned antistatic hard coating agent on a film substrate (base film), and the weight of the antistatic hard coating agent after drying is 2 to 50 g / m 2.
² , preferably 5 to 30 g / m ² (2 to 5 in terms of film thickness
It can be obtained by coating so as to have a thickness of 0 μm, preferably 5 to 30 μm), drying and then irradiating with radiation to form a cured film. Examples of the film substrate include polyester, polypropylene, polyethylene, polyacrylate, polycarbonate, triacetyl cellulose, polyether sulfone, and cycloolefin polymer. The film may be a sheet having a certain thickness.

The antistatic hard coating agent can be applied by, for example, bar coater coating, Mayer bar coating, air knife coating, gravure coating, reverse gravure coating, offset printing, flexographic printing, screen printing, etc. Is mentioned. At this time, the film used may have a pattern or an easily adhesive layer.

In the method for producing an antistatic hard coat film of the present invention, the integrated product of the antistatic hard coat agent and the film obtained above is cured before the curing step to obtain a relative humidity of 35 to 70.
% Humidification in an atmosphere. The usual hard coating agent coating process is diluted with a solvent,
After coating, there is a drying step, and then the resin is cured with a radiation irradiator such as an ultraviolet irradiator. In this case, a humidification step is provided between the drying step and the curing step by irradiation with radiation. Further, in the case of a solventless hard coat agent, a drying step is not necessary, and therefore a humidification step is provided between the coating step and the curing step. The humidifying method is not particularly limited, and the integrated product may be humidified in a humidifier, preferably in a constant temperature and constant humidity machine.
Humidification time is usually about 1 second to 30 minutes, preferably 10 seconds to
Room temperature is sufficient for about 10 minutes.

The antistatic hard coating agent preferably used in the present invention has a smaller amount of conductive metal oxide added than the conventional antistatic hard coating agent (15 to 35% by weight in the solid content of the hard coating agent), In such a case, if the humidity in the humidifying step is less than 35%, the surface resistance value of the antistatic film becomes 1 × 10E10Ω / □ or more, which is not preferable. Further, when the amount of the conductive metal oxide used exceeds 35% by weight, the surface resistance value becomes a satisfactory value, but since the amount of the conductive metal oxide increases, the decrease of the transmittance or the reflectance Rise may be seen. According to the present invention, the surface resistance value can be reduced to 1 × 10E7 to 1 × 10E8 Ω / square by just humidifying for a few seconds (1 to 2 seconds or more) immediately before curing. On the other hand, when the humidity exceeds 70%, a whitening phenomenon occurs and the haze value increases, which is not preferable.

The radiation to be applied is, for example, ultraviolet rays,
Examples include electron beams. When curing by ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high pressure mercury lamp, a metal halide lamp, etc. as a light source is used,
The amount of light, the arrangement of light sources, etc. are adjusted as necessary. When a high pressure mercury lamp is used, it is preferable to cure one lamp having a light amount of 80 to 160 W / cm at a transportation speed of 5 to 60 m / min.

The film of the present invention thus obtained is a light-shielding film for automobiles, a surface film for whiteboard,
It can be used as a functional film for a system kitchen surface antifouling film, a touch panel, a liquid crystal display, a CRT flat TV, and the like, and particularly when used on the surface of a display such as a CRT or LCD, it has excellent foreign matter adhesion prevention performance.

[0035]

EXAMPLES Next, the present invention will be described in more detail by way of examples. In the following, "parts" means "parts by weight" unless otherwise specified.

Synthesis Example 1 (Synthesis of polyfunctional urethane (meth) acrylate (A)) Pentaerythritol triacrylate (KAYARAD) was placed in a round bottom flask equipped with a stirrer, a cooling tube and a thermometer.
PET-30; Nippon Kayaku Co., Ltd. 1020 parts, dibutyltin dilaurate 0.6 part, and methquinone 0.6 part were put, and it heated and stirred at 80 degreeC. Then, 177.8 parts of isophorone diisocyanate (IPDI) was added dropwise over 1 hour, and further stirred for 2 hours to obtain urethane acrylate (A-1). The isocyanate value was 0.3 or less.

