JP2007231112A - Liquid curable composition, cured film, and layered product for destaticizing - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid curable composition capable of exhibiting sufficient destaticizing properties even with a small amount of electroconductive particles compounded therewith, having excellent curability, and capable of forming a cured film having excellent destaticizing properties, hardness and scratch resistance, and also having both of transparency and surface resistivity. <P>SOLUTION: The radiation-curable composition comprises the following components (A) to (D) when the total of the components except the solvent in the composition is 100 mass%: (A) ≥1 mass% and <25 mass% of particles (PTO particles) having 10-100 nm average primary particle diameter, and containing phosphorus-containing tin oxide as a main component; (B) 74-98 mass% of a compound having two or more polymerizable unsaturated groups in the molecule; (C) 0.1-15 mass% photopolymerization initiator having ≤5,000 L/mol×cm molar absorption coefficient at 313 nm; and (D) a solvent of 50-10,000 pts.mass based on 100 pts.mass of the total amount except the solvent (D). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid curable composition. More specifically, it is excellent in 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 resin, etc.), metal, wood, paper, glass, ceramics, surface, etc., to form a coating (film) with excellent antistatic properties, hardness, scratch resistance and transparency The present invention relates to a liquid curable composition to be obtained, a cured film obtained by curing the composition, and an antistatic laminate.

Conventionally, from the viewpoint of ensuring the performance of information communication equipment and taking safety measures, a radiation curable composition has been used on the equipment surface to provide a coating film (hard coat) having scratch resistance and adhesion, and a coating having an antistatic function. A film (antistatic film) is formed.
In recent years, there has been remarkable development and generalization of information communication devices, and further improvements in performance and productivity of hard coats, antistatic films and the like have been demanded.

In particular, optical articles such as plastic lenses are required to prevent the adhesion of dust due to static electricity, and to improve the reduction in transmittance due to reflection, and the display panel also prevents the adhesion of dust 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) ) A trifunctional acrylic acid ester, a monofunctional ethylenically unsaturated group-containing compound, a photopolymerization initiator, and an optical disk material containing conductive powder (Patent Document 5), antimony-doped dispersed with a silane coupler Conductive paint containing hydrolyzate of tin oxide particles and tetraalkoxysilane, photosensitizer, and organic solvent (Patent Document 6), polymerized in the molecule Reaction product of alkoxysilane containing unsaturated group and metal oxide particles, liquid curable resin composition containing trifunctional acrylic compound and radiation polymerization initiator (Patent Document 7), primary particle diameter is 100 nm The following conductive oxide fine powder, easy-dispersible low-boiling solvent of the conductive oxide fine powder, difficult-dispersible low-boiling solvent of the conductive oxide fine powder, and formation of a transparent conductive film containing a binder resin For example (Patent Document 8).

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, in recent years, as a cured film that is required to have all the functions of a hard coat and an antistatic film, it is not always necessary. It was not satisfactory enough.

  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 can exhibit sufficient antistatic performance even when the amount of conductive particles is small, has excellent curability, and is applied to the surface of various substrates. Another object of the present invention is to provide a liquid curable composition that is excellent in antistatic properties, hardness, and scratch resistance and that can form a cured film having both transparency and surface resistance.

  As a result of earnest research to solve the above-mentioned problems, the present inventors have found that conductive particles having a specific primary particle size, compounds having a specific polymerizable unsaturated group, photopolymerization initiators having a specific light absorption property, In addition, the inventors have found that by using a composition containing a solvent and a solvent, excellent conductivity can be exhibited even when the amount of conductive particles added is reduced, and the present invention has been completed.

