JP4144477B2 - Liquid curable composition, cured film and antistatic laminate - Google Patents

Description

  The present invention relates to a liquid curable composition, a cured film, and an antistatic laminate. More specifically, it is excellent in curability and various substrates such as plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin). , ABS resin, AS resin, norbornene resin, etc.), metal, wood, paper, glass, ceramics, and other surfaces with excellent antistatic properties, hardness, scratch resistance and transparency ), A cured film, and an antistatic laminate.

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 ester, monofunctional ethylenically unsaturated group-containing compound, photopolymerization initiator, and optical disk material containing conductive powder (Patent Document 5), antimony-containing tin oxide dispersed with silane coupler Conductive paint containing hydrolyzate of particles and tetraalkoxysilane, photosensitizer, and organic solvent (Patent Document 6), polymerizable unsaturated in molecule A liquid curable resin composition containing a reaction product of an alkoxysilane containing silane and metal oxide particles, a trifunctional acrylic compound, and a radiation polymerization initiator (Patent Document 7) having a primary particle size of 100 nm or less A conductive oxide fine powder, an easily dispersible low boiling point solvent of the conductive oxide fine powder, a hardly dispersible low boiling point solvent of the conductive oxide fine powder, and a transparent conductive film forming paint containing a binder resin (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 coating material described in Patent Document 8 is applied and dried to form a transparent conductive film, the organic matrix composed of the binder composition is not provided with a cross-linked structure, so the organic solvent resistance is not 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 ultraviolet transmittance decreases. Problems such as reduced curability, impaired adhesion to the base material, and leveling properties of the coating liquid could not 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, a cured film, and the laminated body for antistatic.

  As a result of earnest research to solve the above-mentioned problems, the present inventor has found that particles containing an oxide containing a specific element as a main component, non-conductive particles, a compound having a specific polymerizable unsaturated group, The present invention has been completed by discovering that the above object can be achieved by using a composition containing component (D) and component (E), which are at least two solvents having different solubility.

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

[1] The following components (A), (B), (C), (D) and (E):
(A) particles mainly composed of an oxide of at least one element selected from the group consisting of indium, antimony, zinc and tin;
(B) silica particles,
(C) Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra Group consisting of (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and tricyclodecanediyldimethanol di (meth) acrylate A compound selected from
(D) a solvent selected from the group consisting of water, ethanol, 1-propanol, isopropyl alcohol, and n-butanol, wherein the solubility at 25 ° C. of component (C) is less than 10% by weight;
(E) A solvent having a solubility at 25 ° C. of 10% by weight or more of component (C) selected from the group consisting of methanol, ethanol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monoethyl ether, and propylene glycol monoethyl ether acetate ,
Containing
The total amount of component (A), component (B) and component (C) is in the range of 15 to 50 parts by weight of component (B) in 100 parts by weight, and components (A), (B) and A liquid curable composition characterized in that (C) is uniformly dispersed or dissolved.
[2] The liquid curable composition according to [1], further including a photopolymerization initiator (F) in addition to the components (A) to (E).
[3] The liquid curing according to [1] or [2], wherein the component (A) is particles mainly composed of antimony-containing tin oxide (ATO) or indium-containing tin oxide (ITO). Sex composition.
[4] The liquid curable composition according to any one of [1] to [3], wherein at least one of the components (A) and (B) is surface-treated with a surface treatment agent. .
[5] 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 according to [4].
-X-C (= Y) -NH- Formula (1)
[Wherein, X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]
[6] The group represented by the formula (1) is —O—C (═O) —NH—, —O—C (═S) —NH—, and —S—C (═O) —NH—. The liquid curable composition according to [5], which is at least one group selected from the group consisting of:
[7] Any of [1] to [6], wherein the component (D) is water and the content in the total solvent contained in the composition is 0.1 to 50% by weight. A liquid curable composition according to any one of the above.
[8] Any one of [1] to [6], wherein the component (D) is an organic solvent, and the content in the total solvent contained in the composition is 5 to 95% by weight. The liquid curable composition as described in 1.
[9] A cured film obtained by curing the liquid curable composition according to any one of [1] to [8], and having a surface resistance value of 1 × 10 ¹² Ω / □ or less.
[10] A cured film comprising a step of irradiating the liquid curable composition according to any one of [1] to [8] with radiation to cure the composition to form a cured film. Manufacturing method.
[11] An antistatic laminate having a cured film layer obtained by curing the liquid curable composition according to any one of [1] to [8].
[12] The antistatic laminate according to [11], wherein the thickness of the cured film layer is 0.1 to 20 μm.