Examples 1 to 3 and Comparative Example 1 The materials shown in Table 1 were blended to obtain an antistatic hard coat agent (hereinafter referred to as "paint" in Table 2).

[0038] Table 1 Compounding amount                                 Example Comparative Example                       1 2 3 1 (A-1) 33.0 20.0 15.7 DPHA * 1 33.0 10.0 HDDA * 2 5.4 5.4 5.4 3.0 CX-Z600M-3F2 * 3 16.7 16.7 21.7 50.0 Irg.184 * 4 1.5 1.5 1.5 1.5 1.2 PE * 5 30.0 30.0 30.0 30.0 Methanol 13.3 13.3 11.3 ST103PA * 6 0.1 0.1 0.1 0.1 0.1

Note) * 1: DPHA; manufactured by Nippon Kayaku Co., Ltd., KAYARAD
DPHA (dipentaerythritol hexaacrylate) * 2: HDDA; manufactured by Kayaku Sartomer Co., Ltd., KS-HD
DA (1,6-hexanediol diacrylate) * 3: CX-Z600M-3F2; NISSAN CHEMICAL INDUSTRIAL CO., LTD., CELUX CX-Z600M-3F2 (methanol dispersion sol of zinc antimonate, solid content 60%) * 4: Irg. 184; manufactured by Ciba Specialty Chemicals (1-hydroxy-cyclohexyl-phenyl-ketone) * 5: PE; manufactured by Kuraray Co., Ltd., Arcosolv PE (propylene glycol monoethyl ether) * 6: ST103PA; Toray Dow Corning ( stock)
Made, silicon-based leveling agent

Examples 5 to 9 and Comparative Examples 2 to 3 Using the antistatic hard coat agents obtained in Examples 1 to 3 and Comparative Example 1, a polyester for easy adhesion treatment was carried out using a bar coater (No. 14). Film (manufactured by Toyobo Co., Ltd.):
A-4300, film thickness 188 μm), left in a drying oven at 80 ° C. for 1 minute, humidified with a thermo-hygrostat at a predetermined humidity for a predetermined time, and then in an air atmosphere, a 120 W / cm high pressure mercury lamp 10 cm. Ultraviolet rays were radiated from the distance of 5 m / min at a conveyor speed to obtain a film having a cured film (5 to 10 μm). Tests were performed on pencil hardness, scratch resistance, adhesion, appearance, total light transmittance, haze value, surface resistance value, and reflectance when humidified at each humidity.

(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, a pencil is placed on a polyester film having a cured film (15 μm) to be measured at a 45 ° angle and a load of 1 kg is applied from the top to 5 mm.
It was scratched to some extent and the degree of scratches was confirmed. The measurement was performed 5 times. Evaluation 5/5: No scratches in 5 out of 5 times 0/5: All scratches occurred in 5 times

(Scratch resistance test) Steel wool # 000
0, a load of 200 g / cm ² is applied, and it is reciprocated 10 times.
The condition of the scratch was visually evaluated. Evaluation ○: No scratch X: Scratch occurred

(Adhesion) According to JIS K 5400,
Make 11 crosswise cuts on the surface of the film at intervals of 1 mm to make 100 crosscuts. After the cellophane tape was brought into close contact with the surface of the tape, the number of squares remaining without peeling was displayed when the tape was peeled off at once.

(Appearance) Surface cracks, whitening, clouding, etc. were visually evaluated. Evaluation ◯: Good Δ: Occurrence of minute cracks X: Occurrence of remarkable cracks

(Total light transmittance, haze value) Haze meter It was measured using TC-H3DPK manufactured by Tokyo Denshoku Co., Ltd.

(Reflectance) Spectrophotometer Shimadzu Corporation
The reflectance at a wavelength of 550 nm is measured using a UV3100PC manufactured by KK.

(Surface resistance value) Resistivity meter Mitsubishi Chemical Corporation
It measured using HIRESTA IP made from.