That is, the present invention provides the following liquid curable composition, cured film and antistatic laminate.
1. A radiation curable composition containing the following components (A) to (D), with the total amount other than the solvent (D) in the composition being 100% by mass.
(A) Particles mainly composed of phosphorus-containing tin oxide having an average primary particle diameter of 10 nm to 100 nm (hereinafter referred to as “PTO particles”): 1% by mass or more and less than 25% by mass (B) 2 in the molecule Compounds having the above polymerizable unsaturated groups: 74 to 98% by mass
(C) Photopolymerization initiator having a molar extinction coefficient at 313 nm of 5000 L / mol · cm or less: 0.1 to 15% by mass
(D) Solvent: 50 to 10,000 parts by mass with respect to 100 parts by mass of the total amount of the composition other than (D) solvent. The component (C) is 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone 1) or more selected from the group consisting of 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, The radiation-curable composition according to 1.
3. 3. The radiation curable composition according to 1 or 2, wherein the component (B) contains a compound having 6 or more polymerizable unsaturated groups in the molecule.
4). A cured film having a surface resistance value of 1 × 10 ¹² Ω / □ or less, obtained by curing the radiation curable composition according to any one of 1 to 3 above.
5). The manufacturing method of the cured film which has the process of irradiating a radiation curable composition in any one of said 1-3, and hardening this composition.
6). An antistatic laminate comprising a substrate and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, wherein at least a part of the PTO particles is a substrate of the cured resin layer An antistatic laminate that is concentrated and distributed on the opposite interface.
7). An antistatic laminate, wherein the cured resin layer is obtained by curing the radiation curable composition according to any one of 1 to 3 above.
8). 8. The antistatic laminate according to 7, wherein the surface resistance value is 1 × 10 ¹² Ω / □ or less.
9. An antistatic laminate comprising a substrate and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, wherein at least a part of the PTO particles is a substrate of the cured resin layer A process for applying a radiation-curable composition according to any one of 1 to 3 on a substrate, and a method for producing an antistatic laminate that is concentrated and distributed on the opposite side of the interface, and the radiation A method for producing an antistatic laminate, which comprises a step of irradiating a curable composition with radiation to cure the composition.

  According to the present invention, even if the content of the conductive particles is low, it is possible to obtain a cured film that has high transparency, can exhibit sufficient conductivity, and is excellent in antistatic performance.

Hereinafter, embodiments of the present invention will be specifically described.
I. Liquid curable composition The liquid curable composition of the present invention comprises a conductive particle (component (A)) having a primary particle size of 10 nm to 100 nm, a compound having two or more polymerizable unsaturated groups in the molecule (component (B)), a photopolymerization initiator (component (C)) and a solvent (component (D)).
Hereinafter, each component will be specifically described.

1. Ingredient (A)
The component (A) used for this invention is an essential component in order to express the electroconductivity of the cured film of the liquid curable composition obtained. Component (A) includes phosphorus-containing tin oxide (PTO), antimony-containing tin oxide (ATO), tin-containing indium oxide (ITO), antimony-containing titanium, fluorine-containing tin oxide (FTO), zinc antimonate, indium-doped oxide Particles mainly composed of metal oxides such as zinc, ruthenium oxide, rhenium oxide, silver oxide, nickel oxide and copper oxide can be used. Particles containing phosphorus-containing tin oxide (PTO) as a main component (hereinafter referred to as “PTO particles”) are preferable because of good antistatic performance.

  As a commercial item as a powder of phosphorus content tin oxide (PTO) particles, for example, the product name: ELCOM TL-30S (PTO) manufactured by Catalyst Kasei Kogyo Co., Ltd. The product name: EP SP2 manufactured by Mitsubishi Materials Corporation Can be mentioned.

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

  As a commercial item which disperse | distributed the oxide particle used as a component (A) to the solvent, the catalyst chemical industry Co., Ltd. product name: ELCOM JX-1001PTV (PTO of propylene glycol monomethyl ether dispersion | distribution) can be mentioned, for example. .

The average primary particle diameter of the component (A) is 10 to 100 nm. Preferably it is 10-50 nm. The particle diameter is measured with a transmission electron microscope. If the particle diameter is less than 10 nm, the conductivity may be insufficient, and if it exceeds 100 nm, precipitation may occur in the composition or the smoothness of the coating film may be reduced.
In addition, 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 size is 10-50 nm as the short axis average particle size and 100 as the long axis number average particle size. It is preferably ˜2,000 nm. If the long axis particle diameter exceeds 2,000 nm, sedimentation may occur in the composition.