  As described above, according to the present invention, a coating film (film) having excellent storage stability and curability, and excellent antistatic properties, hardness, scratch resistance, and transparency is provided on the surface of various substrates. The liquid curable composition which can be formed, a cured film, and the laminated body for antistatic can be provided.

Hereinafter, embodiments of the present invention will be specifically described.
I. Liquid curable composition The liquid curable composition of the present invention is a particle (component (A)), which is mainly composed of an oxide of at least one element selected from the group consisting of indium, antimony, zinc and tin, non-conductive. Particles (component (B)), a compound having two or more polymerizable unsaturated groups in the molecule (component (C)), and a solvent (component (D)) in which the solubility of component (C) is less than 10% by weight And a solvent (component (E)) having a solubility of 10% by weight or more in component (C), and components (A), (B), and (C) are uniformly dispersed or dissolved in the liquid. It is characterized by.
Hereinafter, each component will be described more specifically.

1. Ingredient (A)
Component (A) used in the present invention is an oxidation of at least one element selected from the group consisting of indium, antimony, zinc and tin from the viewpoint of conductivity and transparency of the cured film of the resulting liquid curable composition. It is a particle mainly composed of an object. These oxide particles are conductive particles.

  Specific oxide particles used as the component (A) include, for example, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), fluorine-containing tin oxide (FTO), phosphorus-containing tin oxide (PTO), Mention may be made of at least one kind of particles selected from the group consisting of zinc antimonate (AZO), indium-containing zinc oxide (IZO) and zinc oxide. Of these, antimony-containing tin oxide (ATO) and tin-containing indium oxide (ITO) are preferable. These can be used alone or in combination of two or more.

  As a commercial item as such an oxide particle powder, for example, Mitsubishi Materials Corporation trade name: T-1 (ITO), Mitsui Kinzoku Co., Ltd. trade name: Pastoran (ITO, ATO), Product names: SN-100P (ATO) manufactured by Ishihara Sangyo Co., Ltd. Product names: Nanotech ITO, manufactured by Nissan Chemical Industries, Ltd. Product names: ATO, FTO, etc.

  The oxide particles used as the component (A) can be used in a state of being dispersed in a powder or a solvent. However, since uniform dispersibility is easily obtained, the oxide particles are preferably used in a state of being dispersed in a solvent.

  Examples of commercially available products in which the oxide particles used as the component (A) are dispersed in a solvent include, for example, trade names: MTC filler 12867 (ATO with water dispersion), MHI filler # 8954MS (ATO with methyl ethyl ketone dispersion) ), Ishihara Sangyo Co., Ltd. Product name: SN-100D (ATO with water dispersion), SNS-10I (ATO with isopropyl alcohol dispersion), SNS-10B (ATO with isobutanol dispersion), SNS-10M (methyl ethyl ketone dispersion) ATO), FSS-10M (isopropyl alcohol-dispersed ATO), manufactured by Nissan Chemical Industries, Ltd. Trade name: Celnax CX-Z401M (methanol-dispersed zinc antimonate), Cellax CX-Z200IP (isopropyl alcohol-dispersed antimonic acid) Zinc), made by Mitsui Kinzoku Co., Ltd. Trade name: Pastran type A (ITO) aqueous dispersion, methanol dispersion, isopropyl alcohol dispersion, methyl ethyl ketone dispersion, toluene dispersion and the like.

The oxide particles used as the component (A) may be oxide 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 alkoxysilane compounds, tetrabutoxy titanium, tetrabutoxy zirconium, tetraisopropoxy aluminum, and the like. These can be used individually by 1 type or in combination of 2 or more types.

