JP2006348069A - Liquid curable composition and its cured film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid curable composition excellent in curing properties and capable of forming a coated film excellent in antistatic properties, hardness, scratch resistance and transparency on the surfaces of various kinds of base materials and its cured film and a laminate for antistatic. <P>SOLUTION: The liquid curable composition comprises (A) particles containing tin-containing indium oxide (ITO) having ≤20 nm primary particle diameter and ≤50 nm secondary particle diameter as a main component, (B) a compound having two or more polymerizable unsaturated groups in the molecule, (C) a photopolymerization initiator and (D) a solvent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid curable composition and a cured film thereof. More specifically, it has excellent curability and various substrates such as plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene series. Resin, etc.), a liquid curable composition capable of forming a coating (film) excellent in antistatic property, hardness, scratch resistance and transparency on the surface of metal, wood, paper, glass, ceramics, slate, etc. It relates to the cured film.

Conventionally, from the viewpoint of ensuring the performance of information communication equipment and safety measures, a radiation-curable composition has been used on the equipment surface to provide a scratch-resistant and adhesive coating (hard coat) or an antistatic coating. A film (antistatic film) is formed.
In addition, in order to impart an antireflection function to an optical article, a multilayer structure (antireflection film) of a low refractive index layer and a high refractive index layer is formed on the surface of the optical article.
In recent years, there has been remarkable development and general use of information communication devices, and further improvements in performance and productivity of hard coats, antistatic films, antireflection films and the like have been demanded.

In particular, optical articles such as plastic lenses are required to prevent dust adhesion due to static electricity and to improve the reduction in transmittance due to reflection, and display panels also prevent dust adhesion due to static electricity. Therefore, prevention of reflection on the screen has been demanded.
In response to these demands, various radiation curable materials have been proposed with a focus on high productivity and curing at room temperature.

  As such a technique, for example, a composition containing a sulfonic acid and a phosphoric acid monomer as an ion conductive component (Patent Document 1), a composition containing a chain metal powder (Patent Document 2), an oxidation A composition mainly composed of tin particles, polyfunctional acrylate, and a copolymer of methyl methacrylate and polyether acrylate (Patent Document 3), and a conductive coating composition containing a pigment coated with a conductive polymer (Patent Document 4) ) Trifunctional acrylic acid ester, monofunctional ethylenically unsaturated group-containing compound, photopolymerization initiator, and optical disk material containing conductive powder (Patent Document 5), containing antimony dispersed with a silane coupler Conductive paint containing hydrolyzate of tin oxide particles and tetraalkoxysilane, photosensitizer, and organic solvent (Patent Document 6), polymerizable in molecule Reaction product of alkoxysilane containing saturated groups and metal oxide particles, liquid curable resin composition containing trifunctional acrylic compound and radiation polymerization initiator (Patent Document 7), primary particle size of 100 nm or less A conductive oxide fine powder, an easily dispersible low boiling solvent of the conductive oxide fine powder, a hardly dispersible low boiling solvent of the conductive oxide fine powder, and a transparent conductive film forming material containing a binder resin A paint (patent document 8) etc. can be mentioned.

JP 47-34539 A JP 55-78070 A Japanese Patent Laid-Open No. 60-60166 Japanese Patent Laid-Open No. 2-194071 JP-A-4-172634 Japanese Unexamined Patent Publication No. Hei 6-264209 JP 2000-143924 A JP 2001-131485 A

  However, although such conventional techniques each exhibit a certain effect, a cured film that is required to have all functions as a hard coat, an antistatic film, and an antireflection film in recent years. As such, it was not always satisfactory.

  For example, the conventional techniques as described in the above prior art documents have the following problems. The composition described in Patent Document 1 uses an ion conductive material, but the antistatic performance is not sufficient, and the performance varies due to drying. Since the composition described in Patent Document 2 disperses a chain-like metal powder having a large particle size, transparency is lowered. Since the composition described in Patent Document 3 contains a large amount of non-curable dispersant, the strength of the cured film decreases. Since the material described in Patent Document 5 contains high-concentration chargeable inorganic particles, transparency is lowered. The paint described in Patent Document 6 has insufficient long-term storage stability. Patent Document 7 does not disclose any method for producing a composition having antistatic performance. When the transparent conductive film is formed by applying and drying the paint described in Patent Document 8, the organic matrix made of the binder composition is not provided with a cross-linked structure, so it cannot be said that the organic solvent resistance is sufficient.

  Increasing the amount of conductive particles to increase the antistatic performance can be easily conceived, but in that case, the transparency decreases due to the increase in visible light absorption by the cured film, and the UV transmittance decreases. The problems that the curability is lowered, the adhesion to the base material, and the leveling property of the coating liquid are impaired cannot be avoided. On the other hand, when the blending amount of the conductive particles is reduced, sufficient antistatic performance is not exhibited.

  The present invention has been made in view of the above-described problems, and has a coating film (coating) excellent in curability and excellent in antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. It aims at providing the liquid curable composition which can be formed, and its cured film.

  As a result of earnest research to solve the above-mentioned problems, the present inventor has found that tin-containing indium oxide particles having a specific particle size, a compound having two or more polymerizable unsaturated groups in the molecule, a photopolymerization initiator, and It has been found that by using a composition containing a solvent, a cured film that exhibits antistatic performance and does not impair transparency can be obtained even if the blending amount of the conductive particles is small as compared with the prior art. Was completed.