The compounding quantity of a component (A) is 1 mass% or more and less than 25 mass% by making the total amount except the (D) solvent in a composition into 100 mass%. Preferably, it is 1-20 mass%, More preferably, it is 2-15 mass%, Most preferably, it is 3-9 mass%.
If the blending amount is less than 1% by mass, the antistatic property may be inferior, and if it is 25% by mass or more, the transparency may decrease.
Here, the compounding quantity of component (A), (B) and (C) says the compounding quantity as the solid content.

When the composition of the present invention is applied onto a substrate and then cured by irradiation with radiation to form a cured film, the PTO particles of component (A) are on the interface opposite to the substrate of the cured film (hereinafter, “ It is referred to as the “air interface”). As a result, a portion having a relatively low distribution density of PTO particles (number of PTO particles per unit volume) and a portion having a relatively high distribution density of PTO particles are formed. Here, “relative” means the relative relationship between these two parts.
The portion where the distribution density of the PTO particles is relatively low is in contact with the base material and forms most of the cured film in the thickness direction. On the other hand, the portion where the distribution density of the PTO particles is relatively high forms a portion occupying a thickness corresponding to about 1 to several tens of PTO particles in the vicinity of the air interface. Form a region in which the secondary aggregates are substantially aligned. The thickness of the portion where the distribution density of such PTO particles is relatively high is typically about 1/10 of the cured resin layer when PTO particles having an average primary particle diameter of about 20 nm are used. . When PTO particles are thus distributed, a surface resistance value of 1 × 10 ¹² Ω / □ or less is obtained. Although the amount of PTO particles in the composition is low, it is considered that PTO particles are concentrated in a part of the cured film to form a conductive layer. Typical cured film cross sections observed with a transmission electron microscope are shown in FIGS.

In the present invention, the component (A) is preferably oxide particles surface-treated with a surface treatment agent. By performing the surface treatment, the scratch resistance of the cured product can be improved.
Surface treatment can be used by a well-known method (for example, refer Unexamined-Japanese-Patent No. 2003-105034).
In the present invention, 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 can be preferably used as the surface treatment agent.
-X-C (= Y) -NH- (1)
[In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]

Examples of the polymerizable unsaturated group include a (meth) acryloyl group and a vinyl group.
Specifically, the group represented by Formula (1) includes [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (═O). ) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [—S—C (═S) —NH—]. It is a seed. Among these, [—O—C (═O) —NH—], [—O—C (═S) —NH—] or [—S—C (═O) —NH—] is preferable. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, the [—O—C (═O) —NH—] group is essential, the [—O—C (═S) —NH—] group and the [—S—C (═O). ) -NH-] group is preferably used in combination. The group [—X—C (═Y) —NH—] represented by the formula (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion to the material and heat resistance.

As a compound which produces | generates a silanol group, the compound which the alkoxy group, the aryloxy group, the acetoxy group, the amino group, the halogen atom, etc. couple | bonded with the silicon atom can be mentioned. A compound in which an alkoxy group or an aryloxy group is bonded to a silicon atom, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
The silanol group-generating site of the silanol group or the compound that generates the silanol group is a structural unit that binds to the silica particles by a condensation reaction that occurs following a condensation reaction or hydrolysis.

  Specific examples of the surface treating agent include compounds represented by the following formula (2).

In the formula (2), R ¹ and R ² may be the same or different and each represents a hydrogen atom or an alkyl group or aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, Examples thereof include phenyl and xylyl groups. Here, j is an integer of 1 to 3.

Examples of the group represented by [(R ¹ O) _j R ² _3-j Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, and a dimethylmethoxysilyl group. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ³ is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms, and may contain a chain, branched or cyclic structure. Specific examples include methylene, ethylene, propylene, butylene, hexamethylene, cyclohexylene, phenylene, xylylene, dodecamethylene and the like.
R ⁴ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500. Specific examples include a chain polyalkylene group such as hexamethylene, octamethylene, and dodecamethylene; an alicyclic or polycyclic divalent organic group such as cyclohexylene and norbornylene; and 2 such as phenylene, naphthylene, biphenylene, and polyphenylene. Valent aromatic group; and these alkyl group-substituted and aryl group-substituted products. These divalent organic groups may contain an atomic group containing an element other than carbon and hydrogen atoms, and may contain a polyether bond, a polyester bond, a polyamide bond, and a polycarbonate bond.
R ⁵ is a (k + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species. K is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  Specific examples of the compound represented by the formula (2) include compounds represented by the following formula (3) or the following formula (4).