  Specific examples of the alkoxysilane compound include a group of 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 group, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, etc., compound group having a mercapto group in the molecule, methyltrimethoxysilane, methyltriethoxysilane, phenyl Trimetoki Alkyl silanes such as silane, and the like. Among these surface treatment agents, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, etc. are surface-treated oxides. This is preferable from the viewpoint of dispersion stability of the particles.

  As a commercial item as powder of the surface-treated oxide particle, Ishihara Sangyo Co., Ltd. brand name: SN-102P (ATO), FS-12P, etc. can be mentioned, for example.

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- Formula (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.

式中、Ｒ^１はメチル基、Ｒ^２は炭素数１〜６のアルキル基、Ｒ^３は水素原子又はメチル基、ｍは１又は２、ｎは１〜５の整数、Ｘは炭素数１〜６の２価のアルキレン基、Ｙは鎖状、環状、分岐状いずれかの炭素数３〜１４の２価の炭化水素基、Ｚは２〜６価の鎖状、環状、分岐状いずれかの炭素数２〜１４の２価の炭化水素基である。Ｚ内には、エーテル結合を含んでもよい。 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 divalent alkylene group, Y is a chain, cyclic or branched divalent hydrocarbon group of 3 to 14 carbon atoms, Z is a 2-6 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, after producing an intermediate bonded with a thiourethane bond by reaction of mercaptoalkoxysilane and diisocyanate, a urethane bond is formed by reaction of the remaining isocyanate with a hydroxyl group-containing polyfunctional (meth) acrylate. A method for producing a combined product can be mentioned.

  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 alkoxysilane, Toray Dow Corning Co., Ltd. brand name: SH6062 can be mentioned, for example.

  Examples of 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 diisocyanate 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 of 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, the surface-treated oxide particles can be produced by hydrolyzing the surface treatment agent in the presence of (A) oxide particles. A preferable production method is a method in which water is added to a mixture of (A) oxide particles, a surface treatment agent, and an organic solvent, and the mixture is hydrolyzed.
In this production method, the alkoxy group is once converted into a silanol group (Si—OH) by hydrolysis of the surface treatment agent, and this silanol group reacts with the metal hydroxide (M—OH) on the oxide particles. It is presumed that the surface treatment agent is fixed on the particles by forming a metalloxane bond (M—O—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 the (A) oxide 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 relative to the total alkoxy equivalent in the surface treatment agent, and 0.5 to 5.0 parts by weight with respect to 100 parts by weight of the surface treatment agent. It is preferable to add. 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 the (A) oxide particles dispersed in the organic solvent in advance are used, they can be used 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 acids 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 oxide 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 and the like, acetone dimethyl ketal, diethyl Examples thereof include ketone dimethyl ketone, 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) oxide particles.

Since the (A) oxide 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—). Thus, it is estimated that (A) the oxide particles are fixed on the surface.
In the present invention, (A) oxide particles surface-treated with a reactive surface treatment agent are particularly referred to as reactive particles (RA).

  The primary particle size of the component (A) is 0.1 μm or less as a value obtained by measuring the dry powder by the BET adsorption method when the shape is spherical regardless of the presence or absence of the surface treatment of the oxide particles, preferably 0.001 to 0.05 μm. When it exceeds 0.1 μm, sedimentation occurs in the composition, and the smoothness of the coating film decreases. When the shape is elongated like a needle, the dried powder is observed with an electron microscope, and the value obtained as the number average particle diameter is 0.005 to 0.1 μm as the short axis average particle diameter, the number average particle diameter as the long axis Is preferably 0.1 to 3 μm. If the long axis particle diameter exceeds 3 μm, sedimentation may occur in the composition.

  The blending amount of component (A) is not particularly limited, but is preferably 1 to 50 parts by weight, more preferably 3 to 45 parts in 100 parts by weight of the total amount of component (A), component (B), and component (C). Parts by weight. The same applies to the case where the component (A) is surface-treated. When the blending amount is less than 1 part by weight, the antistatic property may be inferior, and when it exceeds 50 parts by weight, the film forming property of the coating film may be inferior. Here, the compounding quantity of a component (A), (B) and a component (C) says the compounding quantity as the solid content.