  That is, the present invention provides the following liquid curable composition and cured film thereof.

[1] The following components (A), (B), (C) and (D):
(A) Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less and a secondary particle size of 50 nm or less (B) Two or more polymerizable unsaturated groups in the molecule Compound (C) Photopolymerization initiator (D) Liquid curable composition containing a solvent.
[2] The liquid curable composition according to the above [1], wherein the content of the component (A) is 5 to 40% by weight in the total solid components.
[3] The liquid curable composition according to the above [1] or [2], wherein the component (A) is oxide particles surface-treated with a surface treatment agent.
[4] In the above [3], the surface treatment agent is a compound having two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or a group that generates a silanol group by hydrolysis. The liquid curable composition as described.
-X-C (= Y) -NH- (1)
[Wherein, X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]
[5] A cured film obtained by curing the liquid curable composition according to any one of [1] to [4].
[6] The cured film according to the above [5], which has a surface resistance value of 1 × 10 ¹² Ω / □ or less.
[7] A method for producing a cured film, comprising a step of irradiating the liquid curable composition according to any one of [1] to [4] with radiation to cure the composition.

According to the present invention, a liquid curable composition having excellent curability and capable of forming a coating film (film) having excellent antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. And a cured film thereof.
According to the liquid curable composition of the present invention, a cured film having both antistatic properties and transparency requirements can be obtained.

Hereinafter, embodiments of the present invention will be specifically described.
I. Liquid curable composition The liquid curable composition of the present invention (hereinafter sometimes referred to as “the composition of the present invention”) includes the following components (A), (B), (C) and (D):
(A) Tin-containing indium oxide (ITO) particles (B) A compound having two or more polymerizable unsaturated groups in the molecule (C) a photopolymerization initiator (D) a solvent.
Hereinafter, it demonstrates concretely for every component.

1. Ingredient (A)
The component (A) used in the present invention is tin-containing indium oxide (hereinafter sometimes simply referred to as “ITO”) particles. A component (A) is an essential component in order to provide electroconductivity (antistatic property) to the cured film obtained by hardening the composition of this invention. Moreover, the primary particle diameter of ITO particle | grains is 20 nm or less, and a secondary particle diameter is 50 nm or less. By setting the particle diameter of the ITO particles as described above, it is possible to ensure conductivity (antistatic property) and at the same time maintain the transparency of the cured film. If the primary particle size and the secondary particle size of ITO particles exceed 20 nm and 50 nm, respectively, the transparency of the resulting cured film may be impaired.
The primary particle size of the ITO particles is preferably 15 nm or less, and the secondary particle size is preferably 40 nm or less.

The primary particle diameter of the ITO particles of the component (A) is a value measured with a transmission electron microscope when the shape is spherical regardless of the surface treatment described later, and the shape is elongated like a needle shape. In this case, the short axis is observed with a transmission electron microscope, and the value is obtained as the number average particle diameter.
The secondary particle size of the ITO particles of the component (A) is a value determined by a dynamic light scattering particle size distribution measuring device regardless of the presence or absence of a surface treatment described later.

  As a commercial item as such powder of ITO particle | grains, the Fuji Chemical Co., Ltd. brand name: ITO powder etc. can be mentioned, for example.

  The ITO particles used as the component (A) can be used in a state of being dispersed in a powder or a solvent, but it is preferable to use in a state of being dispersed in a solvent because uniform dispersibility is easily obtained.

  As a commercial item which disperse | distributed ITO particle | grains used as a component (A) to the solvent, the Fuji Chemical Co., Ltd. brand name: Hout form NID-20 etc. can be mentioned, for example.

The ITO particles used as the component (A) may be ITO particles surface-treated with a surface treatment agent or the like in order to improve dispersibility in a solvent.
Here, examples of the surface treatment agent include an alkoxysilane compound, tetrabutoxy titanium, tetrabutoxy zirconium, tetraisopropoxy aluminum, and the like. These can be used alone or in combination of two or more.

  Specific examples of the alkoxysilane compound include compounds having an unsaturated double bond in the molecule, such as γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and γ-glycid. A group of compounds having an epoxy group in the molecule such as xylpropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane, and an amino group in the molecule such as γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane. Compound groups having γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc., compounds having a mercapto group in the molecule, alkyltrisilanes such as methyltrimethoxysilane, methyltriethoxysilane, and phenyltrimethoxysilane Etc. Can do. Among these surface treatment agents, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, etc. are surface-treated ITO particles. From the viewpoint of dispersion stability.

Moreover, as a surface treating agent, what has a functional group which copolymerizes or crosslinks with an organic resin (reactive surface treating agent) is also preferable. As such a surface treatment agent, a compound group having an unsaturated double bond in the molecule, two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or hydrolysis may be used. A compound having a group that forms a silanol group is preferred.
-X-C (= Y) -NH- (1)
[Wherein, X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

  The group represented by the formula (1) is preferably a urethane bond [—O—C (═O) —NH—], —O—C (═S) —NH—, and a thiourethane bond [—S—C ( = O) -NH-] is at least one group selected from the group consisting of.