[In the formulas (3) and (4), “Acryl” represents an acryloyl group. ]

  For the synthesis of the surface treating agent used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent. Typically, a mixture of the compound represented by formula (3) and the compound represented by formula (4) is obtained.

2. Ingredient (B)
Component (B) 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 (B), a cured product having excellent scratch resistance and organic solvent resistance can be obtained.

Specific examples of the 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, bis ((meth) acryloyl) Oxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane (also referred to as “tricyclodecanediyldimethanol di (meth) acrylate”), and ethylene oxide of the starting alcohols in making these compounds or Poly (meth) acrylates of propylene oxide adducts, oligoester (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligoether (meth) acrylates, oligourethane (meth) acrylates, and Oligo epoxy (meta ) 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, ditrimethylolpropane tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) ) Acrylate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, and tricyclodecanediyldimethanol di (meth) acrylate. These (B) components may be used individually by 1 type, and may use 2 or more types together.

Among the components (B), compounds having 6 or more polymerizable unsaturated groups in the molecule are particularly preferable.
The blending amount of the component (B) is preferably 74 to 98% by mass, more preferably 80 to 95% by mass, with the total amount other than the solvent (D) in the composition being 100% by mass. When the blending amount of the component (B) is less than 74% by mass, the transparency of the obtained cured product may be lowered, and when it exceeds 98% by mass, the antistatic property may be inferior.

3. Ingredient (C)
Component (C) used in the present invention is a photopolymerization initiator.
Component (C) is a photopolymerization initiator having a molar extinction coefficient at 313 nm of 5,000 L / mol · cm or less. Here, the molar extinction coefficient at 313 nm of the photopolymerization initiator means the ratio of the absorbance and molar concentration of the solution at 313 nm to the 1 cm absorption layer. By using a photopolymerization initiator having such light absorption characteristics, the surface resistance of the cured film can be sufficiently reduced. When a photopolymerization initiator having a molar extinction coefficient at 313 nm exceeding 5,000 L / mol · cm is used, a cured film in which PTO particles are concentrated and distributed at the interface cannot be obtained. Resistance is high and sufficient antistatic performance cannot be obtained.

Although the liquid curable composition of this invention hardens | cures only by irradiating a radiation, a component (C) can further raise a cure rate other than said function.
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.

  Examples of the photopolymerization initiator that can be used as the component (C) include 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, and the like.

  The compounding amount of component (C) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, with the total amount other than the solvent (D) in the composition being 100% by mass. A component (C) can be used individually by 1 type or in combination of 2 or more types.

4). Component (D) Solvent The solvent used in the present invention is not particularly limited, but usually a solvent having a boiling point of 200 ° C. or less at normal pressure is preferred. 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. Specific examples include propylene glycol monomethyl ether (PGME), cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methanol, and the like, and propylene glycol monomethyl ether (PGME), cyclohexanone, and methyl ethyl ketone are preferable.
In addition, when using the dispersion liquid which disperse | distributed the metal oxide particle to the solvent as a component (A), the solvent which is this dispersion medium mixes in a composition, but this dispersion is used as (D) component. These solvents may be used, or different solvents may be added.

  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.

  The compounding amount of the component (D) solvent is 50 to 10,000 parts by mass, preferably 50 to 3,000 parts by mass, with the total amount other than the (D) solvent in the composition being 100 parts by mass.

5). Compounds having other polymerizable unsaturated groups In the composition of the present invention, compounds having other polymerizable unsaturated groups (component (E)) are added as additives other than components (A) to (D). It can mix | blend as needed. 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 (5).
_{^{CH 2 = C (R 11)}} -COO (R 12 O) p -Ph-R 13 Formula (5)
(Wherein R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, and R ¹³ 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.).