The evaluation results are shown in Tables 2-3. Table 2 Evaluation results             Paint Humidity Pencil hardness 2H Scratchability Adhesion Appearance Example 5 Example 1 60% × 10 seconds 5/5 ○ 100 ○ Example 6 Example 1 60% × 30 seconds 5/5 ○ 100 ○ Example 7 Example 2 40% × 30 seconds 5/5 ○ 100 ○ Example 8 Example 2 60% × 30 seconds 5/5 ○ 100 ○ Example 9 Example 3 50% × 10 seconds 5/5 ○ 100 ○ Comparative Example 2 Example 1 25% × 30 seconds 5/5 ○ 100 ○ Comparative Example 3 Comparative Example 1 25% × 30 seconds 5/5 ○ 100 ○

[0049] Table 3 Evaluation results             Full line transmittance Haze Surface resistance (Ω / □) Reflectance Example 5 90% 1.0 3.0 × 10E08 4.5% Example 6 89% 1.1 1.5 × 10E08 4.5% Example 7 90% 0.9 2.4 x 10E08 4.4% Example 8 89% 1.1 1.2 × 10E08 4.4% Example 9 87% 0.9 4.5 × 10E08 4.8% Comparative Example 2 88% 1.0 7.0 × 10E10 4.5% Comparative Example 3 81% 1.3 1.2 × 10E08 7.3%

[0050]

EFFECT OF THE INVENTION The antistatic film of the present invention has good antistatic performance, and is also excellent in scratch resistance and pencil hardness. According to the production method of the present invention, the amount of the conductive metal oxide can be reduced, so that the film can be produced at low cost, the total line transmittance, and the haze can be formed into an antistatic film having good plastic optical components and a touch panel. ,
It is suitable for fields requiring antistatic performance and high hardness such as flat displays and film liquid crystal elements.

Continued front page    F-term (reference) 4F006 AA35 AB37 BA02 BA07 CA04                       CA05 CA07 CA08 DA04 EA01                       EA03                 4J011 AA05 AC04 CA01 CA08 CB00                       CB02 CC08 CC10 PA07 PA16                       PB26 QA13 QA22 QA23 QA24                       QA25 QA26 QA33 QA37 QA38                       QB19 QB20 QB22 QB24 SA02                       SA04 SA06 SA07 SA21 SA22                       SA32 SA34 SA54 SA63 SA64                       SA84 WA02 WA07

Claims (7)

[Claims] 1. A compound (A) having at least two ethylenically unsaturated groups in the molecule and a photopolymerization initiator (B),
An antistatic hard coat film comprising a base film coated with an antistatic hard coat agent containing a conductive metal oxide (C) having a primary particle size of 1 to 200 nm, and then curing the hard coat agent. A method for producing an antistatic hard coat film, comprising a step of humidifying an integrated product of a base film and a hard coat agent in an atmosphere having a relative humidity of 35 to 70% before the curing step. 2. The method according to claim 1, wherein the compound (A) having at least two ethylenically unsaturated groups in the molecule is a reaction product of a hydroxyl group-containing polyfunctional (meth) acrylate and a polyisocyanate compound. . 3. The method according to claim 1, wherein the conductive metal oxide (C) having a primary particle size of 1 to 200 nm is zinc antimonate. 4. The production method according to claim 1, wherein the antistatic hard coating agent contains a diluent (D). 5. An antistatic hard coat film obtained by the method according to any one of claims 1 to 4. 6. The antistatic hard coat film according to claim 5, which has a reflectance of 5% or less, a total line transmittance of 85% or more, and a haze value of 0.5 or less per 1 μm of film thickness. 7. A compound (A) having at least two ethylenically unsaturated groups in the molecule and a photopolymerization initiator (B),
An antistatic hard coating agent containing a conductive metal oxide (C) having a primary particle size of 1 to 200 nanometers, wherein the proportion of the component (C) in the solid content of the hard coating agent is 15 to. An antistatic hard coat agent of 35% by weight.