As such a surface treating agent, for example, urethane bond [—O—C (═O) NH—] and / or thiourethane bond [—S—C (═O) NH—] and two or more in the molecule The alkoxysilane compound which has a polymerizable unsaturated group can be mentioned. Specific examples include compounds represented by the following formula (2).
In the formula, R ¹ is a methyl group, R ² is an alkyl group having 1 to 6 carbon atoms, R ³ is a hydrogen atom or a methyl group, m is 1 or 2, n is an integer of 1 to 5, and X is 1 to 5 carbon atoms. 6 is a divalent alkylene group having 3 to 14 carbon atoms, Y is a chain, cyclic or branched group, and Z is any one of an (n + 1) -valent chain, cyclic or branched group. A divalent hydrocarbon group having 2 to 14 carbon atoms. Z may contain an ether bond.

The compound represented by the formula (2) can be produced by reacting mercaptoalkoxysilanes, diisocyanates and hydroxyl group-containing polyfunctional (meth) acrylates.
As a preferable production method, for example, an intermediate bonded with a thiourethane bond by reaction of mercaptoalkoxysilanes and diisocyanates is produced, and then a urethane bond is formed by reaction of the remaining isocyanate with a hydroxyl group-containing polyfunctional (meth) acrylate. And a method for producing a product bonded with the above.

  The same product can also be obtained by reacting the remaining isocyanate with mercaptoalkoxysilane after first producing an intermediate bonded with a urethane bond by reaction of diisocyanates with hydroxyl group-containing polyfunctional (meth) acrylates. Although it can be obtained, the addition reaction of mercaptoalkoxysilanes and (meth) acrylic groups occurs at the same time, so that the purity is lowered and a gel-like product may be formed.

  Examples of mercaptoalkoxysilanes used in the production of the compound represented by the formula (2) include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltributoxysilane, and γ-mercaptopropyldimethylmethoxy. Examples include silane and γ-mercaptopropylmethyldimethoxysilane. Of these, γ-mercaptopropyltrimethoxysilane and γ-mercaptopropylmethyldimethoxysilane are preferable.

  As a commercial item of mercapto alkoxysilanes, Toray Dow Corning Co., Ltd. brand name: SH6062 can be mentioned, for example.

  Examples of the diisocyanates include 1,4-butylene diisocyanate, 1,6-hexylene diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated bisphenol A diisocyanate, 2,4-toluene diisocyanate, 2,6- And toluene diisocyanate. Among these, 2,4-toluene diisocyanate, isophorone diisocyanate, and hydrogenated xylylene diisocyanate are preferable.

  As a commercial item of a polyisocyanate compound, Mitsui Nisso Urethane Co., Ltd. product name: TDI-80 / 20, TDI-100, MDI-CR100, MDI-CR300, MDI-PH, NDI, Nippon Polyurethane Industry ( Product name: Coronate T, Millionate MT, Millionate MR, HDI, Takeda Pharmaceutical Co., Ltd. Product name: Takenate 600, etc.

  Examples of the hydroxyl group-containing polyfunctional (meth) acrylates include trimethylolpropane di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipenta An example is erythritol penta (meth) acrylate. Of these, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, pentaerythritol tri (meth) acrylate, and dipentaerythritol penta (meth) acrylate are preferable. These form two or more polymerizable unsaturated groups in the compound represented by formula (2).

  These mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates can be used singly or in combination of two or more.

The preferred blending ratio of mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates for producing the compound represented by formula (2) is preferably a molar ratio of diisocyanates to mercaptoalkoxysilanes. It is 0.8-1.5, More preferably, it is 1.0-1.2. When this molar ratio is less than 0.8, the storage stability of the composition may be lowered, and when it exceeds 1.5, the dispersibility may be lowered.
The molar ratio of the hydroxyl group-containing (meth) acrylates to the diisocyanates is preferably 1.0 to 1.5, and more preferably 1.0 to 1.2. When this molar ratio is less than 1.0, gelation may occur, and when it exceeds 1.5, the antistatic property may deteriorate.

  The production of the compound represented by the formula (2) is usually preferably carried out in dry air in order to prevent anaerobic polymerization of the acrylic group and to prevent hydrolysis of the alkoxysilane. The reaction temperature is preferably 0 ° C to 100 ° C, more preferably 20 ° C to 80 ° C.

  In the production of the compound represented by the formula (2), a known catalyst may be added by a urethane reaction for the purpose of shortening the production time. Examples of the catalyst include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin di (2-ethylhexanoate), and octyltin triacetate. The addition amount of the catalyst is 0.01% by weight to 1% by weight with respect to the total amount with the diisocyanates.

  Moreover, you may add a thermal-polymerization inhibitor at the time of manufacture in order to prevent the thermal polymerization of the compound shown in Formula (2). Examples of the thermal polymerization inhibitor include p-methoxyphenol and hydroquinone. The addition amount of the thermal polymerization inhibitor is preferably 0.01% by weight to 1% by weight with respect to the total with the hydroxyl group-containing polyfunctional (meth) acrylates.

The production of the compound represented by the formula (2) can also be carried out in a solvent. The solvent can be appropriately selected from solvents having a boiling point of 200 ° C. or less without reacting with mercaptoalkoxysilanes, diisocyanates, and hydroxyl group-containing polyfunctional (meth) acrylates.
Specific examples of such solvents include ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, esters such as ethyl acetate, butyl acetate and amyl acetate, and hydrocarbons such as toluene and xylene.