  The compounding amount of the component (E) is preferably 0 to 30% by mass, more preferably 0 to 10% by mass, in a total amount of 100% by mass of the solids other than the component (D). When the amount of component (E) exceeds 30% by mass, pencil hardness may be inferior.

6). 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. product name: Irganox 1010, 1035, 1076, 1222, etc. As UV absorber, Ciba Specialty Chemicals Co., Ltd. product 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.

7). 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 conductive particles as the component (A), the antistatic function, that is, the surface resistance when a cured film is maintained, while maintaining a value of 10 ¹² Ω / □ or less, the scratch resistance Can be improved.

  Such non-conductive particles are not particularly limited as long as they are particles other than the conductive particles that are the component (A). Preferably, oxide particles or metal particles other than the component (A) are used. Specifically, an oxide particle containing two or more elements 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. There may be mentioned physical particles.

  The primary particle diameter of the non-conductive particles is preferably 0.1 μm or less, more preferably 0.001 to 0.05 μm, as a value determined by 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.

Commercially available non-conductive particles, for example, silicon oxide particles (for example, silica particles), colloidal silica, manufactured by Nissan Chemical Industries, Ltd. Product 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. Can do. Further, as powder silica, product names manufactured by Nippon Aerosil Co., Ltd .: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. Product names: 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.
In addition, as an aqueous dispersion of aluminum oxide (alumina), manufactured by Nissan Chemical Industries, Ltd. Trade name: Alumina Sol-100, -200, -520; As a dispersion of zirconium oxide, manufactured by Sumitomo Osaka Cement Co., Ltd. ( (Toluene, methyl ethyl ketone-dispersed zirconia sol); As cerium oxide aqueous dispersion, manufactured by Taki Chemical Co., Ltd. Product name: Niedal; As powders and solvent dispersions of alumina, zirconium oxide, titanium oxide, etc. Product name: Nanotech etc. can be mentioned.

  The blending ratio of the nonconductive particles is preferably 0.1 to 70 parts by mass, more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the component (A) and the component (B).

8). Method for Preparing Composition The composition of the present invention comprises (A) conductive particles, (B) a compound having two or more polymerizable unsaturated groups in the molecule, (C) a photopolymerization initiator, and (D) a solvent. And, if necessary, (E) Other compounds having a polymerizable unsaturated group, additives, and non-conductive particles can be added and mixed at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll.

II. Cured Film / 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. If 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 the visible ray source include direct sunlight, lamps, fluorescent lamps, and lasers. Examples of the ultraviolet ray source include mercury lamps, halide lamps, and lasers, and electron beam source. For example, a method using thermoelectrons generated from a commercially available tungsten filament, a cold cathode method in which a 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 that collides accelerated electrons 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.

  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.

The antistatic laminate of the present invention is an antistatic laminate having a base material and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, and at least one of the PTO particles. The portion is concentrated and distributed on the interface of the cured resin layer opposite to the substrate. Here, the cured resin layer refers to a layer containing a cured product obtained by curing a radiation curable resin or a thermosetting resin. Preferably, such an antistatic laminate can be produced by forming the cured film of the present invention on a substrate. In this case, the thickness of the cured film is preferably 0.1 to 20 μm. In applications where the abrasion resistance on the outermost surface such as touch panels and CRTs is important, it is relatively thick, preferably 2 to 20 μm. On the other hand, when used as an antistatic film of an optical film, the thickness is preferably 0.1 to 10 μm.
The surface resistance of the antistatic laminate of the present invention is preferably 1 × 10 ¹² Ω / □ or less, more preferably 1 × 10 ¹¹ Ω / □ or less. If 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.
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 is not particularly limited, such as metal, ceramics, glass, plastic, wood, slate, etc., but as a material capable of exhibiting high productivity and industrial usefulness such as radiation curability, for example, film, fiber-like It is preferably applied to a substrate. Particularly preferred materials are plastic film and plastic plate. Examples of such plastics include polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, polystyrene, polyester such as polyethylene terephthalate, polyolefin, triacetyl cellulose resin, diallyl carbonate of diethylene glycol (CR-39), ABS, and the like. Examples thereof include resins, AS resins, polyamides, epoxy resins, melamine resins, and cyclized polyolefin resins (for example, norbornene resins).