2. Ingredient (B)
The component (B) non-conductive particles used in the present invention are not particularly limited as long as the particles do not have conductivity. Oxide particles or metal particles are preferable. On the other hand, the component (A) is different from the component (B) in that it is a conductive particle. Specific examples of the component (B) include two or more kinds selected from the group consisting of oxide particles such as silicon oxide, aluminum oxide, zirconium oxide, titanium oxide and cerium oxide, or silicon, aluminum, zirconium, titanium and cerium. Examples thereof include oxide particles containing these elements. By using such a component (B), a cured product having excellent scratch resistance and a low haze value can be obtained. That is, by using the component (B) together with the oxide particles as the component (A), while maintaining a value of 10 ¹² Ω / □ or less as an antistatic function, that is, a surface resistance when a cured film is obtained, Scratch resistance can be improved and a low haze value can be achieved. Of these components (B), silica particles are preferred from the viewpoints of film formability and transparency of the cured film of the resulting liquid curable composition.

  The nonconductive particles may be mixed with the composition of the present invention after hydrolyzing the nonconductive particles and the 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.

  Commercially available products of such component (B) include 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 and the like. 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 names: 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.

In order to improve the dispersibility in a solvent, or to copolymerize or cross-link with an organic resin, the non-conductive particles used as the component (B) are the above-described method for treating oxide particles as the component (A); Similarly, surface treatment can be performed.
In the present invention, (B) non-conductive particles surface-treated with a reactive surface treatment agent are particularly referred to as reactive non-conductive particles (RB).

  The primary particle diameter of the component (B) is 0.1 μm or less as a value obtained by measuring the dry powder by the BET adsorption method when the shape is spherical regardless of the presence or absence of surface treatment of the particles, and preferably 0 0.001 to 0.05 μm. When it exceeds 0.1 μm, sedimentation may occur in the composition or the smoothness of the coating film may be lowered.

The blending ratio of component (B) is preferably 3 to 65 parts by weight, more preferably 5 to 50 parts by weight, more preferably 100 parts by weight of the total amount of component (A), component (B) and component (C). Is 15 to 50 parts by weight.

3. Ingredient (C)
Component (C) used in the present invention is a compound having two or more polymerizable unsaturated groups in the molecule from the viewpoint of film formability and transparency of the cured film of the liquid curable composition to be obtained. By using such a component (C), a cured product having excellent scratch resistance and organic solvent resistance can be obtained.

Specific examples of the component (C) 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 (C) components may be used individually by 1 type, and may use 2 or more types together.

  The amount of component (C) is preferably 10 to 96 parts by weight, more preferably 20 to 92 parts by weight, in a total amount of 100 parts by weight of component (A), component (B), and component (C). . If the amount of component (C) is less than 10 parts by weight, the resulting cured product may have poor transparency, and if it exceeds 96 parts by weight, the antistatic property may be inferior.

4). Solvent The solvent used in the present invention comprises a solvent (component (D)) in which the solubility of component (C) is less than 10% by weight, preferably less than 8% by weight, depending on the type of component (C); C) and a solvent (component (E)) having a solubility of 10% by weight or more, preferably 40% by weight or more. That is, whether the specific solvent is component (D) or component (E) is determined by the type of component (C). Here, the solubility is defined by the saturated solubility of the component (C) at 25 ° C. Specifically, it can obtain | require by measuring the solid content density | concentration of the component (C) in the solution which consists of a component (C) and a solvent.

  The total solvent composed of the solvent (D) and the solvent (E) in the liquid curable composition of the present invention has a total concentration of component (A), component (B) and component (C) of 0.5 to 0.5. It is added to 75% by weight. That is, the amount of all solvents added is a value within the range of 33.3 to 19,900 parts by weight when the total amount of component (A), component (B) and component (C) is 100 parts by weight. Is preferred. The reason for this is that when the total amount of the solvent added is less than 33.3 parts by weight, the viscosity of the composition may increase and the coating property may decrease, whereas when it exceeds 19,900 parts by weight, the resulting cured product This is because the thickness of the object is too thin and sufficient hardness may not be exhibited. However, this value is an essential condition that the component (A), the component (B), and the component (C) are uniformly dispersed or dissolved in the composition, and the specific solvent concentration depends on the component (C ) May vary depending on the type.