In the present invention, (A) the surface-treated ITO particles can be produced by hydrolyzing the surface treatment agent in the presence of ITO particles. A preferable production method is (A) a method in which water is added to a mixture of ITO particles, a surface treatment agent, and an organic solvent, and the mixture is hydrolyzed.
In this production method, by hydrolysis of the surface treatment agent, the alkoxy group is once converted into a silanol group (Si—OH), and this silanol group reacts with the metal hydroxide (M—OH) on the ITO particles, It is presumed that the surface treatment agent is fixed on the ITO particles by forming a metalloxane bond (MO-Si).

  The compounding amount of the surface treatment agent is preferably 0.1 to 50 parts by weight, and more preferably 1 to 35 parts by weight with respect to 100 parts by weight of (A) ITO particles. If the surface treatment agent is less than 0.1 parts by weight, the cured film may have insufficient wear resistance, and if it exceeds 50 parts by weight, the antistatic performance may be insufficient.

  The amount of water is preferably 0.5 to 1.5 equivalents based on the total alkoxy equivalents in the surface treatment agent, and 0.5 to 5.0 weights per 100 parts by weight of the surface treatment agent. It is preferable to add a part. The water used is preferably ion exchange water or distilled water.

  The hydrolysis reaction can be carried out in the presence of an organic solvent by heating and stirring at a temperature of 0 ° C. to the boiling point of the component, usually 30 to 100 ° C. for 1 to 24 hours. As the organic solvent, when (A) ITO particles dispersed in an organic solvent in advance are used, it can be carried out as they are, but an organic solvent may be added separately.

In addition, when performing a hydrolysis, in order to accelerate | stimulate reaction, you may add an acid or a base as a catalyst.
Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, methanesulfonic acid, toluenesulfonic acid, phthalic acid, malic acid, tartaric acid, malonic acid, formic acid, oxalic acid, methacrylic acid, acrylic acid, itaconic acid And organic salts such as tetramethylammonium hydrochloride and tetrabutylammonium hydrochloride.
Examples of the base include amines such as aqueous ammonia, triethylamine, tributylamine, and triethanolamine. A preferable catalyst is an acid, and an organic acid is more preferable. The amount of these catalysts added is preferably 0.001 to 1 part by weight, more preferably 0.01 to 0.1 part by weight, based on 100 parts by weight of the alkoxysilane compound.

By adding a dehydrating agent at the end of the hydrolysis reaction, (A) the hydrolyzate of the surface treatment agent can be more effectively fixed on the ITO particles.
Examples of the dehydrating agent include organic carboxylic acid orthoesters and ketals. Specifically, for example, orthoformate methyl ester, orthoformate ethyl ester, orthoacetic acid methyl ester, orthoacetic acid ethyl ester, etc., acetone dimethyl ketal, diethyl ketone dimethyl, etc. Examples include ketal, acetophenone dimethyl ketal, cyclohexanone dimethyl ketal, cyclohexanone diethyl ketal, and benzophenone dimethyl ketal. Among them, preferred are organic carboxylic acid orthoesters, and more preferred are orthoformate methyl ester and orthoformate ethyl ester.

  These dehydrating agents can be added in an amount of not less than 10 moles and not more than 10 moles, preferably not less than 1 mole and not more than 3 moles of the water content in the composition. If it is less than the equivalent mole, the storage stability may not be sufficiently improved. These dehydrating agents are preferably added after the preparation of the composition. This promotes the storage stability of the composition and the formation of chemical bonds between the silanol groups in the hydrolyzate of the surface treatment agent and (A) ITO particles.

Since the (A) ITO particles surface-treated with such a surface treatment agent have extremely good dispersibility in a solvent, the surface treatment agent is chemically bonded via a siloxy group (Si—O—). (A) It is estimated that it is fixed to the surface of the ITO particles.
In the present invention, the (A) ITO particles surface-treated with the reactive surface treatment agent are particularly referred to as reactive particles (RA).

  The blending amount of component (A) is not particularly limited, but is preferably 5 to 40% by weight, more preferably 7 to 35% by weight, based on 100% by weight of the total solid content of the composition of the present invention. The same applies to the case where the component (A) is surface-treated. When the blending amount is less than 5% by weight, the antistatic property may be inferior, and when it exceeds 40 parts by weight, the film forming property of the coating film may be inferior. Here, the compounding quantity of a component (A) says the compounding quantity as the solid content, and does not contain a dispersion medium.

2. Ingredient (B)
Component (B) used in the present invention is a compound having two or more polymerizable unsaturated groups in the molecule, and imparts film formability and transparency to a cured film obtained by curing the composition of the present invention. It is an ingredient to do. By using such a component (B), a cured product having excellent scratch resistance and organic solvent resistance can be obtained.

Specific examples of component (B) include (meth) acrylic esters and vinyl compounds.
(Meth) acrylic esters include trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane diyldimethanol Di (meth) acrylates, poly (meth) acrylates of ethylene oxide or propylene oxide adducts of starting alcohols in the production of these compounds, oligoesters having two or more (meth) acryloyl groups in the molecule (meta ) Acrylates, oligoether (meth) acrylates, oligourethane (meth) acrylates, oligoepoxy (meth) acrylates, and the like.
Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether. Among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra ( (Meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and tricyclodecanediyldimethanol di (meth) acrylate are preferred. These (B) components may be used individually by 1 type, and may use 2 or more types together.