  Examples of application of the cured film and the antistatic laminate of the present invention include, for example, a protective film for a touch panel, a transfer foil, a hard coat for an optical disk, a window film for an automobile, an antistatic protective film for a lens, a cosmetic container, and the like. The surface protective film of a designable container can be used as a hard coat mainly for the purpose of preventing scratches on the product surface and preventing dust adhesion due to static electricity.

  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, “part” and “%” respectively represent “part by mass” and “% by mass” unless otherwise specified.

Example 1
(1) Production of liquid curable composition In a container shielded from ultraviolet rays, a phosphorus-containing tin oxide dispersion (ELCOM JX-1001PTV, produced by Catalyst Kasei Kogyo Co., Ltd., dispersion solvent propylene glycol monomethyl ether, phosphorus-containing tin oxide 30 mass) 6.7 parts, dipentaerythritol hexaacrylate (trade name KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd., hereinafter may be referred to as B-1) .) 93.4 parts, 4.5 parts of 1-hydroxycyclohexyl phenyl ketone (hereinafter sometimes referred to as C-1), and 95 parts of methanol were stirred at 50 ° C. for 2 hours to obtain a uniform solution. A composition was obtained.
2 g of the obtained composition was weighed in an aluminum dish, dried on a hot plate at 140 ° C. for 1 hour and weighed to determine the solid content, which was 35% by mass. Also, 2 g of the composition was weighed into a magnetic crucible, preliminarily dried for 30 minutes on a hot plate at 80 ° C., and the inorganic content in the solid content was determined from the inorganic residue after calcination in a muffle furnace at 750 ° C. for 1 hour. As a result, it was 60 mass%.

(2) Production of cured film film The composition obtained in (1) above was applied onto an ARTON film G7810 (manufactured by JSR Corporation, film thickness 188 μm) using a wire bar coater, Drying was performed at 80 ° C. for 3 minutes. Next, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp in the atmosphere to produce a film having a cured film (hard coat layer) with a thickness of 3 μm.

(3) Physical property evaluation of cured film film The total light transmittance, haze, pencil hardness and surface resistance of the cured film film obtained in (2) above were evaluated according to the following criteria.
(A) Total light transmittance and haze The total light transmittance (%) and haze (%) of a cured film film were measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). did. The obtained results are shown in Table 1.
(B) Pencil hardness The cured film film was placed on a glass substrate, and the pencil hardness was evaluated according to JIS K5600-5-4. The obtained results are shown in Table 1.
(C) Surface resistance The surface resistance (Ω / □) of the cured film film was measured using a high resistance meter (Agilent Technology Co., Ltd. Agilent 4339B) and Resistivity Cell 16008B (Agilent Technology Co., Ltd.). Used and measured under the condition of an applied voltage of 100V. The obtained results are shown in Table 1.
(D) Uneven distribution of PTO particles The cross section of the obtained cured film is observed with a transmission electron microscope, and the case where the PTO particles are concentrated and distributed in the vicinity of the interface on the opposite side of the substrate of the cured film is expressed as “ ○ ”, otherwise“ × ”.

Examples 2-12 and Comparative Examples 1-4
Except having used the component shown in Table 1, it carried out similarly to Example 1, and manufactured the liquid curable composition of Examples 2-12 and Comparative Examples 1-4, produced a cured film, and evaluated the physical property of a cured film Went. The obtained results are shown in Table 1. Moreover, the transmission electron micrographs of the cured film sections obtained in Examples 2 and 3 and Comparative Example 3 are shown in FIGS. 1, 2, and 3, respectively. The upper part of each figure is an air interface. In FIGS. 1 and 2, PTO particles are concentrated and distributed in the vicinity of the interface. In FIG. 3, the PTO particles are not concentrated in the vicinity of the interface, and secondary aggregates are almost uniformly distributed inside the cured film.