  The solvent is not particularly limited, but 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 individually by 1 type or in combination of 2 or more types.

  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 and propylene glycol monoethyl ether acetate. 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.

5. Ingredient (D)
As described above, the component (D) used in the present invention is a solvent in which the solubility of the component (C) used is less than 10% by weight. Some specific examples are given below.
For example, when dipentaerythritol hexa (meth) acrylate is used as the component (C), water whose solubility is less than 0.1% by weight, and hexane which is 0.3% by weight are used as the component (D). be able to.
When trimethylolpropane tri (meth) acrylate is used as the component (C), water having a solubility of less than 0.1% by weight can be used as the component (D).
Ingredient (C
), When pentaerythritol tri (meth) acrylate is used, water having a solubility of 0.8 wt% and hexane having a weight of 0.6 wt% can be used as the component (D).
When tricyclodecanediyldimethanol di (meth) acrylate is used as the component (C), water having a solubility of less than 0.1% by weight can be used as the component (D).
When tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate is used as component (C), its solubility is 1% by weight water, 2% by weight ethanol, 8% by weight 1-propanol, 7% by weight of isopropyl alcohol and 6% by weight of n-butanol can be used as component (D).
Among these solvents, water, organic solvents such as ethanol, 1-propanol, isopropyl alcohol, and n-butanol are preferable from the viewpoint of the conductivity of a cured product obtained from the liquid curable composition.

  In this invention, when a component (D) is water, it is preferable that content in all the solvents contained in a composition is 0.1 to 50 weight%, and it is 5 to 30 weight%. More preferred. On the other hand, when the component (D) is an organic solvent, the content in the total solvent contained in the composition is preferably 5 to 95% by weight, and more preferably 8 to 90% by weight.

6). Ingredient (E)
The component (E) used for this invention is a solvent whose solubility of the component (C) to be used is 10 weight% or more as mentioned above. Some specific examples are given below.
As the component (C), for example, when using dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, etc., as the component (E), for example, methanol, ethanol, Alcohols such as 1-propanol, isopropyl alcohol, isobutanol, n-butanol, tert-butanol, ethoxyethanol, butoxyethanol, diethylene glycol monoethyl ether, diacetone alcohol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl amyl ketone Ketones such as dibutyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, etc. Esters such as ethyl acetate, butyl acetate, ethyl lactate, methyl acetoacetate and ethyl acetoacetate; Hydrocarbons such as toluene and xylene; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Amides such as pyrrolidone can be used.
For example, when tricyclodecanediyldimethanol di (meth) acrylate is used as the component (C), examples of the component (E) include the alcohols, ketones, ethers, esters, amides, and hexane described above. Hydrocarbons such as toluene and xylene can be used.
For example, when tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate is used as the component (C), examples of the component (E) include alcohols such as methanol, the above ketones, ethers, and esters. , Hydrocarbons, amides and the like can be used.
Among these solvents, methanol, ethanol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate and the like are preferable from the viewpoint of liquid stability of the liquid curable composition.

  The blending ratio of component (D) and component (E) varies depending on the type of component (C), but it is usually preferably 5:95 to 50:50, more preferably 5:95 by weight. ~ 30: 70. As a combination of the component (D) and the component (E), the boiling point of the component (D) is preferably higher than the boiling point of the component (E). Moreover, each of a component (D) and a component (E) may use a multiple types of solvent together.

7). Ingredient (F)
Although the liquid curable composition of this invention hardens | cures only by irradiating a radiation, in order to further raise a cure rate, you may mix | blend a photoinitiator as a component (F).
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 (F) is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 100 parts by weight based on the total amount of component (A), component (B) and component (C). 10 parts by weight. A component (F) can be used individually by 1 type or in combination of 2 or more types.

  Examples of the component (F) 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)- Examples include 2,4,4-trimethylpentylphosphine oxide.