  The amount of component (B) is preferably 55 to 94% by weight, more preferably 60 to 92% by weight, based on 100% by weight of the total solid content of the composition of the present invention. If the amount of component (B) is less than 55% by weight, the resulting cured product may have poor transparency, and if it exceeds 94% by weight, the antistatic property may be inferior.

3. Ingredient (C)
Component (C) is a photopolymerization initiator, and is added to increase the curing rate when the composition of the present invention is cured by irradiation with radiation.
In the present invention, radiation means visible light, ultraviolet light, far ultraviolet light, X-rays, electron beams, α rays, β rays, γ rays, and the like.

  The amount of component (C) is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight, based on 100% by weight of the total solid content of the composition of the present invention. A component (C) can be used individually by 1 type or in combination of 2 or more types.

  Examples of the component (C) include 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4- Chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chloro Oxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 4,4-trimethylpentylphosphine oxide and the like.

4). Ingredient (D)
Component (D) used in the present invention is a solvent, and is a component for adjusting the fluidity of the composition of the present invention.

  The solvent which is the component (D) in the composition of the present invention is preferably added so that the concentration of the total solid content of the composition is 0.5 to 75% by weight. That is, (D) The amount of the solvent added is preferably in the range of 33.3 to 19,900 parts by weight when the total solid content of the composition of the present invention is 100 parts by weight. The reason for this is that (D) when the amount of the solvent added is less than 33.3 parts by weight, the viscosity of the composition may increase and the coatability may decrease, while when it exceeds 19,900 parts by weight, This is because the thickness of the cured product is too thin and sufficient hardness may not be exhibited.

  Although the kind of solvent is not specifically limited, Usually, a solvent having a boiling point of 200 ° C. or less at normal pressure is preferable. Specifically, water, alcohols, ketones, ethers, esters, hydrocarbons, amides and the like are used. These can be used alone or in combination of two or more.

  Examples of alcohols include methanol, ethanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, benzyl alcohol, and phenethyl alcohol. Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Examples of ethers include dibutyl ether, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether (PGME), and the like. Examples of the esters include ethyl acetate, butyl acetate, ethyl lactate, methyl acetoacetate, and ethyl acetoacetate. Examples of hydrocarbons include toluene and xylene. Examples of amides include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

  In the case where the ITO particles of component (A) are dispersed in a dispersion medium, the dispersion medium may be used as it is as the solvent of component (D), or only a solvent different from the dispersion medium is used. You may use, Furthermore, you may use a dispersion medium and another solvent together as a solvent of a component (D).

5. Compound having other polymerizable unsaturated group The composition of the present invention requires a compound having other polymerizable unsaturated group (component (E)) as a component other than components (A) to (D). It can be blended according to. Here, the component (E) is a compound having one polymerizable unsaturated group in the molecule.
Specific examples of the component (E) include, for example, vinyl group-containing lactams such as N-vinylpyrrolidone and N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, cyclohexyl (meth) acrylate and other alicyclic structure-containing (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine , Vinylimidazole, vinylpyridine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl ( Acrylate), propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl ( (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl ( (Meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate Relate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) ) Acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (Meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, Examples thereof include hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and a compound represented by the following formula (3).
_{^{CH 2 = C (R 4)}} -COO (R 5 O) p -Ph-R 6 (3)
(Wherein R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ⁶ represents a hydrogen atom or 1 to 12 carbon atoms, preferably 1 -9 represents an alkyl group, Ph represents a phenylene group, and p represents a number of 0 to 12, preferably 1 to 8.)

  As a commercial item of an ingredient (E), Aronix M-101, M-102, M-111, M-113, M-114, M-117 (above, the product made by Toa Gosei Co., Ltd.); Biscote LA, STA, IBXA, 2-MTA, # 192, # 193 (Osaka Organic Chemical Co., Ltd.); NK Ester AMP-10G, AMP-20G, AMP-60G (above, Shin-Nakamura Chemical Co., Ltd.); Light acrylate L -A, SA, IB-XA, PO-A, PO-200A, NP-4EA, NP-8EA (above, manufactured by Kyoeisha Chemical Co., Ltd.); FA-511, FA-512A, FA-513A (above And Hitachi Chemical Co., Ltd.).

6). Non-conductive particles In the present invention, the non-conductive particles or the non-conductive particles and the alkoxysilane compound are reacted in an organic solvent as long as the liquid curable composition does not cause problems such as separation and gelation. You may use together the particle | grains obtained.

By using the non-conductive particles together with the ITO particles as the component (A), the anti-static function, that is, the scratch resistance while maintaining a value of 10 ¹³ Ω / □ or less as the surface resistance when a cured film is formed. Can be improved.

  Specific examples of such non-conductive particles include oxide particles such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, and cerium oxide, or a group consisting of silicon, aluminum, zirconium, titanium, and cerium. Examples thereof include oxide particles containing two or more selected elements.