The abbreviations in Table 1 are as follows.
B-1: Dipentaerythritol hexaacrylate C-1: 1-hydroxycyclohexyl phenyl ketone (molar extinction coefficient at 313 nm: 80 L / mol · cm)
C′-4: 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one (molar extinction coefficient at 313 nm: 17,000 L / mol · cm)
Dispersant: Dispersant included in phosphorus-containing tin oxide dispersion ELCOM JX-1001 PTV PGME: Propylene glycol monomethyl ether

From the results shown in Table 1, no significant difference was observed between the examples and the comparative examples with respect to the total light transmittance and pencil hardness, but the photopolymerization initiation with a molar extinction coefficient at 313 nm exceeding 5,000 L / mol · cm. In the comparative example using the agent C′-4 or C′-5, the surface resistance value of the cured film is on the order of 10 ¹⁴ , whereas the molar extinction coefficient at 313 nm is 5,000 L / mol · cm or less. In the examples using the polymerization initiators C-1 to C-3 (component (C) in the present invention), it is remarkably low on the order of 10 ⁶ to 10 ⁹ , indicating that the antistatic performance is excellent.

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. Can be provided.
The cured film of the present invention mainly includes, for example, a protective film for a touch panel, a transfer foil, a hard coat for an optical disk, a window film for an automobile, an antistatic protective film for a lens, a surface protective film for a high-design container such as a cosmetic container, etc. It can be used as a hard coat for the purpose of preventing scratches on the product surface and preventing dust from adhering to static electricity.
The antistatic laminate of the present invention can be used, for example, for high-design containers such as touch panels, transfer foils, optical disk hard coats, automobile window films, cosmetic containers, and the like.

2 is a transmission electron micrograph showing a cross section of a cured film obtained in Example 2. FIG. 3 is a transmission electron micrograph showing a cross section of a cured film obtained in Example 3. FIG. 4 is a transmission electron micrograph showing a cross section of a cured film obtained in Comparative Example 3.

Claims (9)

A radiation curable composition containing the following components (A) to (D), with the total amount other than the solvent (D) in the composition being 100% by mass.
(A) Particles mainly composed of phosphorus-containing tin oxide having an average primary particle diameter of 10 nm to 100 nm (hereinafter referred to as “PTO particles”): 1% by mass or more and less than 25% by mass (B) 2 in the molecule Compounds having the above polymerizable unsaturated groups: 74 to 98% by mass
(C) Photopolymerization initiator having a molar extinction coefficient at 313 nm of 5000 L / mol · cm or less: 0.1 to 15% by mass
(D) Solvent: 50 to 10,000 parts by mass with 100 parts by mass as the total amount of the composition other than (D) solvent   The component (C) is 1-hydroxycyclohexyl phenyl ketone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone ), 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-hydroxy-2-methyl-1-phenyl-propan-1-one, Item 2. A radiation curable composition according to Item 1.   The radiation curable composition of Claim 1 or 2 in which the said (B) component contains the compound which has a 6 or more polymerizable unsaturated group in a molecule | numerator. A cured film having a surface resistance value of 1 × 10 ¹² Ω / □ or less, obtained by curing the radiation curable composition according to claim 1.   The manufacturing method of the cured film which has a process which irradiates a radiation curable composition of any one of Claims 1-3, and hardens this composition.   An antistatic laminate comprising a substrate and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, wherein at least a part of the PTO particles is a substrate of the cured resin layer An antistatic laminate that is concentrated and distributed on the opposite interface.   An antistatic laminate, wherein the cured resin layer is obtained by curing the radiation curable composition according to any one of claims 1 to 3. The antistatic laminate according to claim 7, wherein the surface resistance value is 1 × 10 ¹² Ω / □ or less. An antistatic laminate comprising a substrate and a cured resin layer containing PTO particles having an average primary particle diameter of 10 nm to 100 nm, wherein at least a part of the PTO particles is a substrate of the cured resin layer The manufacturing method of the laminated body for antistatics which concentrates and distributes on the interface opposite side, Comprising: The process of apply | coating the radiation-curable composition of any one of Claims 1-3 on a base material. And the manufacturing method of the laminated body for antistatic which has the process of irradiating a radiation to this radiation-curable composition and hardening this composition.