8). Compounds having other polymerizable unsaturated groups In the composition of the present invention, compounds having other polymerizable unsaturated groups (component (G)) are added as additives other than components (A) to (F). It can mix | blend as needed. Here, the component (G) is a compound having one polymerizable unsaturated group in the molecule.
Specific examples of component (G) 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 Formula (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 a component (G), Aronix M-101, M-102, M-111, M-113, M-114, M-117 (above, Toagosei Co., Ltd. product); Viscoat 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.).

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

The liquid curable composition of the present invention contains the respective solvents of component (D) and component (E), and is obtained by utilizing the difference in solubility of component (C) between these solvents. When the composition is applied and dried, the component (C) is intentionally separated, and as a result, the oxide particles as the component (A) can be unevenly distributed in the dry film. Therefore, in the cured film and laminated body of this invention, effective electroconductivity is realizable with the addition amount of a smaller component (A). Moreover, since the addition amount of a component (A) can be reduced, there is little absorption and scattering of the light by a component (A), and a more transparent film | membrane can be formed. Further, by containing non-conductive particles as component (B), the anti-static function, that is, the scratch resistance is improved while maintaining a value of 10 ¹² Ω / □ or less as the surface resistance when a cured film is formed. And a low haze value can be achieved.

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 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.

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, triacetyl cellulose resin, diallyl carbonate of diethylene glycol (CR-39), ABS resin, AS resin. , Polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene resin), and the like.

  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, protective films for touch panels, transfer foils, hard coatings for optical disks, automotive wind films, antistatic protective films for lenses, and high-design containers such as cosmetic containers. Use as a hard coat mainly for the purpose of preventing surface damage such as surface protection film and adhesion of dust due to static electricity, and for various display panels such as CRT, liquid crystal display panel, plasma display panel, electroluminescence display panel, etc. As an antireflection film for antistatic use, and as an antireflection film for antistatic use for plastic lenses, polarizing films, solar battery panels and the like.

  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.

  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 base materials; a sealing material; a binder material for printing inks and the like.

  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.

[Synthesis Example 1]
Synthesis of reactive surface treating agent 20.6 parts of isophorone diisocyanate was added to dry air with respect to a solution consisting of 7.8 parts of γ-mercaptopropyltrimethoxysilane and 0.2 part of dibutyltin dilaurate in a vessel equipped with a stirrer. The solution was added dropwise at 50 ° C. for 1 hour, and further stirred at 60 ° C. for 3 hours.
71.4 parts of pentaerythritol triacrylate was added dropwise thereto at 30 ° C. for 1 hour, and the mixture was further stirred at 60 ° C. for 3 hours to obtain a reaction solution.
The product in this reaction solution, that is, the amount of residual isocyanate in the reactive surface treatment agent was measured by FT-IR. It was 0.1% by weight or less, and it was confirmed that each reaction was performed almost quantitatively. did. Moreover, it confirmed that it had a thiourethane bond, a urethane bond, an alkoxysilyl group, and a polymerizable unsaturated group in the molecule.

[Synthesis Example 2]
Synthesis of reactive silica sol (RB) In a container equipped with a stirrer, 8.7 parts of the reactive surface treatment agent synthesized in Synthesis Example 1, methyl ethyl ketone silica sol (manufactured by Nissan Chemical Industries, Ltd., trade name: MEK-ST, number average) After stirring a mixture of 91.3 parts (particle size 0.022 μm, silica concentration 30%) and 0.1 part of ion-exchanged water at 60 ° C. for 3 hours, 1.4 parts of methyl orthoformate was added, and 1 A methyl ethyl ketone dispersion of reactive particles (RB-1) was obtained by heating and stirring at the same temperature for the time. Further, this dispersion was subjected to solvent substitution with methanol using an evaporator. 2 g of this methanol dispersion was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour and weighed to determine the solid content, which was 35%. Also, 2 g of this dispersion was weighed into 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. When determined, it was 76% by weight.

[ Examples 2 to 4, Comparative Examples 1 to 3 ]
Hereinafter, preparation examples of the liquid curable composition of the present invention are shown in Examples 2 to 5 , and comparative preparation examples are shown in Comparative Examples 1 to 3 . Table 1 shows the blending weight ratio of each component. The numerical values of the blending amounts in Table 1 are parts by weight.