  The primary particle size of the non-conductive particles is preferably 0.1 μm or less, more preferably 0.001 to 0.05 μm, as a value obtained by observation with a transmission electron microscope. When it exceeds 0.1 μm, sedimentation may occur in the composition or the smoothness of the coating film may be lowered.

  When mix | blending nonelectroconductive particle | grains with the composition of this invention, you may mix, after hydrolyzing a nonelectroconductive particle and an alkoxysilane compound in an organic solvent. This treatment improves the dispersion stability of the non-conductive particles. The hydrolysis treatment of the non-conductive particles and the alkoxysilane compound in the organic solvent can be performed in the same manner as the method for treating the oxide particles as the component (A) described above.

Examples of commercially available non-conductive particles include silicon oxide particles (for example, silica particles), colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, NBA- ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc. it can. Moreover, as a powder silica, Nippon Aerosil Co., Ltd. product name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. Product name: Sildex H31, H32, H51, H52, H121 H122, manufactured by Nippon Silica Kogyo Co., Ltd., trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade name: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd., trade names: SG flakes, and the like.
Moreover, as an aqueous dispersion of aluminum oxide (alumina), product name: Alumina Sol-100, -200, -520 manufactured by Nissan Chemical Industries, Ltd .; As a dispersion of zirconium oxide, manufactured by Sumitomo Osaka Cement Co., Ltd. ( (Toluene, methyl ethyl ketone-dispersed zirconia sol); As a cerium oxide aqueous dispersion, manufactured by Taki Chemical Co., Ltd. Product name: Niedal; As a powder and solvent dispersion of alumina, zirconium oxide, titanium oxide, etc. Product name: Nanotech etc. can be mentioned.

  The blending ratio of the non-conductive particles is preferably 0.1 to 35% by weight, more preferably 0.5 to 30% by weight in 100% by weight of the total solid content of the composition of the present invention.

7). Additives In the composition of the present invention, as other additives, antioxidants, ultraviolet absorbers, light stabilizers, thermal polymerization inhibitors, leveling agents, surfactants, lubricants and the like are blended as necessary. be able to. As antioxidant, Ciba Specialty Chemicals Co., Ltd. trade name: Irganox 1010, 1035, 1076, 1222, etc. As ultraviolet absorbers, Ciba Specialty Chemicals Co., Ltd. trade name: Tinuvin P234, 320, 326, 327, 328, 213, 329, manufactured by Sipro Kasei Co., Ltd., trade name: Seasorb 102, 103, 501, 202, 712, etc., as light stabilizers, manufactured by Ciba Specialty Chemicals Co., Ltd., trade names: Tinuvin 292, 144, 622LD, Sankyo Co., Ltd. product name: Sanol LS770, LS440, Sumitomo Chemical Co., Ltd. product name: Sumisorb TM-061.

  The viscosity of the composition of the present invention thus obtained is usually 1 to 20,000 mPa · s, preferably 1 to 1,000 mPa · s at 25 ° C.

  As described above, the solid content excluding the solvent (D) of the composition of the present invention is preferably in the range of 0.5 to 75% by weight. If the solid content is less than 0.5% by weight, the thickness of the resulting cured product may be too thin and sufficient hardness may not be exhibited. If it exceeds 75% by weight, the viscosity of the composition increases. The applicability may decrease.

8). Method for preparing liquid curable composition The liquid curable composition of the present invention comprises the above components (A) to (D), and, if necessary, compounds having other polymerizable unsaturated groups, non-conductive particles. It can be obtained by adding and mixing other additives.

II. Cured Film and Antistatic Laminate The cured film of the present invention can be obtained by applying and drying the liquid curable composition described above, and then irradiating it with radiation to cure the composition.
The surface resistance of the obtained cured film is usually 1 × 10 ¹² Ω / □ or less, preferably 1 × 10 ¹⁰ Ω / □ or less, more preferably 1 × 10 ⁸ Ω / □ or less. When the surface resistance exceeds 1 × 10 ¹² Ω / □, the antistatic performance is not sufficient, and dust may be easily attached or the attached dust may not be easily removed.

  Although there is no restriction | limiting in particular as a coating method of a composition, For example, well-known methods, such as roll coating, spray coating, flow coating, dipping, screen printing, inkjet printing, are applicable.

The radiation source used for curing the composition is not particularly limited as long as it can be cured in a short time after the composition is applied.
Examples of visible ray sources include direct sunlight, lamps, fluorescent lamps, and lasers. Examples of ultraviolet ray sources include mercury lamps, halide lamps, and lasers, and electron beam sources. For example, a method using thermoelectrons generated from a commercially available tungsten filament, a cold cathode method in which metal is generated through a high voltage pulse, and a secondary electron generated by collision of ionized gaseous molecules with a metal electrode. Secondary electron system using
Examples of the source of α-rays, β-rays, and γ-rays include fission materials such as ⁶⁰ Co. For the γ-rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations may be irradiated alone or in combination of two or more, or one or more kinds of radiation may be irradiated after a certain period of time.

The thickness of the cured film is preferably 0.1 to 20 μm. It is relatively thick, preferably 2 to 15 μm, in applications that place importance on scratch resistance on the outermost surface such as touch panels and CRTs. On the other hand, when used as an antistatic film of an optical film, the thickness is preferably 0.1 to 10 μm.
Moreover, when using for an optical film, transparency is required and it is preferable that a total light transmittance is 85% or more.

  The substrate to which the cured film of the present invention is applied is not particularly limited, such as metal, ceramics, glass, plastic, wood, slate, etc., but as a material that is highly productive, radiation curable, and can exhibit industrial utility, For example, it is preferably applied to a film or a fiber-like substrate. Particularly preferred materials are plastic film and plastic plate. Examples of such plastics include polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, polyethylene terephthalate (PET) resin, triacetyl cellulose resin, and diethylene carbonate diallyl carbonate (CR-39). ), ABS resin, AS resin, polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene resin), and the like.

In addition, the base material which apply | coats the liquid curable composition of this invention has a preferable base material which performed the easy-adhesion process on the surface where a liquid curable composition is apply | coated. When the composition of the present invention is applied to a substrate that has been subjected to an easy adhesion treatment, the ITO particles of the component (A) are unevenly distributed on the substrate side.
Examples of the easy adhesion treatment include treatment such as corona discharge treatment and easy adhesion layer coating treatment.
As a preferable commercially available base material subjected to easy adhesion treatment, polyester film A4300 (manufactured by Toyobo Co., Ltd.) and the like can be mentioned.

  By applying and curing the liquid curable composition of the present invention on a polyester film A4300 (manufactured by Toyobo Co., Ltd.) that has been subjected to easy adhesion treatment, the ITO particles of component (A) are unevenly distributed on the substrate side. FIG. 1 shows an electron micrograph of a cross section of the cured film showing a typical state. In FIG. 1, the lower part is the base material side, the upper part is the air side, and it can be seen that the ITO particles are unevenly distributed on the base material side.

  When providing an optical article with an antireflection function, a method of forming a low refractive index layer or a multilayer structure of a low refractive index layer and a high refractive index layer is formed on a base material or a hard-coated base material. Although the cured film of the present invention is formed on a substrate, it is a layer of an antistatic laminate that imparts an antireflection function to an optical article. Use as a structure is also useful. That is, an antistatic laminate having antireflection performance can be formed by using the cured film of the present invention in combination with a film having a lower refractive index.

  As such an antistatic laminate, for example, the low refractive index layer formed on the cured film of the present invention has a thickness of 0.05 to 0.20 μm and a refractive index of 1.30 to 1. And a laminate using a coating layer of .45. Further, as the high refractive index layer formed on the cured film of the present invention, a coating layer having a thickness of 0.05 to 0.20 μm and a refractive index of 1.65 to 2.20 is used. Examples of the low refractive index layer formed on the refractive index layer include a laminate using a coat layer having a thickness of 0.05 to 0.20 μm and a refractive index of 1.30 to 1.45. it can.

  In the production of an antistatic laminate, in order to further provide other functions such as a non-glare effect, a light selective absorption effect, weather resistance, durability, transferability, etc., for example, a light scattering property of 1 μm or more It is possible to add a layer containing particles, add a layer containing a dye, add a layer containing an ultraviolet absorber, add an adhesive layer, add an adhesive layer and a release layer, etc. Furthermore, these function-imparting components can be added as one component of the antistatic curable composition of the present invention.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, parts and% respectively represent parts by weight and% by weight unless otherwise specified.

Example 1
(1) Production of liquid curable composition In a container shielded from ultraviolet rays, tin-containing indium oxide dispersion (Hout Form NID-20 manufactured by Fuji Chemical Co., Ltd., dispersion solvent isopropyl alcohol, tin-containing indium oxide 20% by weight, Average primary particle size 13 nm, hereinafter may be referred to as ITO particle-1) 50 parts, dipentaerythritol hexaacrylate (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., hereinafter may be referred to as B-1) 86 parts, 2.5 parts of 1-hydroxycyclohexyl phenyl ketone, 1.5 parts of 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 141.8 parts of isopropyl alcohol and By stirring 51.3 parts of propylene glycol monomethyl ether at 50 ° C. for 2 hours, uniform To obtain a composition of the liquid. 2 g of this composition was weighed on an aluminum pan, dried on a hot plate at 170 ° C. for 1 hour, and weighed to determine the solid content, which was 30% by weight. In addition, 2 g of this composition was weighed in a magnetic crucible, pre-dried on a hot plate at 80 ° C. for 30 minutes, and baked in a muffle furnace at 750 ° C. for 1 hour to determine the inorganic content in the solid content. When determined, it was 10% by weight.

Examples 2-3 and Comparative Examples 1-3
By the same operation method, each composition of Examples 2-3 and Comparative Examples 1-3 shown in Table 1 was obtained.
In Table 1, the blending amount of the ITO particles and the dispersant represents only the solid content in the added dispersion, and the dispersion medium is included in the blending amount of the solvent.

<Production of cured film>
Composition obtained in Examples 1 to 3 and Comparative Examples 1 to 3 on polyester film A4300 (manufactured by Toyobo Co., Ltd., film thickness 188 μm) subjected to surface easy adhesion treatment using a wire bar coater Each product was coated and dried in an oven at 80 ° C. for 3 minutes to form a coating film. Subsequently, the coating film was cured with ultraviolet rays under a light irradiation condition of 1 J / cm ² using a metal halide lamp in the atmosphere to form a cured film (hard coat layer) having a thickness of 3 μm.