(1) Preparation of liquid curable composition In a container shielded from ultraviolet rays, antimony-containing tin oxide dispersion (manufactured by Ishihara Sangyo Co., Ltd., SN-100D, dispersion solvent: water, antimony-containing tin oxide content: 30% by weight , average particle size: 20nm) (a-1) 57.3 parts of methanol dispersion liquid 28.6 parts of reactive silica sol obtained in synthesis example 2 (RB-1), dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Product name KAYARAD DPHA) (C-1) 72.8 parts, water 40.7 parts, methanol 397.1 parts, 1-hydroxycyclohexyl phenyl ketone (F-1) 5.5 parts, and 2- By stirring 2.8 parts of methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (F-2) at 50 ° C. for 2 hours, a uniform solution composition (in Table 1) ratio A composition of Comparative Example 3) was obtained. When the solid content and the inorganic content in the solid content of this composition were measured in the same manner as in Synthesis Example 2, they were 18% by weight and 16% by weight, respectively.
In order to confirm the solubility of C-1 in a solvent, 5 g of C-1 was mixed with 5 g of water or 5 g of methanol at room temperature and left at room temperature for 3 days. The supernatant of the obtained mixture was dried on a hot plate at 120 ° C. for 1 hour and weighed to determine the solid content, which was 0.1% by weight or less and 50% by weight, respectively. That is, the solubility of C-1 in water and methanol was 0.1% by weight or less (less than 10% by weight) and 50% by weight (10% by weight or more), respectively.

By the same operation method, each composition of Examples 2-5 and Comparative Examples 1 and 2 shown in Table 1 was obtained.
In the composition of Comparative Example 1, A-1 and C-1 were separated from the solvent.

(2) Production of cured film The composition obtained in the above (1) was coated on a polyester film A4300 (manufactured by Toyobo Co., Ltd., film thickness: 188 μm) using a wire bar coater, and oven The film was dried at 80 ° C. for 3 minutes to form a coating film. Subsequently, the coating film was UV-cured under a light irradiation condition of 1 J / cm ^{2 in} the atmosphere using a metal halide lamp to form a cured film (hard coat layer) having a film thickness shown in Table 1.
In the composition of Comparative Example 1, a cured film and a laminate described later could not be produced.

(3) Production of laminate (antistatic laminate having antireflection ability) Polyester film A4300 (manufactured by Toyobo Co., Ltd., membrane) was obtained by using the wire bar coater for the composition obtained in (1) above. The film was coated on a thickness of 188 μm, and dried in an oven at 80 ° C. for 3 minutes to form a coating film. Subsequently, the coating film was UV-cured under a light irradiation condition of 1 J / cm ^{2 in} the atmosphere using a metal halide lamp to form a cured film (hard coat layer) having a film thickness shown in Table 1.
Further, a low refractive index coating material (Opstar JN7215 manufactured by JSR Corporation, solid content: 3%, refractive index of cured film: 1.41) is applied on the cured film using a wire bar coater (# 6). And air-dried at room temperature for 5 minutes to form a coating film. This coating film was heated using an oven at 140 ° C. for 10 minutes to form a low refractive index film having a film thickness of 0.1 μm, and an antistatic laminate having antireflection performance was obtained.

(4) Evaluation of cured film and laminate The obtained cured film and laminate were evaluated for scratch resistance, total light transmittance, haze and surface resistance according to the following criteria. Moreover, the reflectance of the laminated body was evaluated by the measurement method shown below.

(I) Scratch resistance The surface of the cured product was rubbed 100 times with # 0000 steel wool under a load of 200 g / cm ² , and the scratch resistance was visually evaluated from the following criteria. The obtained results are shown in Table 1.
Evaluation 5: No occurrence of scratches was observed.
Evaluation 4: Generation of 1 to 5 scratches was observed.
Evaluation 3: Generation of 6 to 50 scratches was observed.
Evaluation 2: Generation of 51 to 100 scratches was observed.
Evaluation 1: Coating film peeling was observed.
A scratch resistance of evaluation 3 or higher is practically acceptable, and a scratch resistance of evaluation 4 or higher is preferable because of excellent practical durability. If so, it can be said that it is more preferable because practical durability is remarkably improved.