<Evaluation of cured film>
The total cured light transmittance, haze, and surface resistance of the obtained cured film were evaluated according to the following criteria. The obtained results are shown in Table 1.
(1) Total light transmittance, haze The total light transmittance (%) and haze (%) of the cured film were measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). .
(2) The pencil hardness of the cured film of the pencil hardness was evaluated in accordance with JIS K5600-5-4, and the film cured on the glass substrate was evaluated.
(3) Surface resistance The surface resistance (Ω / □) of the cured film was measured using a high resistance meter (Agilent Technology Co., Ltd. Agilent 4339B) and Resistivity Cell 16008B (Agilent Technology Co., Ltd.). The measurement was performed under the condition of an applied voltage of 100V.

The contents of the abbreviations in Table 1 are shown below.
ITO particle-1: manufactured by Fuji Chemical Co., Ltd. Hout form NID-20 (primary particle size: 13 nm, secondary particle size: 25 nm IPA dispersion)
Dispersant 1: Dispersant included in Hout Foam NID-20 manufactured by Fuji Chemical Co., Ltd. ITO particle-2: Pastoran manufactured by Mitsui Kinzoku Mine Co., Ltd. (primary particle size: 30 nm, secondary particle size: 150 nm, water dispersion)
Dispersant 2: Dispersant contained in Pastoran (ITO particle-2) manufactured by Mitsui Mining Co., Ltd. ITO particle-3: Nanotech manufactured by CI Kasei Co., Ltd. (primary particle size: 25 nm, secondary particle size: 80 nm EtOH dispersion body)
Dispersant 3: Dispersant included in Nanotech manufactured by C-I Kasei Co., Ltd. ITO particle-4: Pastoran manufactured by Mitsui Mining Co., Ltd. (primary particle size: 30 nm, secondary particle size: 300 nm MeOH dispersion)
Dispersant 4: Dispersant contained in Pastoran (ITO particle-4) manufactured by Mitsui Mining Co., Ltd. PGME: Propylene glycol monomethyl ether IPA: Isopropanol MeOH: Methanol EtOH: Ethanol

From the results of Table 1, Comparative Examples 1 and 3 have a surface resistance of 10 ⁷ Ω / □, which is very small, but has a large haze and inferior transparency. In Comparative Example 2, on the contrary, the haze is relatively low, but the surface resistance is as large as 10 ¹⁴ Ω / □, and the antistatic property is inferior.
On the other hand, in Examples 1 to 3, the surface resistance is all on the order of 10 ¹¹ Ω / □, and the haze is as low as 0.1% or 0.2%, so that both antistatic properties and transparency are required. It can be seen that it has characteristics satisfying

  As described above, according to the present invention, a liquid that can form a coating film having excellent curability and excellent antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. A curable composition, a cured film, and an antistatic laminate can be provided.

  Since the cured film of the present invention has excellent scratch resistance and adhesion, it is useful as a hard coat. Further, since it has an excellent antistatic function, it is useful as an antistatic film by being disposed on a substrate of various shapes such as a film, a plate, or a lens.

  Examples of application of the cured film of the present invention include, for example, the surface of a highly designed container such as a protective film for a touch panel, a transfer foil, a hard coat for an optical disk, an automotive window film, an antistatic protective film for a lens, and a cosmetic container. Use as a hard coat mainly for the purpose of preventing scratches on the product surface and preventing dust from being attached due to static electricity, and for various display panels such as CRTs, liquid crystal display panels, plasma display panels, electroluminescence display panels, etc. Examples thereof include use as an antireflection film for antistatic use, use as an antireflection film for antistatic use such as a plastic lens, a polarizing film, and a solar battery panel.

  The antistatic laminate of the present invention has scratches (scratches) on, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic housings, plastic containers, floor materials as building interior materials, wall materials, artificial marble, etc. It can be suitably used as a hard coating material for prevention and contamination prevention; an adhesive for various substrates, a sealing material; a binder material for printing ink, and the like.

FIG. 1 is an electron micrograph of a cured film cross section showing a typical state in which the ITO particles of component (A) are unevenly distributed on the substrate side.

Claims (7)

The following components (A), (B), (C) and (D):
(A) Particles mainly composed of tin-containing indium oxide (ITO) having a primary particle size of 20 nm or less and a secondary particle size of 50 nm or less (B) Two or more polymerizable unsaturated groups in the molecule Compound (C) Photopolymerization initiator (D) Liquid curable composition containing a solvent.   The liquid curable composition according to claim 1, wherein the content of the component (A) is 5 to 40% by weight in the total solid components.   The liquid curable composition according to claim 1 or 2, wherein the component (A) is an oxide particle surface-treated with a surface treatment agent. The liquid curing according to claim 3, wherein the surface treatment agent is a compound having two or more polymerizable unsaturated groups, a group represented by the following formula (1), and a silanol group or a group that generates a silanol group by hydrolysis. Sex composition.
-X-C (= Y) -NH- (1)
[Wherein, X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]   The cured film formed by hardening | curing the liquid curable composition as described in any one of Claims 1-4. The cured film according to claim 5, having a surface resistance value of 1 × 10 ¹² Ω / □ or less. The manufacturing method of the cured film which has a process which irradiates a liquid curable composition as described in any one of Claims 1-4, and hardens this composition.