(Ii) Reflectance The reflectivity (minimum reflectivity in the measurement wavelength range) of the laminate was measured using a spectroscopic reflectivity measurement device (a spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, Hitachi, Ltd. ( Measured in the wavelength range of 340 to 700 nm in accordance with JIS K7105 (Measurement method A).
That is, the minimum reflectance in the laminate (antireflection film) at each wavelength was measured with the reflectance in the aluminum deposited film as a reference (100%). The obtained results are shown in Table 1.

(Iii) Total light transmittance and haze The total light transmittance and haze of the cured film and the laminate were measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). The obtained results are shown in Table 1.

(Iv) Surface resistance The surface resistance (Ω / □) of the cured film and the laminate was measured using a high resistance meter (Agilent Technology, Inc., Agilent 4339B) and Resistivity Cell 16008B (Agilent Technology, Inc.). ) And applied voltage 100V. The obtained results are shown in Table 1.

In Table 1, the oxide particles (A) and the silica particles (B) indicate the dry weight of fine powder (excluding the organic solvent) contained in the charged amount of each dispersed sol.
The contents of the abbreviations in Table 1 are shown below.
A-1: Water-dispersed ATO sol (manufactured by Ishihara Sangyo Co., Ltd. SN-100D ATO content: 30% by weight, number average primary particle size: 20 nm)
RB-1: Reactive silica sol produced in Synthesis Example 2 C-1: Dipentaerythritol hexaacrylate F-1: 1-hydroxycyclohexyl phenyl ketone F-2: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone -1

Claims (12)

The following components (A), (B), (C), (D) and (E):
(A) particles mainly composed of an oxide of at least one element selected from the group consisting of indium, antimony, zinc and tin;
(B) silica particles,
(C) Dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra Group consisting of (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and tricyclodecanediyldimethanol di (meth) acrylate compound selected from (D) water, ethanol, 1-propanol, is selected from the group consisting of isopropyl alcohol, and n- butanol, dissolved in 25 ° C. component (C) Solvents degree is less than 10 wt%,
(E) A solvent having a solubility at 25 ° C. of 10% by weight or more of component (C) selected from the group consisting of methanol, ethanol, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monoethyl ether, and propylene glycol monoethyl ether acetate ,
Containing
The total amount of component (A), component (B) and component (C) is in the range of 15 to 50 parts by weight of component (B) in 100 parts by weight, and components (A), (B) and A liquid curable composition characterized in that (C) is uniformly dispersed or dissolved.   The liquid curable composition according to claim 1, further comprising a photopolymerization initiator (F) in addition to the components (A) to (E).   The liquid curable composition according to claim 1 or 2, wherein the component (A) is particles mainly composed of antimony-containing tin oxide (ATO) or indium-containing tin oxide (ITO).   The liquid curable composition according to any one of claims 1 to 3, wherein at least one of the components (A) and (B) is surface-treated with a surface treatment agent. 5. 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 in 1.
-X-C (= Y) -NH- Formula (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 a group consisting of —O—C (═O) —NH—, —O—C (═S) —NH— and —S—C (═O) —NH—. The liquid curable composition according to claim 5, wherein the liquid curable composition is at least one group selected from the group consisting of:   The said component (D) is water, and content in all the solvents contained in a composition is 0.1 to 50 weight%, It is any one of Claims 1-6 characterized by the above-mentioned. Liquid curable composition.   The said component (D) is an organic solvent, and content in all the solvents contained in a composition is 5 to 95 weight%, It is any one of Claims 1-6 characterized by the above-mentioned. Liquid curable composition. A cured film obtained by curing the liquid curable composition according to any one of claims 1 to 8 , and having a surface resistance value of 1 × 10 ¹² Ω / □ or less. A method for producing a cured film comprising the step of irradiating the liquid curable composition according to any one of claims 1 to 8 with radiation to cure the composition to form a cured film. . The laminated body for antistatic which has a cured film layer formed by hardening | curing the liquid curable composition as described in any one of Claims 1-8 . The antistatic laminate according to claim 11 , wherein the cured film layer has a thickness of 0.1 to 20 μm.